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By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By K. J. Brondyke, P. D. Hess

Two processes have been developed for improving the quality of molten-aluminum alloys before casting. The Filtration Process. which involves passing molten metal through a packed bed of granular filter material, is a rapid means of removing finely divided particles. It has the most potential in those instances where removal of inclusions is of primary importance. The Combination Fillration-Inert Gas Fluxing Process inuolzles introduction of an inert gas so that it will diffuse countercurrent to metal flow through the filter bed of granular material. Dissolved hydrogen is removed from the metal in addition to removal of finely divided particles. The Combination Process is most useful where both inclusion removal and attainment of conistently low-hydrogen-content metal are important. Metal treated by the Combination Process is of higher and more uniform quality than heretofore attainable with prolonged chlorine fluxing. Costs of the Combination Process can, for the most part, be offset by savings derived from high recoveries and increased production of superior-quality products. IMPROVEMENT in the quality of molten-aluminum alloys is secured generally through the use of some fluxing practice in a crucible, holding furnace, or ladle involving either gaseous or solid fluxing media. Typical fluxing agents may include the gases nitrogen, argon, or chlorine used either singly or as mixtures and the solids aluminum chloride or hexachloroethane. Regardless of the fluxing means used, the primary objectives are the adequate removal of both metallic and nonmetallic inclusions and reduction of hydrogen content to an acceptably low level. The ultimate goal is to produce ingots and cast products of high quality free from inclusions and porosity. The development of ultrasonics for measurement of internal quality, tightening of quality controls, and the application of the aluminum alloys to new or different commercial fields have been responsible for an ever increasing demand for improvement of quality of both cast and fabricated products. This demand for high quality has not been restricted to any single type of product. On the contrary, the demand encompasses about the entire variety of products including those for fabrication, those to be machined, buffed, or finished for decorative purposes, and those for critical applications where both surface and internal quality is of utmost importance. In many instances products acceptable in the 40's would now be scrapped as unacceptable by these higher present-day standards. With this ever increasing demand for higher quality, it became apparent at Alcoa that conventional means of melt treatment were inadequate in many instances and new approaches were necessary. Consequently the research program was intensified with attention focused on metal treatment during transfer in order to reduce the furnace processing time to a minimum in an effort to attain the desired results at a minimum of additional expense. As a result of this intensive research program which covered numerous variations and adaptations of conventional methods in addition to new methods of melt treatment, several new processes were developed, two of which will be described here. The first of these, a method of melt filtration, was patented in February, 1959.l The second process involving combination filtration—inert gas fluxing was patented in June, 1962. 2 Other melt-treatment processes developed during this period of investigation were patented as listed.3 FILTRATION PROCESS General Description. The Filtration Process, which involves passing molten metal through a packed bed of granular filter material, is a rapid method of effectively removing finely divided particles. It is an impingement-type filter; hence the size of the particles removed from the metal are considerably smaller than the interstices of the

