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By J. Stuart Warner

The reaction COSO4(c)?CoO(c) + So3(g)was investigated from 950° to 1170OK by two different methods. The sulfate was decomposed in a previously evacuated space and Pso3 calculated from the measured total pressure on the assumption that Pso2 = 2P02. The sulfate was also decomposed under conditions of controlled oxygen pressure. The difference in the results obtained by these experimental techniques is attributed to the effects of thermal diffusion. The standard free energy change for the reaction is given by ?F° = 66,292 + 17.273T log T — 102.57 T (±300 cal/mole). It was found by DTA and X-ray diffraction studies that CoS04 undergoes a transformation at 617°± 4°C. THE metal sulfates may decompose directly to the oxide or pass through one or more intermediate basic sulfates. Provided the oxidation state of the cation does not change in the course of the reaction, the decompositions may be described in general as follows: One of the major objectives of this work was to determine the validity of Eq. [3] as much of the existing sulfate data has been calculated from decomposition pressures by Eq. [5]. The type of apparatus generally used for these measurements consists of a reaction vessel at high temperature which communicates with a manometer at room temperature. A temperature gradient is thus imposed on the gas phase causing thermal diffusion which brings about a partial separation of the different gaseous species present in an initially uniform mixture. The basic theory and experimental facts associated with this phenomenon are summarized elsewhere1 and it will suffice to state here that the heavier gaseous species diffuses down the temperature gradient. Since thermal diffusion destroys the homogeneity of the gas phase, it is not necessarily true that Pso2 = 2Po2 in any particular volume element of the gas phase even though there are twice as many molecules of SO, as of 0, in the gas phase considered as a whole. Under these conditions, the decomposing sulfate gives off SO, which dissociates to SO, and 0, and all three species are distributed throughout the system by thermal diffusion. However, the sulfate will continue to dissociate until the equilibrium value of PSo3 is established on the hot zone. Thermal diffusion may distribute SO2 and O2 throughout the gas phase in any way so long as Eq. [2b] is satisfied in the hot zone; i.e. Pso2(Po2)1/2=K3pso3. When a steady state is reached, we can characterize Pso2 in that

Jan 1, 1962

By Lars Rossemyr, Terkel Rosenqvist

The equilibrium Mn + 2 IiCl = MnCl2(g) + H2 has been studied at 1090°C for pure manganese and for Mn-Si alloys. For this reoction a standard free energy of Fo1363, = - 19,700 i 300 col ioas found. Combined with other thermal data, the standard free energy of the reaction Mn(s, ß) + Cl2 = MnCl2(g) was derived: Fo=- 56,140 + 9.78 T log T - 40.10 T For the formation of the various manganese silicides the following free energies were obtained. 5 Mn + 3 Si - M1z5Si3 ?F°1363 = -41,500 i 1500 cal Mn + Si - h.lnSi ?F°1363= -10,000 i 500 cnl Mn + 2 Si = MnSiz ?F°1363= -11,500 ± 500 cal In the search for a method suitable for the study of thermodynamic properties of certain alloy systems, it was found that the heterogeneous equilibrium between the alloy and a gas mixture consisting of hydrogen chloride, hydrogen, and volatile metal chlorides has considerable advantages. In addition to giving thermodynamic information about the alloys, such measurements may be used to derive thermodynamic data for the volatile metal chloride itself. The present paper gives some results which were obtained for manganese silicides and manganous chloride. Similar studies are presently being carried out for the iron silicides. The phase diagram of the Mn-Si system is rather well known,' but no information exists to the authors' knowledge about the thermodynamic properties of manganese silicides or about the chemical activities in molten Mn-Si alloys. At elevated temperature, manganese may react with hydrogen chloride according to the equation: Mn(s, ß ) + 2 HC1 = MnC1, (g ) + H2 [ 1] with the equilibrium constant The value of K, may be determined from measurements of the gas composition in equilibrium with pure manganese. When this value is used in connection with measurements on manganese alloys, the chemical activity of manganese in the alloy may be derived. Initial calculations showed that around 1000" to 1200°C the equilibrium constant K1 has a value of a few thousand, i.e., the reaction is shifted far to the right. In order to study this rather unbalanced gas composition, a flow method was used in two slightly different modifications. For all experiments with manganese silicides and for some experiments with pure manganese the apparatus shown on Fig. 1 was used. A bed of the metal or alloy was placed in a tube furnace. The refractory tube had an internal diameter of 14 mm and the bed was 75 mm long. Electrolytic manganese of high purity and silicon, 99.95 pct Si, were used as raw materials. All alloys were prepared by melting weighed amounts of the elements in a high frequency induction furnace in argon atmosphere. The melting was done in a silica crucible which was placed inside a graphite shell. The alloys were crushed to - 10 +40 mesh and analyzed chemically. Also, for the pure elements, the same size fraction was used. A controlled gas mixture of purified hydrogen and from 3 to 12 pct HC1 was passed through the bed where it reacted with manganese according to Eq. [I]. The volatile manganese chloride was collected in a condenser placed in the cooler part of the furnace tube. The gas mixture before and after the furnace was sampled and analyzed by absorption of