Jan 1, 1964

By L. W. Rowe, S. S. Cole

A laboratory bench scale unit is described whereby finely divided chlorinatable residues are held for a short period by a restraining bed of a coarse-grained ore of comparable composition to permit 'flash' chlorination of the high surface area powder. Results on chlorinating a finely divicled titania residue using rutile sand as the restraining bed showed that 92 pct utilization of chlorine and equivalent conversion of TiO2 in the fine residue to Ticl4 were attained with a dust loss of about 3 to 4 pct and an equivalent amount of ch1om'nation of the titanium values in the restraining bed. THE chlorination of coarse grain titaniferous ores; i.e., 20 to 150 mesh sizes in fluidized beds is practiced commercially.' One effective method found for the chlorination of a very fine material in a fluidized bed is the "flash" chlorination technique.' By charging the finely divided charge material into the bottom of an established bed of optimum sized rutile, ilmenite, titanium beneficiate, or even an inert material such as sand, chlorination occurs before the dust can pass through the bed. The major requirement is that the bed be less chlorinatable than the charge. In this process, the charge consists of a finely divided (between one and 50 µ) titania residue obtained from a titaniferous ore beneficiation process. The charge is blended with a 20 pct wt basis addition of 20 to 60 .mesh size low volatile coke (to minimize hydrogen chloride formation) and fed to the bottom of the bed with the chlorine gas stream. A ball check device is used to permit entry of the charge and prevent the bed from discharging when the gas flow is cut off. The coarse pieces of coke serve to reduce compaction in the charge mixture and permit sat]sfactory feeding without plugging or jamming. Feed and gas rates are adjusted to provide for complete reaction of the charge material, with 90 to 95 pct chlorine efficiency, and maintain a gas flow in the range of 0.4 to 0.6 ft per sec. The equipment consisted of a 3-in. diam mullite tube enclosed in an electric furnace. A bow-shaped 3/4 in. Saran tube fed the charge from an air lock type of feed hopper (to prevent the escape of the chlorine gas into feed bin) to the bottom of the bed. The charge rate was set by providing a small awiliary hopper below the feed hopper where a weighed portion of the charge could be discharged in a specified time interval into the main chlorine stream. The chlorine rate was measured by a flowmeter. The reaction tube was filled with a bed of Australian rutile ore, this restraining bed serving two purposes; i.e., it rapidly heated the fresh charge to the reaction temperature and retained the particles in the bed for a sufficient time for selective chlorination to proceed. Due to the fine particle size and open, porous structure of the charge, this reaction was almost instantaneous, and, with proper adjustment of feed and gas rates, very little fine material passed through the bed without reacting and only a very small fraction of the restraining bed was chlorinated. A typical reaction procedure was to fill the bench scale fluidized bed unit with a 1 kg charge of Australian rutile ore analyzing 95.5 pct TiO2, 0.6 pct FeO, a beach sand deposit 40 to 150 mesh size. When fluidized, the bed was approximately 2 ft in depth. The ore was fluidized with a 1:l mixture of chlorine and nitrogen at a rate of 0.40 ft per sec. This gas mixture was necessitated by the comparatively short bed depth; a larger unit, with a deeper bed, could be fluidized with chlorine alone without significant free chlorine loss. Feed rate was 8.0 g per min of beneficiated ilmenite analyzing 85.0 pct TiO2, 2.6 pct FeO plus 1.6 g per min of 20 to 60 mesh petroleum coke. The

Jan 1, 1962

By Ivan B. Cutler, Milton E. Wadsworth

Coprecipitation of anionic and cationic polyelectrolytes has been applied to floccula-tion of several mineral systems. Results obtained in a study of the flocculation of kaolinite and hematite suspensions of polycationic and polyanionic electrolytes are presented. Greatly increased settling rates were observed following precipitation of positive and negative polyelectrolytes on the surface of finely divided minerals in aqueous suspension. The ratios of polycationic to polyanionic electrolytes required to produce maximum sedimentation have been shown to correspond closely with the equivalence points obtained by light scattering studies of systems containing the positive and negative polyelectrolytes by themselves. DISPERSION of colloids has been of interest to surface chemists for many years. Flocculation studies have been employed to evaluate the limits of colloid stability. In water suspensions, colloids become unstable and flocculate when the 5 potential, the potential of the kinetic solvation sheath, falls to a value at which van der Waals forces may act to draw the particles together. This may happen through an adjustment of the pH of the suspension or by addition of a salt. Optimum conditions for rapid formation of large flocs are found in the region of minimum < potential. In addition to these well known considerations, colloids in water suspensions are known to be flocculated by certain large organic macromolecules. These polyelectrolytes in some cases minimize the 5 potential and in other instances increase the attractive forces by supplying sites for hydrogen bonding.&apos; Use of organic polyelectrolytes in flocculation of mineral colloids has increased rapidly in recent years. These materials are now recognized as indispensable aids to fluid-solid separations in many extractive metallurgical operations. They have been found to increase both the settling rate in thickeners and the filtration rate of filters. In the elucidation of the characteristics of these organic reagents as floc-culants in this laboratory, it was discovered that interaction of certain polyelectrolytes had a surprisingly good effect on flocculation of mineral colloids. Experimental Procedure: The anionic flocculants used in this study were Lytron 886 and 887, produced by Monsanto Chemical Co. Both reagents are copolymers of vinyl acetate and maleic anhydride. Lime is added to Lytron 886, whereas Lytron 887 is all organic. These reagents possess two carboxyl groups for each acetate group and are therefore anionic in character. The cationic reagents used were the Peter Cooper Co. 1-X and 2-X glues. The structures are not definitely known, but the re- agents are amines and are cationic in character. The glues were prepared in the chrome-alum form. Both types of reagents may be classified as polyelectrolytes in that they are high molecular weight polymers and ionize in water. All data presented are in terms of sedimentation rate, measured in 250-ml glass-stoppered graduated cylinders. With suitable precautions such measurements are fairly reproducible and provide a sensitive means for selecting important parameters such as PH, reagent concentration, and floc size and density. Agitation was standardized with five complete end over end cycles of the suspensions in the stoppered graduated cylinders.