Jan 1, 1962

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 H. H. Kellogg

0. C. Ralston—The fact that none of the organizations that have worked on these ammoniacal leaching processes have contributed discussion of Mr. Caron's papers today is a matter of some disappointment. Adaptations, modifications and improvements have been made by several organizations or individuals and to complete the record I want to document a number of them. The Nicaro Nickel Co. operated a Government owned plant at Nicaro, Oriente, Cuba, during the past war. A report on the project was written for Reconstruction Finance Corp. and is in the document file collected by the Office of Technical Services, Commerce Department and filed with the Library of Congress, where it can be consulted or bibliofilm or photostat copies obtained by asking for copies of PB 97271. Nicaro Nickel Co. has obtained a series of U.S. Patents, my list (probably incomplete) of which bears the following numbers: 2,400,098; 2,400,114; 2,400,115; 2,400,461; 2,400,612; 2,458,902 and 2,473,795. International Nickel Co. has also studied the problem and U.S. Patent 2,478,942 shows that some of the complications involving occasional low extractions have been unraveled. Forward, Samis, and Kudryk, of the University of British Columbia, have also published a study of copper-nickel sulphide concentrate.' Others are interested and it is evident that this type of hydrometallurgy is likely to find a happy application in the not-too-far distant future. Caron's two papers practically amount to a summation of his life's work on the important subject of nickeliferous iron ores and the American Institute of Mining and Metallurgical Engineers is fortunate to have been chosen the medium of publication. M. Rey—The ammonia leaching process has been the subject of certain studies in New Caledonia, but at the present time, the conditions are not very favorable to its adoption. The process is a combination of a thermal and a hydrometallurgical process. As a result, the first costs and the operative costs are rather high. To counteract this unfavorable situation, it would be necessary to make a very high extraction. But unfortunately, the process is delicate and in spite of all of Caron's valuable work, there are still many unknown factors. It is difficult to obtain regularly a high extraction, exceeding 75 to 80 pct. It would be interesting to have the opinion of Inter-national Nickel on the process and to know what the Dutch are doing in Celebes. M. H. Caron (author's reply)—I am quite familiar with the different types of nickel and cobalt ores as found on New Caledonia, and it may be pointed out that the Celebes ores are quite the same in their properties. Their behavior when treating the ores by the ammonia-leaching process is also alike and in my opinion, there is no reason why a high extraction of the New Caledonian ores could not be obtained if the process is properly applied. For the sake of completeness I may add that one of my patents has not been discussed in the papers. This patent deals particularly with the treatment of serpentine nickel ores. (Netherlands No. 62693 40a, French No. 965.786 April 21. 1948. and Cuban No. 13.625 Jan. 1950.)

Jan 1, 1951

By Leo Brewer, Gerd M. Rosenblatt

Thermodynamic calculations predict the species vaporizing from metal-oxide mixtures when reliable free energy functions, enthalpies of formation, and dissociation energies are available for the possible gaseous and condensed oxide components. Calculations of the oxygen to metal ratio in the vapor phase compared with the oxygen to metal ratio in a liquid metal saturated with oxide impurity are presented The possibility of purifying metals contaminated with oxide by vacuum melting or by distillation is discussed. Kinetic considerations affecting rates are neglected. IN recent years extensive information has been obtained on the thermodynamic stability of gaseous oxides of metals due to a variety of new types of measurement. Perhaps the greatest amount of information has come from the application of mass spec-trometry to the study of high-temperature vapors.' In many instances oxides of quite unusual oxidation states are found to be important in the high-temperature vapors. At low temperatures the standard free energy change for a reaction as given by the equation ?F° = ?H° - T?S° is determined primarily by the AH" value. However, at higher temperatures where the value of T in the T?S° term is large, the entropy term becomes equal to or greater than the AH term. At low temperatures only reactions for which AH is negative or only slightly endothermic are of importance. This restricts the main equilibrium species largely to those with completed octets or those with the principle oxidation number of the element. At

Jan 1, 1962

By T. R. Ingraham

The thermal decomposition of cupric sulfate and of cupric oxysulfate has been examined by deter-mining the equilibrium gas pressure generated over each pure compound. The equilibrium data have been used to calculate the thermodynamic properties of both compounds, and the results have been combined with previously published data to establish a predominance-volume diagram for the Cu-S-O system over the normal range of roasting temperature and gas composition used in the treatment of copper minerals. Copper oxysulfate recrystal-lizes at 1100°K with an apparently irreversible en-dothermic heat requirement of 2.9 * 0.3 kcal per mole. WHEN mixed sulfide minerals containing copper are roasted, either of two procedures may be followed, depending on the nature of the other metals. In the first procedure, the roasting is controlled to produce a maximum amount of water-soluble copper sulfate which may be removed selectively from the water-insoluble compounds of the other metals. In the second, control is directed toward the production of water-soluble sulfates of the other metals and an insoluble salt of copper. Effective control of either of these processes would be enhanced by knowledge of the thermal stability of cupric sulfate and of cupric oxysulfate. In this paper, established data for the thermal stability of cuprous and cupric sulfide and of cuprous and cupric oxide will be combined with new data for the therma1 stability of cupric sulfate and cupric oxysulfate, to designate the volumes of stability of the significant compounds in the Cu-S-O system in the temperature range 750° to 950°K. EXPERIMENTAL Materials, Apparatus, and Procedure. The copper source material used in all experiments was Fisher Certified Reagent Grade "anhydrous" cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared from the normal sulfate by two procedures. In the first, equimolar quantities of cupric oxide (prepared by decomposition of the sulfate) and cupric sulfate were ground together and heated under vacuum in a sealed silica vessel at 800°C. This procedure was subject to failure because of explosion of the silica vessels due to the pressure of the final traces of water released from the sulfate on the initiation of its decomposition. The second procedure involved roasting the cupric sulfate, with frequent rabbling, in a muffle furnace at 725°C for a period of 48 hr. This produced an excellent product, which was confirmed as copper oxysulfate by X-ray and chemical analyses. The experimental technique used was that of measuring the total pressure exerted by the sulfur trioxide, sulfur dioxide, and oxygen produced by the following reactions: 2 CuS04 = cuo • CuSO4 + SO3 [1] cuo . CuSO4 = 2 cuo + SO3 [2] SO3= SO2 + 1/2 O2 [3] The apparatus used in the experiments has been described previously.1-3 Its main feature of a U-tube mercury manometer in which the mercury is protected from corrosion by enclosure in a flexible Pyrex bellows. Before beginning a run, the interior of the apparatus, including the bellows-manometer and all connecting tubing, was thoroughly washed with hydrochloric acid and distilled water to remove any

Jan 1, 1965

By H. H. Podgurski

Above 200°C the observed increase in the apparent solubility of hydrogen in low alloy steels caused by cold work is attributed to the formation of methane in microvoids. This methane can be isolated quantitatively, and furthermore, the amount of methane is in accord with the equilibrium 2H2 + Fe3C = CH4 + 3Fe. The micro-void volume, calculated from the methane content via the equation of state for methane, corresponds approximately to that calculated from the measured density decrement produced by cold work. THIS investigation was undertaken with the intent of employing the hydrogen atom as a probe in detecting specific crystallographic defects in cold worked steel. It was expected that different degrees of chemical interaction of hydrogen with the various types of defects could be utilized. The original aim was to assign concentration values to defect sites. The success of this approach requires that experimental conditions can be attained under which lattice-dissolved hydrogen equilibrates primarily with only one type of defect. A set of experiments which appeared potentially to embody these requirements was described several years ago by Keeler and Davis.1 They noted in the case of a mild steel (low carbon) that the solubility of hydrogen between 200° and 400°C near atmospheric pressure was notably increased by cold working the steel. The observed solubility was an order of magnitude greater than the normal lattice solubility. * Although the Keeler and Davis studies suggested that the density decrement effected by their cold-working operation might be related to the anomalous solubility of hydrogen, they offered no explanation of the relationship between the two effects. Prior to this work, Darken and smith3 had noted a similar effect of cold work upon enhanced sorption of hydrogen by steel when charged by acid pickling. In the light of present-day concepts, interaction between lattice-dissolved hydrogen and dislocations was strongly suggested. More recently, Hill and Johnson,4 working with a