Jan 1, 1957

By C. G. Dunn, F. W. Daniels

IN recent publications1-5 the existence and behavior of subgrain boundaries in high-purity metals has been clearly brought to light. Lacombe and Beaujardl by means of special etching methods disclosed in polycrystalline sheets of aluminum the existence of substructures differing in orientation by small amounts (about 1/4"). Boundaries of these structures at relatively high temperatures had the remarkable property&apos; of moving about while the ordinary boundaries remained stationary. Cahn2 also observed substructures in bent and annealed single crystals of aluminum, zinc, magnesium, and rock salt. The position of subboundaries could be explained in terms of a dislocation mechanism of polygonization in which dislocations move into lines at right angles to the bent glide planes thereby relieving elastic stresses in these planes. Guinier and Tennevin8,6 disclosed the further interesting feature that polygonized structures coarsened significantly upon prolonged annealing. Somewhat similar subgrain phenomena have been observed in silicon iron of commercial purity. Although some evidence for the development of macro-mosaic structures in silicon iron already has been reported by one of the authors6,7 under the phenom-enological term "crystal recovery," much better evidence recently has been obtained due to improved etching techniques. In addition, phenomena regarding structural changes have been uncovered. The present investigation is divided into three parts: (1) The phenomenon of Laue spot sharpening on annealing cold-rolled crystals, (2) the phenomena of polygonization and subgrain coarsening The material used in the present investigation was high-grade commercial silicon iron sheet of nominal composition, 3.3 pct Si, 0.004 C, 0.011 P, 0.010 S, 0.04 Mn, 0.01 Al, 0.04 Cu, 0.01 Sn. Large single crystals of this material Were prepared for cold-rolling or bending as scheduled. Cold-rolling of 12 pct was carried out on a laboratory 8-in, diam rolling mill. The bending deformations were performed by pressing the crystals between a solid Fig. 2—lllustrative foue patterns to show Laue spot sharpening. a (Left)—Specimen as cold rolled, b (right)—After 48 hr at 1400°C. round bar and a mating half cylinder, both heavily greased. Individual specimens were cut from the deformed crystals, and the cut edges were deeply etched prior to annealing. Laue photographs were made using 40-kv tungsten radiation. The technique used to disclose the various subboundaries was an electropolish and electroetch in a bath of chrome-acetic acid.&apos; The anodic polishing done at 22 v was immediately followed by etching at a reduced voltage, which was dependent upon the nature of the subboundaries. Phenomenon of Laue Spot Sharpening on Annealing Cold-Rolled Crystals Fig. 1 gives the initial and final orientations of the specimens cold-rolled 12 pct. Each specimen was annealed at a temperature and for a time which caused significant structural changes as evidenced by alterations in Laue patterns. Representative Laue patterns and micrographs showing the essential changes are given in Figs. 2, 3, and 4. The essential points to be derived from these illustrations follow: 1. Annealing at 950°C clearly develops a substructure with the orientation of the cold-rolled specimen. 2. The subboundaries formed obviously separate regions of nearly the same orientation. Some of the subboundaries appear as a sequence of dots similar to those observed in aluminum by Lacombe and Beaujard,&apos; but whether this is due to extremely small differences in orientation is not known at present. 3. The substructure coarsens upon prolonged annealing. 4. Prolonged annealing also causes a decrease in orientation spread according to Laue spot sharpening&apos;

Jan 1, 1952

By Molly Gleiser

The standard free energies of formation of some gaseous metal oxides together with those of their condensed oxides have been plotted against temperature. The heats of formation of the gaseozcs oxides are tabulated. An explanation is given of the use of the data to predict the importance of the gaseous metal oxides at high tenzperatures. RECENT mass spectrometric work1 has resulted in the detection of several hitherto unknown gaseous oxides and the measurement of their free energies of formation. Of especial interest is the fact that several of the refractories in common use either as crucibles or furnace tubes, and metals used in Knudsen cells and in furnace windings, have been found to have one or more stable gaseous oxides. In view of the present emphasis on high-temperature techniques, the development of vacuum metallurgy.z heating by electron bombardment and plasma jets, and the resultant shift to ever higher temperatures, it is no longer possible to plan experiments without taking into consideration the significance of the presence of these gases in the system, the reactions they undergo. and their contribution to the vapor pressure. A good example of what went wrong in earlier work, when the existence of these gaseous molecules was not yet known, is presented by the work of Hoch, Nakata, and Johnston. Hoch and coworkers attempted to measure the vapor pressure of solid ZrO2 by letting the vapor in equilibrium with zir-conia effuse from a tantalum Knudsen cell. The free energies of formation of solid zirconia and tantala are such that a short calculation showed that the reaction