Jan 1, 1962

By T. R. A. Gokcen

THE possibilities of separating and purifying metals by high vacuum distillation were examined by Kroll.1 He suggested vacuum treatment for the removal of zinc from the lead produced after Parkes desilverizing. The St. Joseph Lead Co. developed the first commercial vacuum dezincing process at their Herculaneum refinery, as described by Isbell.² The Broken Hill Associated Smelters at Port Pirie, Australia, has, after several years of pilot plant operations and fundamental investigations, developed a continuous process, which will be described briefly in a forthcoming publication." As the full-scale continuous vacuum dezincing plant at Port Pirie is still experimental, publication of full practical details of the plant will be deferred until the unit is operating as a normal part of the continuous refinery. This paper deals only with theoretical aspects of vacuum distillation processes, with particular reference to vacuum dezincing. The method of mathematical analysis is of general interest as it may be applicable to other metallurgical separations which have been investigated recently.4-6 Evaporation Processes At about atmospheric pressure, or higher, most liquids possess a boiling point—a temperature at which any heat put into the liquid is absorbed only as latent heat, not as specific heat. If a steady heat input is supplied, the liquid's temperature rises to this value, then remains constant while bubbles of vapor form beneath the surface. The rate of evaporation is determined solely by the rate of heat transfer to the liquid; the temperature of boiling is determined by the partial pressures of the volatile constituents in the liquid, and the total pressure above the surface. If the rate of heat transfer to the liquid is increased, the temperature remains constant, and the rate of boiling increases. When evaporating metals under vacuum, however, the partial pressures concerned are generally so small that boiling does not occur, because at even a fraction of a millimeter below the surface the hydrostatic pressure is usually too great to permit the formation of a pocket of vapor. In addition, the high thermal conductivity of metals tends to prevent the local superheating which is necessary for bubble formation.' Although this effect is doubtless also exerted when boiling metals at higher pressures, the magnitude will be less because the degree of superheat required to form bubbles is very much less at the higher temperatures involved. Under vacuum, therefore, evaporation of volatile constituents takes place only from the exposed surface, and the rate of evaporation depends upon the surface area, the surface concentration of volatile constituents, the surface temperature, and the partial pressures of volatile constituents immediately above the surface. If the heat input is raised above a certain level, the effect is not to increase the evaporation rate at constant temperature, but to raise the temperature of the liquid until at some higher level an increased rate of evaporation (and thus of latent heat absorption) again balances the heat input rate.? Many substances (including metals) have a very large intrinsic evaporation rate at quite low temperatures—far below their normal boiling points. However, at atmospheric pressure, the large numbers of atoms evaporated are almost completely deflected back into the liquid (or solid) surface by air molecules. Thus the back condensation rate is practically equal to the gross evaporation rate, and the net evaporation rate is practically zero. It can therefore be seen that an overall distillation rate depends not only upon the intrinsic evaporation rate, but also upon the ability of the volatile atoms to move away from the evaporating surface. This movement is facilitated by the provision of a condensing surface close by. Vacuum Distillation: The function of the vacuum above the evaporating surface is to remove foreign molecules, so that the chances of deflection of an evaporated atom back into its source are reduced. When the residual gas pressure is reduced so far that the evaporated atoms have a high probability of reaching a nearby condensing surface without suffering collision with a foreign molecule, the state of affairs is termed "molecular distillation." This process is practiced commercially today for the purification of numerous organic chemical products of high unit value, but not, to the writer's knowledge, for any metallurgical separation. When the degree of vacuum produced in a still is not sufficient to promote molecular distillation, then the evaporated molecules must diffuse through the

Jan 1, 1954

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 A. W. Bethune, L. M. Pidgeon

The equilibrium vapor pressure of zinc has been determined over the systems: ZnS(s) + Fe(s) = FeS(s) + Zn (vapor) and ZnS(s) + 2Cu(s) = Cu2S(s) + Zn (vapor) by reacting the components in an evacuated tube containing a thin copper fiber, and allowing equilibrium to be established with respect to the brass formed and the zinc in the vapor phase. The composition of the brass formed was determined and equilibrium vapor pressure values obtained from existing data. Between 850' and 1000°C, values for the first reaction ranged from 8 to 58 mm Hg; for the second reaction from 1.8 to 22 mm Hg. THE direct reduction of metallic sulphides may be indicated by an equation of the form MS + X = XS + M [1] where X is some suitable reducing agent. In the case where M is a metal of relatively high volatility, the use of vacuum will displace the equilibrium to the right at comparatively low temperatures in the face of the usually unfavorable thermochemistry. For this technique to be feasible, MS, X, and XS, must of course be nonvolatile compared to M. In this regard, zinc becomes an obvious metal both from the point of view of its volatility and the fact that most commercial ore deposits of this metal occur as the sulphide, and its direct reduction would avoid the expensive roasting process necessary prior to present day reduction methods. Two reducing agents are of interest, namely copper and iron, with the former having the added attraction of being relatively easily regenerated by oxidation in the copper converter. The possibility of these reactions has been considered before. Imbert1 patented a process whereby zinc sulphide was reduced by either copper or iron. The process as described took place at atmospheric pressure and, at the high temperatures required, the system was molten, resulting in the formation of a matte with the consequent reduction in the activities of the reactants. Peterson2 did further experimental work on these reactions and, although promising results were obtained on a small scale, attempts to increase the size of the furnace led to excessive "blue powder" formation. The early workers failed to realize the large reduction in temperature afforded by the use of vacuum and its desirable results. More recently, the direct reduction of zinc sulphide by iron has been the subject of a thermody-namic investigation by Kelley,3 and Gross and War-rington' have studied the kinetics of the reaction in the temperature range 900" to 1000°C, their experiments being conducted using vacuum and indicating that the reaction would proceed practically to completion in 1 to 3 hr, depending on the temperature. A qualitative examination of the system ZnS-Cu carried out at this University indicated that 98 pct of the theoretical zinc in the charge could be recovered in 1 hr at 1000°C when operating under reduced pressure. The purpose of this research program was to study the equilibrium of the two reactions. During the investigation, reference to the experimental work of Schenk5 was found but, due to lack of detail in the report, it was felt that it would be desirable to continue the equilibrium measurements. Selection of Method The measurement of vapor pressure of metals presents obvious problems resulting from the high temperatures which must be employed. In the present case, the production of the "reaction pressure" introduces a further difficulty since a chemical reaction must proceed before any metal vapor pressure is produced, resulting in depletion of the re-

Jan 1, 1954

By Donald Ofte, L. J. Wittenberg

The absolute viscosity coefficients and activation energies for viscous flow of bismuth, lead, and zinc are reported. The viscosities were measured in an oscillating cup viscosimeter from nearly 1000°C to within 1 deg of the melting point of zinc; 2 deg of the melting point of lead; and in the supercooled condition of bismuth, 9 deg below the melting point. Two methods of relating the change in the viscosity coeflicient with temperature were compared. From the plot of the logarithm of viscosity (77) as a function of reciprocal absolute temperature (1/T), the equations of the lines which fit the data are: AS a part of the Reactor Fuels and Materials Research program at Mound Laboratory, precise measurements of the physical properties of liquid metals are of interest because the desirability for a low vapor pressure liquid coolant in high-temperature nuclear power plants has focused attention on the properties of the liquid metals.' Also, a clearer understanding of the liquid metal state can be achieved when better measurements are available. For these reasons, the viscosity values of certain liquid metals have been determined. The viscosities of the liquid metals, bismuth, lead, and zinc are measured in an oscillating cup viscosi-meter. In this apparatus the liquid is sealed in a right-circular cylindrical cup which is attached to a torsion fiber so that the system forms a torsion pendulum. The damping effect of the molten metal upon the normal oscillations of the torsion pendulum is a function of the viscosity of the liquid. This method is advantageous because of the small amount of sample required (8 to 10 cc), the ease of remote operation of the apparatus in a vacuum system, and the containment of the liquid metal in a hermetically sealed, nonreactive, tantalum crucible. With the liquid metal sealed in the crucible, loss of liquid by vaporization and chemical reactions with atmospheric gases are prevented. Additionally, an absolute viscosity determination is obtained which avoids the sources of possible error in a relative measurement. The difficulties in a relative method include the repetitious cup calibrations, and the uncertainty inherent in the practice of calibration of the apparatus at room temperature and extrapolation to the high temperatures necessary for the investigation of most liquid metals. The oscillating cup viscosimeter was first described by Meyer in 1891.2 The first complete mathematical treatment offering an absolute measurement of viscosity with this type of apparatus was proposed by Andrade and chiong3 in 1936 for an oscillating sphere filled with a liquid. This solution was modified to include a right circular cylinder by Hopkins and Toye4 in 1950, and R. Roscoe5 in 1958. Roscoe's treatment for the calculation of the viscosity of a liquid at a particular temperature from the logarithmic decrement and period of oscillation of the torsion pendulum was used in this investigation. A detailed description of the method of calculating the viscosity from these measurements has been reported earlier.' This calculation has been programmed for the IBM 704 and IBM 1620 computers for expedition of the otherwise laborious calculations. APPARATUS The cutaway view of the apparatus in Fig. 1 shows the suspension system within the high vacuum enclosure. The low residual gas pressure. maintained between 1 x 10-4 and 5 X 10-6 mm Hg during a determination, avoided both air drag on the pendulum and

Jan 1, 1963

By A. W. Schlechten, C. M. Hsiao

The apparent vapor pressures of a number of metal sulphides were determined by measuring their rate of weight loss when they were heated under vacuum. The calculated pressures are due in some instances to the volatility of the sulphide and in others to the decomposition pressure. FIE direct reduction of metallic sulphides, as in the precipitation method for lead or antimony, is not a widely used process today. However, it might be employed for the production of a number of metals if the operation were carried out under reduced pressures. Two general procedures are possible; the reducing agent could form a stable nonvolatile sulphide from which the valuable metal could be removed by volatilization or liquation. The other approach would be to choose a reducing agent which would form a sulphide that could be volatilized away from the valuable metal. A vacuum operation would serve to protect the sulphides and metals from oxidation and would increase the evaporation rates. A related process is the separation of metallic sulphides by selective volatilization either at atmospheric pressure or under vacuum. This procedure is already used commercially for the elimination of lead and cadmium as PbS and CdS from zinc calcines; it might well have other applications. To predict such processes it is necessary to know the relative volatilities of the metallic sulphides and to know whether they volatilize as sulphides or whether the predominant weight loss is due to decomposition. Such data would also be of value in studying problems such as the use of sulphides for refractories, as described by Brewer,] or in the evaluation of the theory of ore deposition from the vapor state, as proposed by Brown.' Qualitative statements concerning the volatility of metallic sulphides can be found frequently in the literature and are well summarized by Mellor, but accurate determinations of rates of evaporation or vapor pressures are very scarce. Kelly" lists vapor pressure data only for PbS; his reference being to the work of Schenck and Albers,4 who measured the vapor pressure of PbS by a dynamic method between 850" and 995°C. More recently Veselovskii5 has determined the vapor pressures of the sulphides of antimony, lead, cadmium, and zinc at temperatures ranging from 360" to 1000°C using Knudsen's method. A second Russian worker, Pogorelyi,6 determined the vapor pressures of CdS and ZnS at temperatures from 900" to 1250°C. The results obtained by these workers are shown in subsequent graphs in comparison with the data of this paper. Brewer and coworkers1 have studied some of the metallic sulphides to determine their suitability as refractories in vacuum. Veselovskii's determinations on PbS checked well with those of Schenck and Albers, and his determinations of CdS check almost exactly with Pogo-relyi. For the vapor pressure of ZnS the data of Veselovskii and that of Pogorelyi are in fair agreement, as shown in Fig. 1, but it should be pointed out that Lumsden7 has discovered that the equation given by Veselovskii for the vapor pressure of ZnS: - 14,200 log P9.495 is in error by a factor of ten when compared to the experimental data. In contrast with the scarcity of data on vapor pressures, the decomposition pressures of many metal sulphides have been determined and are summarized by Smithells.8 Theoretical Considerations The experiments described in this paper consisted of determinations of the rate of weight loss of certain metallic sulphides under very low pressures at different temperatures. These data plus observation and analyses of the products reveal the mechanism of the weight loss and also provide a basis for the calculation of the vapor pressure or apparent vapor pressures of the sulphides.