Jan 1, 1962

By Richard J. Borg

The vapor pressure of Cd in equilibrium with CdSb in the presence of excess Sb has been measured using the Knudsen effusion method over the temperature range 276° to 379°C. The free energy of formation of CdSb is given by AF° = -1.58 + 1.53 x l0-4 T, kcal per mole. The enthalpy and entropy are obtained from the temperature coefficient of the .free energy. CADMIUM and antimony have almost imperceptible mutual solid solubility but form a single stable intermediate phase, CdSb. This phase, according to Han-sen,l extends from about 49.5 at. pct to 50 at. pct Cd at 300°C and has the orthorhombic structure. The free energy of formation of CdSb can be calculated from the vapor pressure of Cd for compositions which contain less than 49 at. pct Cd. The appropriate reaction and formulae are given by Eqs. [I] and [2]- CdSb(s, ~ Cd(g)-, +Sb(s) [1] Since Sb is in its standard state, Af - N,,AF&apos;-,, = NcdRT In a,, = NcdRT InP/PO [2] In Eq. [2], P, is the vapor pressure of Cd in equilibrium with the alloy, and Po is the vapor pressure in equilibrium with pure solid Cd. It is implicit in this calculation that the free energy only slightly changes within the narrow limits of the single phase field. Thus, the value obtained from the antimony-rich boundary is truly representative of the stoi-chiometric compound. The results reported herein are obtained from a mixture near the eutectic composition, i.e. 59 at. pct Sb. Only two previous investigations" of the free energy of formation of CdSb have been made. Both relied upon the electromotive force method, and measurements were made over relatively narrow temperature ranges which strongly influences the reliability of the values of AH and aS. EXPERIMENTAL The eutectic composition is prepared by fusing reagent grade Cd and Sb by induction heating in vacuo with the starting materials held in a graphite crucible having a threaded lid. The material obtained from the initial melt is pulverized, sealed under high vacuum in a pyrex capsule, and annealed at 420°C for two weeks. X-ray analysis"gives the following lattize parameters: a = 6.436A, b = 8.230& and c = 8.498A using Cu Ka radiation with A = 1.54056. These values are in fair agreement with the result? previously reported by Al~in:4 i.e. a = 6.471A, b = 8.253A, and c = 8.526A. Vapor pressures are measured using an apparatus which has been described elsewhere,= however, with a single important modification. Knudsen effusion cells are made of pyrex with knife-edged orifices made by grinding the convex surface of the lid on #600 emery paper. Photographs taken at known magnifications using a Leitz metallograph enable the determination of the orifice area. Numerous calibration measurements of the vapor pressure of pure Cd give close agreement with values previously reported5,= thus indicating that no significant error can be ascribed to the substitution of glass cells for metal cells used in previous work. Because the vapor pressure of Cd is reliably established and because it is difficult to obtain Clausing factors for the glass cells, the final values used for the orifice areas are calculated from the calibration measurements of the vapor pressure of pure Cd. Effusion runs are started in an atmosphere of purified helium which is quickly evacuated as soon as the cell attains thermal equilibrium. Less than one minute is necessary to obtain high vacuum after evacuation begins, and the temperature seldom varies by more than 0.5oC from the value obtained prior to pumping out the helium. RESULTS The results of this investigation along with other pertinent data are tabulated in Table I. Fig. 2 is the familiar graph of log P against T-10 K. At least mean squares analysis of the data presented in Table I yields the following equation: log1DJP = 8.790 - 6472 x T"1 [3] The deviations of the individual measurements from the values calculated with Eq. 131 are given in column six of Table I; the average deviation is 4.0% of the calculated value. Although the partial molal properties change significantly with composition within the single phase region, the integral thermodynamic value should remain relatively constant. Hence the results of the following calculations, which use the data obtained for the eutectic composition, are probably representative of the equi-atomic compound. Eq. [4] describes the vapor pressure of pure Cd as a function of temperature and may be combined with Eq. [3] to