Jan 1, 1953

By E. A. Has, E. Mcl. Tittmann

Double roasting of sinter carrying a high percentage of lead concentrates, gave rise to the problem of removing the sheets of metallic lead formed in the wind boxes. The solution of the problem has been found in the water sealed wind boxes. The metallic lead is granulated and can be removed without seriously interfering with the operation of the machine and eliminates necessity of men going in wind boxes with air guns. THE practice of double sintering the charge for lead blast furnaces, which is now standard throughout the lead smelting industry, has introduced the rather difficult problem of cleaning the wind boxes on sintering machines used for the final pass. Two factors have more recently accentuated this problem: (1) the growing demand of workmen for better working conditions and less arduous labor, and (2) the growing dearth of crude lead ores and the improved grade of lead concentrates demand a charge carrying the maximum percentage of lead. One to 2 pct of such high lead charges (30 to 40) when processed on machines in reasonably good condition will pass through the grates and report in the wind boxes. One-half to three-quarters of this material will be metallic lead reduced by the coke breeze or other fuel mixed with the charge. This lead forms large cakes or chunks which are hard to remove and which substantially increase the time the machine is out of operation for cleaning the wind boxes. A high lead fall can reduce the operating time 30 pct. As a specific example, a 30 ft machine having 63 in. pallets, and equipped with three conventional wind boxes, requires 3 to 4 hr per day for removing the accumulation in the wind boxes when operated as a final pass machine. This same machine when operated on raw charge requires less than an hour per day for cleaning. To eliminate formation of large chunks of lead in the wind boxes of the final pass machines and time lost in cleaning the boxes, R. C. Rutherford of the Chihuahua smelter of the American Smelting and Refining Co., devised and patented* a wind box having a water bath to granulate the lead as it falls from the grate bars. Later, C. H. Harris of the San Luis plant made and patentedt an improvement on Rutherford's device in which the water bath seals the wind box in a manner permitting the latter to be readily cleaned without destroying the vacuum. The first machine to our knowledge to use the water bath box was at the Chihuahua plant along the lines of the Rutherford patent. In 1942, a machine was placed in operation at the El Paso plant which incorporated the features of both Rutherford and Harris. This machine is 40 ft long equipped with pallets 63 x 24 in., and having 4 wind boxes 10 ft 4 in. x 7 ft 2 in. x 51 ft 3 in. in size (fig. 1). The air from the fourth box is returned to the first three, and the gas from the first three discharged to a baghouse. The machine has conventional drive, discharge hopper,

Jan 1, 1951

By R. A. Davidson, L. Silverman

RESIDENTS of many urban centers are becoming increasingly aware of the obscuring effect of fume and smoke discharge from power, metallurgical, chemical, and other industries; and they, as well as the legislatures of these affected cities, are agitating for cleaner air. Management's most pressing problem is to find an economical way to reduce process effluents in response to the growing pressure from population and legislative demands. The removal must be done, if possible, without handicap to the current operation, since the costs of relocating are often excessive or prohibitive. In fume recovery or disposal, an important item to consider is whether or not the material being discharged has any value. If it has commercial value, the cost of its recovery may offset or aid amortization. For this reason, in making a study of the specific problem in hand, a major factor was the nature of the material emanating from the stack: in particular, its particle size, size range, and its chemical and physical composition, as well as its potential value and utility when recovered (in either a wet or dry state). Should the product have no commercial value, it must be disposed of at minimum cost in a way to prevent recontamination. Initial studies were therefore made to determine stack concentrations and volumes of material evolved from the operations. The next phase of the study concerned the physical and chemical nature of the collected fume. The third portion of this paper describes the wet and dry collector studies undertaken to recover the fume. Cleaning Requirements for Ferroalloy Furnace Operation The basic need for any effluent collection equipment is the highest possible efficiency and the lowest tolerable resistance when the power consumption involved is considered. Since the electric furnace effluent is largely composed of fume of small size (less than 0.5u), it has high light obscuring properties, and even low concentrations will cause some loss of visibility and be evident to nearby residents. The permissible limit for fly ash emission in many cities is based on a weight value (viz, approximately 0.4 grains per cu ft), but the smoke density values are dependent upon a shade of color. In the case of the Los Angeles County code, emission is restricted to pounds per pound of material processed per hour basis (but not exceeding 40 lb per hr for any one given plant operation). If an average particle size of the fume from ferro-silicon alloy electric furnaces is assumed to be 0.4u (as shown later, this is the approximate mean size) and an average loading of 1 grain per cu ft (stp), each cubic foot of stack gas will contain approximately 75x10 10 particles (based on assumed, and confirmed, spherical shape and a standard deviation of unity). When it is realized that the air in metropolitan areas, which are also general industrial areas, contains approximately 5x108 particles, the tremendous light scattering effect of this concentration becomes apparent. Consequently, nearly 100 pct collection would be necessary to equal the average concentration. Fortunately, however, discharge from a high point above ground (50 to 100 ft) will result in at least a thousandfold dilution, or the stack concentration reaching the ground in the foregoing case might result in a ground concentration of ' particles. If the concentration at the source could be reduced by a factor of 100 (99 pct efficiency of collection), then a concentration of 75x10" particles would be diluted to 7.5x10' which would be very satisfactory. An efficiency of 90 pct (factor of 10 decontamination) at the source would result in a discharge of 75x109 articles which upon dilution yields 75x10 which is still 15 times the general air value. Another approach to this consideration is to use the value of concentration of 0.005 grains per cu ft for the value of a visible effluent as cited by Kayse.1 To attain this value with an average loading of 1 grain per cu ft would require an efficiency of 99.5 pct. Since the foregoing value is not based on any reported size of fume particles, it is felt that the numbers' approach given previously is more reliable. These calculations serve to indicate the desirability of thorough cleaning, preferably at the source, and with efficiencies well above 90 pct, preferably above 95 pct (dilution 1:20). One of the most important items in any control program is to reduce the concentrations as close to their sources as possible. The use of better furnace design, deeper coverage over the electrodes, and the prevention of blows or breaks in the surface all help to reduce dissemination; consequently, all of these improvements should be made, if possible, to cut down the effluent load. In addition, in order to minimize the volume of contaminated air that has to be cleaned, the furnace should be enclosed as much as possible. Test Arrangements Before fundamental studies with collectors were made, a furnace stack selected for the test program was sampled to determine the gas temperatures and

Jan 1, 1956

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 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

By M. I. Sherman, J. D. H. Strickland

USE of a hydrometallurgical approach to the oxidation of sulfide ores and extraction of metals therefrom may have advantages over the more common smelting techniques when a low grade deposit is difficult to concentrate or the subsequent separation of metals, coexisting in the ore, is laborious by any known smelting operation. For economic reasons, the most promising oxidants are either atmospheric oxygen or electric power. The use of oxygen, or air under pressure, has recently been revised. Pyrrhotite has been converted to iron oxide and elementary sulfur' and a variety of sulfides have been treated by Forward and co-workers.2-4 Generally sulfate is the end form of the sulfur but with galena in an acid medium, elementary sulfur can be formed." For economic reasons chlorine and ferric iron salts are about the only possible alternatives to the atmosphere as oxidizing agents for base metal sulfides. If aqueous solutions of chlorine or ferric iron are employed, the reduction products can be oxidized electrolytically in situ and used again, thus acting as catalysts for electric power as oxidant. The use of ferric salts for this purpose is established hydrometallurgical practicea but, although chlorine gas has been employed in the dry state at an elevated temperature, its use in aqueous solution at or near room temperature has not found favor. The reaction of chlorine water with the soluble sulfide ion has been studied by several workers,7-9 and both sulfate and elemental sulfur are found as end products, the latter being favored by the presence of a low concentration of oxidant relative to that of sulfide in solutions of about pH 9 to 10. Of direct bearing on the work in hand are an early American patent" and a recent Austrian patent." The former advocates stirring powdered ore with an aqueous solution of ferric chloride chlorine oxides and chlorine. In the latter it is claimed that both metal and sulfur can be obtained by electrolysis, in a diaphragm cell, of a metal ore slurry in brine. Details in these patents are scant and no data or explanation is given for the mechanism of the reaction which, in the Austrian work, is attributed to the (unlikely) action of nascent chlorine at the anode surface. No mention is made of possible differences in behaviour between various ores. Apparatus A complication encountered when working with chlorine water is that a serious loss of chlorine occurs by gas partitioning unless an enclosed system is used and any air space in the apparatus is kept very small and constant. Arrangements were made, therefore, to take out samples for analysis without letting air into the system to replace the liquid removed. For convenience in studying a heterogeneous reaction the apparatus was so designed that a reproducible controlled stirring rate could be maintained and the ratio of surface area of ore to volume of solution was approximately constant throughout any experiment. The apparatus used is shown in Fig. 1. The ground ore was placed in the horizontal cylindrical vessel, A, of about 1 liter capacity, heated by a constant temperature circulating bath pumping water through the concentric jacket, B. By adding chro-mate to this water, an ultraviolet radiation filter effectively surrounded the reaction vessel, greatly reducing any possible photochemical decomposition of chlorine solutions. Stirring was effected by glass paddles, C, attached by an axle to a magnet which was rotated by another powerful Alnico magnet, D, outside the glass end, this magnet being itself rotated by an electric motor electronically controlled to constant speed. Speed could be varied from about 150 to 900 rpm and was measured and held to within 1 pct of a given value. The end of the reaction vessel remote from the stirring magnet was closed by another one-ended glass cylinder, E, connected by thin polyethylene bellows, F, clamped by screw clamps and watertight rubber gaskets to the main vessel. Through E, a glass electrode and calomel electrode projected into the solution and a hypodermic syringe pierced a small bung and allowed acid or alkaline to be added to maintain a constant pH. By pushing the fully extended bellows until the two cylinders touched, from 50 to 100 ml of solution could be forced out through a sintered disk into the three-way tap system, G, either to waste (for flushing purposes) or up into a 10 ml burette where the solution could subsequently be measured out for analysis. The ore samples were introduced at H, the tube being stoppered by a thermometer of —1 to +52ºC range, graduated to 0.1°C intervals. To prevent ore from being ground in the end bearings of the stirrer these bearings were pro-