Jan 1, 1962

By Molly Gleiser, John Chipman

The standard free energy of formation of WC was obtained from determination of the equilibrium WC + CO2 = W + 2CO between 1215° and 1266°K. Its uallie is -8340 * 300 cal Per mole over the above range of temperature. AS a part of a program devoted to measuring the stabilities of the carbides, a study was made of the free energy of formation of tungsten carbide, WC. The homogeneity range of this compound is very small,&apos; and it is generally accepted and is dealt with here as a stoichiometric compound. The heat of formation, ?H°f, of WC has been accurately measured by Huff, Squitieri, and snyder.2 The only attempt, however, to measure the free energy of formation of this compound was made by Schenck, Kurzen, and wesselkock3 who brought tungsten carbides into equilibrium with H2 and CH4. Unfortunately their results are not sufficiently accurate nor consistent enough to permit the calculation of free energies. METHOD Heating mixtures of tungsten and carbon powders in hydrogen for 4 days at 1050°C led to formation of some WC without any trace of W2C. It was deduced, therefore, that at least below this temperature W2C will not be formed during experiments with mixtures of tungsten and WC. This was subsequently shown to be correct. The method chosen was the measurement of the equilibrium of the reaction

Jan 1, 1962

By J. W. Evans

ONE of the most important and frequent calculations that the extractive metallurgist is called upon to make is that of the standard free energy change of a reaction (?F°). For many reactions of metallurgical interest, the lengthy arithmetical calculations have been eliminated by the use of free energy-temperature diagrams which have been constructed by Ellingham,1 Richardson and Jeffes,2 Kellogg,3 and Osborn4 (e.g., for oxides, sulphides, halides) from critical surveys of existing data. The speed and simplicity of making calculations with these graphs make them of great practical value and, this should be stressed, in the majority of cases no greater accuracy is obtained by the individual calculations from specific heat data, entropies, and heats of reaction. With the increasing industrial application of vacuum methods to the winning of metals, notably at present magnesium and the alkaline earth metals, it is necessary to calculate low metal vapor pressures above reaction mixtures. The existing free energy diagrams usually give values where the solid and liquid metals are at unit activity. To obtain the free energy change associated with the reaction Metal (solid or liquid) = Metal (gas) it is customary to calculate this from either vapor pressure equations or from the appropriate free energy functions. This paper presents graphically the free energies of vaporization of a number of metals of economic importance which can be used in conjunction with other free energy diagrams. Certain metals have been excluded on the following grounds: titanium, tungsten, molybdenum, and platinum have very high heats of vaporization and boiling points and the uncertainty of these values arising from difficulties of high temperature measurements makes free energy values of doubtful accuracy; the data for cobalt, vanadium, and zirconium are uncertain; finally, arsenic, antimony, and bismuth could not be conveniently included. because of the presence of mixtures of polyatomic and mona-tomic vapors in the temperature range considered. Free Energy Diagram In Fig. 1, the standard free energies of vaporization per mol (?F°T) have been plotted for the temperature range 0" to 2000°C for the reaction M (solid or liquid) = M (gas) The data have been obtained from the free energy functions — (F-H298)/T for the solid, liquid, and gaseous elements and the heats of vaporization at 298°K, i.e., ?H298 (vapor). The values of these functions have been taken without change from the recent critical survey by Brewer;&apos; the bulk of this data is from Kelley7 with adjustments in the light of more recent work. Values of the function — (F-H298) /T at T = 298°, 500°, 1000°, 1500°, and 2000°K were employed. Where possible, a further independent value was obtained by using the boiling point, i.e., where ?F°T = 0. All calculations are based on the assumption that the metal vapors are monatomic and that the boiling points refer to those temperatures at which the partial pressure of the monatomic vapor above the metal is 760 mm. For the alkali metals, e.g., sodium, potassium, and lithium, diatomic gas molecules are present as minor species; details of these are discussed by Brewer." On the basis of the above values and allowing for the change in slope at the melting point, straight line graphs were constructed and extrapolated to 2000°C. The deviation from a straight line did not exceed ±500 cal, which in all cases appears less than the probable error in the ?F°T values.