Jan 1, 1958

By Joseph B. Story, John T. Clarke

A modification, of the Kelvin bridge using an inductor was used to measure the conductivities of molten sodium chloride, calcium chloride, and mixtures thereof. A capillary-type four-lead fused quartz dipping cell was constructed. The effect of a small amount of potassium chloride on the conductivity of the melt was determined. IN the electrowinning of sodium and chlorine from sodium chloride in Downs cells, calcium chloride is added to the sodium chloride in an approximately equimolar amount to permit cell operation at a lower temperature. This lower temperature improves current efficiency and ease of operation, but decreases voltage efficiency by decreasing the electrical conductivity of the melt. A knowledge of the electrical conductivity of the Downs cell melt is necessary to the understanding of Downs cell operation, for the IR voltage drop across the melt is responsible for a significant part of the electrical power consumed by the cell. The work of previous investigators on fused sodium chloride-calcium chloride mixtures was reviewed from the standpoint of consistency with the results of others on the conductivities of the pure constituents. The electrical conductivity of pure fused sodium chloride has been established with accuracy by Van Artsdalen and Yaffe,1 by Edwards, Taylor, Russell, and Maranville,2 and by Lee and Pearson.3 It has also been studied by a number of other investigators.4-13 The best values for calcium chloride are believed to be those of Lee and Pearson,3 since the sodium chloride and potassium chloride conductivity values given by them check the best literature values. A number of other investigators have also reported values for calcium chloride.'-"."' Electrical conductivity data for fused sodium chloride-calcium chloride mixtures have been reported by Sandonnini,12 Vereshchetina and Luz-hnaya,18 Ryschkewitsch,11 Barzakovskii,5 and Alaby-shev and Kulakovskaya.15 Sandonnini reports no data at temperatures lower than 850°C. The conductivity values reported by Vereshchetina and Luz-hnaya, by Ryschkewitsch, and by Barzakovskii for pure sodium chloride and for pure calcium chlor- ide vary somewhat from the literature values believed to be best and the sodium chloride-calcium mixture data of these authors and of Alabyshev and Kulakovskaya (who give no data for the pure compounds) show significant variations. In view of these facts, it seemed that an investigation of the electrical conductivities of fused sodium chloride-calcium mixtures would be worthwhile. Apparatus Bridge System—The bridge used,in this investigation is diagrammed in Fig. 1. In general, the elaborations of this bridge over the simple Wheatstone bridge were for the purposes of a) eliminating lead resistances or making them accurately measurable, and b) eliminating major capacitative and inductive effects or balancing them against each other. Lead resistances in the lower arms of the bridge were kept as low as possible by making the leads short and of low resistance wire. This could not be done in the cell arm of the bridge because of the remoteness of the cell from the other bridge components and because of the high-resistance nickel or chrome1 wires used in the cell. Since maximum sensitivity is attained when the resistances of the four arms of the bridge are equal, 50-O resistors were used in the lower arms of the bridge when fused salt conductivities were being measured, and 1000-O resistors were used when the cell was being calibrated with normal aqueous KCl solution. The cell resistance was of the order of 50 ohms with fused salts and of the order of 1000 ohms with normal aqueous KC1 solution. The resistors used were non-inductive and accurate to 50.05 pct (General Radio Co. Types 500-C and 500-H). The lead resistance between point A in the cell and point E at the measuring resistor was eliminated by using the kelvin bridge principle; that is, the voltape drop across the lead from point A to point E was divided between the cell arm of the bridge and the measuring arm of the bridge in proporation to the resistaxes in the lower arms of the bridge.

Jan 1, 1958