Jan 1, 1954

By G. H. Turner, R. C. Bell, E. Peters

Zinc oxide activities in a typical lead blast furnace slag have been calculated from plant operating data. These activities were used to assess the probable effect of fuel composition, oxygen enrichment, and air preheating on the efficiency and capacity of the slag-fuming operation. THE physical chemistry of zinc fuming has been examined with three objectives in mind: 1—to predict conditions favorable to increasing furnace capacity, 2—to predict the changes required to fume zinc more economically, and 3—to explain reported differences in the efficiencies of various slag-fuming plants. This study, made at ail in the plants and laboratories of The Consolidated Mining and Smelting Co. of Canada Ltd., developed from a program undertaken some three years ago on behalf of the AIME Extractive Metallurgy Div. subcommittee on slag fuming. Lead metallurgists first became interested in the recovery of zinc from lead blast furnace slags in 1905 and 1906. An excellent review of the early experimental work has been made by Courtney,&apos; who described blast furnace, reverberatory furnace, and converter methods of fuming zinc from slag. Some of the investigators did not appreciate the importance of reducing the zinc oxide content of the slag to metal in order to fume it, since they tried compressed air blast without fuel in their earliest attempts. However, by 1908, the importance of reducing the zinc was established.&apos; In 1925, the Waelz process for the recovery of zinc oxide from oxidized zinc ores was developed in Germany.&apos; This process was not readily adaptable to lead blast furnace slags because of the difficulty in handling fusible charges in a kiln. What appears to have been the first slag-fuming operation as it is known was commenced by the Anaconda Copper Mining Co. at East Helena, Mont. in 1927." The first Trail furnace was completed in 1930, and this was followed by the construction of several other slag-fuming plants. During the period in which slag fuming has been extensively employed, little development of the chemistry of this process as a whole has taken place. Several good papers on the petrography of lead blast furnace slags have been published,""= but these studies could do little more than establish the forms in which lead and zinc occur in the initial charge and final products of the slag-fuming operation. In recent years, zinc-smelting problems have been ap- proached from a thermodynamic point of view. Maier has published an excellent thermodynamic treatment of zinc smelting." The important thermodynamic properties of zinc and its compounds have been determined and checked by other investigators.&apos; However, to the best of the authors&apos; knowledge, no thermodynamic treatment of the fuming of zinc from slag has been published. A thermodynamic study of any process requires that the essential chemistry of that process be known. In slag fuming there appear to be some differences of opinion as to whether the active reducing agent is elemental carbon or carbon monoxide. Furthermore, some observers have noted that high volatile coals appear to be more efficient than low volatile coals, indicating that hydrogen is also an important factor in the reducing efficiency of a fuel. That both hydrogen and carbon monoxide are effective reducing agents for the zinc oxide content of lead blast furnace slags can be demonstrated readily by introducing these gases into a slag bath held in a neutral vessel at 2100°F (1150°C). Elemental carbon also will reduce zinc oxide, but it is improbable that much free carbon is available for reduction of zinc, as the reaction between the finely powdered coal and air should be largely completed before the solid coal particles reach the slag. Some large-scale fuming experiments using gaseous hydrocarbons have been carried out by other investigators, but, as far as is known, these have not been developed yet into operating processes. The thermodynamic treatment in this paper is based on the following reactions: 1—to supply the thermal requirements C+V2O2- CO [1] C + 0,-CO, [2] H2+ ~z0,-H,O 131 and 2—to reduce ZnO ZnO + CO + Zn + CO, c41 ZnO + H, e Zn + H,O. [51 The furnace-gas composition also is controlled by the equilibrium constant of the familiar water-gas reaction H,O + CO + CO, + H2. C6l In order for the thermodynamic calculations to be quantitatively applicable, it is necessary that the chemical reactions to which they are being applied

Jan 1, 1956

By M. H. Caron

BASIC U. S. Patent 1,487,145 on ammonia leaching of nickel ores was issued to the author on March 18, 1924. Equivalent patents in other countries were obtained later. The Dutch Syndicate Brikcarbo became interested in the process in 1935; and a couple of years later the late Dr. H. Foster Bain sent samples of Surigao laterite iron ore to Delft and witnessed tests made there on this material for the Philippines Commonwealth. As a result, the author was asked in April 1940 by Dr. Bain to go to the Philippines to erect and take charge of a pilot plant for the process. The World War prevented carrying out this proposal. The Dorr Co. also became interested in the process at about the same period. The investigations by the Freeport Sulphur Co. on the process as applied to the Cuban nickeliferous laterites, which resulted in the Nicaro enterprise, and the results of this operation have been well described elsewhere.1,²,³,4,5 This Nicaro plant was, in operation for almost two years, and during this period produced about 10 pct of the world nickel production from laterites containing 1.35 pct nickel. This plant and its operation were war measures and, in view of this, activities were suspended in April 1947. The results obtained fully demonstrated the technical feasibility of the process and its economical aspects on a commercial scale. In this respect, it should be understood that it is probable that improvements may be made by further development, and that there are possibilities for advantageous application of the process to garnierite and similar ores with higher values in nickel than the laterite iron ores at Nicaro. While the articles cited above have given a certain amount of information, no general article containing all the important process data has been pub- lished. Since the process is of more than local interest, a fuller knowledge of the fundamental and practical factors of the method may be welcome to those interested in this new field of metals technology. The author, accordingly, takes pleasure in submitting this article to the AIME as it represents in a condensed form the results of many years of research. The brief outlines of the fundamental and other factors and the explanation of observed phenomena are presented with as little discussion of details as possible, consistent with clarity. It is a special satisfaction to the author to make some contribution of his own in return for the benefits of the many valuable publications issued by the Institute during his thirty years of membership. Ores Adapted for Ammonia Leaching: All nickel and cobalt ores which originate from weathering of peridotites or similar basic rocks having sufficient values are suitable for treatment by the ammonia leaching process after a preliminary reduction under proper conditions. The formation of these deposits was probably as follows: In the course of time the basic rocks were attacked by atmospheric agencies; MgO and SiO2 were gradually leached out, and secondary nickel minerals formed, such as garnierite, a hydrated silicate of nickel and magnesia. These secondary products are, however, not stable. They decompose in a further stage of weathering and ultimately only a relatively small residue of insoluble oxides remains, known as laterite iron ore with a small nickel content and very little cobalt. Under these mantles of laterite, richer nickel values may be found, usually indicated by the occurrence of garnierite. The more the ore is disintegrated by nature, the higher the iron content and the better the nickel extractions that may be expected therefrom. Table I shows extractions that may be expected from different types of ores, assuming treatment of -200 mesh products and that all precautions have been taken for obtaining maximum extractions. As for the distribution of the various nickel minerals and compounds that may be present, great variations may occur from locality to locality as well as vertically in a deposit. From such "run of

Jan 1, 1951

By M. H. Caron

D. C. Ralston—The fact that none of the organizations that have worked on these ammoniacal leaching processes have contributed discussion of Mr. Caron&apos;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.&apos; 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&apos;s two papers practically amount to a summation of his life&apos;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&apos;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&apos;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 J. H. Rushton, L. H. Mahony

Principles of fluid motion and turbulence which have been found to be of use in mixing and agitation problems are discussed, as well as suggested applications in extractive-metallurgy processes. Various types of impellers are described, together with other conditions that affect flow pattern and turbulence. The choice of equipment for particular requirements is considered, and equations for power input are given. Modern heavy-duty mixing and agitation equipment can take an increasingly important part in such extractive-metallurgy processes as solids handling, crystallizing and leaching, chemical operations, and flotation. Application of mixing and fluid-mechanics principles to extraction methods can lead to greater process rates and a resultant saving in time and money. MIXERS are being applied with increasing frequency to problems in the metallurgical industries. The increase represents in part the modernization of mechanical equipment used through the application of unitized drives, modern electric motors and speed reducers, and recently developed materials of construction. Some applications have resulted from process changes and the use of techniques for operations similar to those that have been demonstrated and proven in the chemical industry. Still more applications are being developed through the use of fluid-dynamics principles not previously recognized as applicable to these operations. It is the purpose of this paper to describe those principles of fluid motion and turbulence which have been found to be of use in mixing and agitation problems, and to suggest applications for them in the extractive-metallurgy processes. Modern mixing equipment has been designed to provide the fluid motion consistent with that best suited to different operations.&apos; When properly applied, these more efficient fluid-handling mixers result in lower process-production costs. Metallurgical operations usually involve large amounts of solids. The characteristics of the ore control the process and only enough liquid is added to provide sufficient fluidity for handling and processing. The reactive part of the ore, the mineral value to be extracted, is likely to be low in percentage, and the quantity of reagent required is similarly low, but excessive dilution makes additional reagent necessary and therefore is undesirable. Thus, the primary problems in minerals processing are to handle as high a concentration of solids as possible and to distribute reagents uniformly. These pulps, or slurries, are in a range of solids concentration where hindered settling rates apply, and care must be taken to agitate and mix sufficiently to maintain suspension and flow throughout the equipment. Such slurries have high densities which are the weighted average of the components and viscosities that are spoken of as "effective viscosities" but are difficult to evaluate. It is convenient to separate metallurgical operations involving mixers and agitators into three categories: solids handling, mechanical or physical operations, and chemical operations. In each of these categories fluid motion is required to maintain suspension, to distribute surface-active agents, to blend components and reactants, and to induce high rates of chemical reaction. After a discussion of some basic principles of mixing and agitation, examples of application to the three categories will follow. Fluid Motion The fundamental problems of mixing and agitation of liquids have to do with the mechanics of fluid streams and the means by which they are

Jan 1, 1955

By D. R. Spink

In the preparation of zirconium and hafnium metals, there are many indications that impurity levels control the physical and chemical properties of the metal. The purpose of this work was to develop methods of producing pure raw materials that could be reduced to highly pure metals. Early work by the Carbomcndum Metals Co. and others indicated that certain fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. We have developed workable fused salts along with a continuous and higly efficient scrubber design which can be used to produce very pure zirconium tetrachloride. Metal made from the purified tetrachloride has been shown to approach crystal bar metal in purity. Scrubber designs are discussed with recommended materials of construction. VARIOUS methods have been used to purify zirconium (and hafnium) tetrachloride. Most of these methods involve thermal degassing initially (the removal of more volatile compounds at temperatures below that where zirconium tetrachloride exhibits a significant vapor pressure) followed by a sublimation step (which conveniently leaves the nonvolatiles behind.) While these procedures effect definite purification, such processing is batchwise and does not result in optimum purification. Early work by The Carborundum Metals Co. and others indicated that fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. The objective of this work was to develop a continuous fused-salt scrubbing process that would yield high-purity zirconium and hafnium tetrachlorides. The term "fused salt" refers to the molten state of ionic compounds and as used here, specifically refers to alkali metal and alkaline earth halides. Fused salts, because of their many valuable properties, are becoming increasingly im- portant industrially. These valuable properties of the fused salts are: 1) stability at elevated temperatures; 2)low vapor pressure; 3) low viscosity; 4) ability to dissolve many different materials; and 5) good elctctrical conductivity. All but the last property enhances the use of fused salts as scrubbing agents for zirconium and hafnium tetrachlorides. Fused-salt scrubbing may be defined for our purpose as the intimate contact between a gaseous compound and a molten salt with the purpose of removing impurities from the gaseous compound. In this case, the gaseous compound is zirconium tetrachloride which submlimes at 331°C. When this gas is contacted with a molten salt, impurities such as aluminum, iron, and titanium are removed and the resulting product is considered fused-salt scrubbed. Zirconium and hafnium are sold to a purity specification. Generally speaking, normal production without scrubbing is capable of meeting specifications. There are, however, several considerations That make the knowledge of methods of additional purification highly desirable. These are: 1) the control of product analysis; 2) the production of a pure product for special applications; 3) the salvaging of off-specification material; and 4) the use of raw materials with higher impurity levels than 1 he present raw materials. You will note that items 1 and 2 are somewhat complementary to each other and that item 4 assumes that The present process has impurity removal limitations. To better understand the part that fused-salt scrubbing of zirconium tetrachloride plays in the manufacture of zirconium, Fig. 1 contains an illustrated flow sheet of the industrial production of zirconium metal. In referring to Fig. 1, we can point out the specific benefits derived from our ability to purify zirconium tetrachloride. Purification of the crude (hafnium-containing) zirconium

Jan 1, 1962

By C. Norman Cochran, James L. Brandt

ALTHOUGH gas in aluminum and its effect on aluminum products have been the subject of a number of papers, not many quantitative determinations of the hydrogen content of solid aluminum and its alloys have been recorded in the literature. For solid aluminum samples, four investigators have reported hydrogen contents which appear reasonable compared with the hydrogen solubility of 0.7 ml per 100 g, STP, in molten aluminum at 660°C established by Ransley and Neufeld&apos; and verified by Opie and Grant&apos; and Ransley and Talbot. Sloman," who used a vacuum fusion procedure, reported the hydrogen content of some high purity aluminum as 0.66 ml per 100 g, STP. Griffith and Mallett, employing the tin fusion method, reported the internal hydrogen content of six different aluminum alloys as ranging from less than 0.1 ml per 100 g, STP, for 1100 alloy to 0.7 ml per 100 g, STP, for 4043 alloy (previously 43S, a 5 pct Si alloy). Eborall and Ransley," using a solid extraction of the gases at 600°C, reported hydrogen contents ranging from 0.1 ml per 100 g, STP, to 1 ml per 100 g, STP. Ransley and Talbot reported that several thousand analyses on 99.2 pct and higher purity aluminum as well as Duralumin type alloys indicated hydrogen contents ranging from 0.1 ml per 100 g, STP, to 0.5 ml per 100 g, STP.

Jan 1, 1957

By Leonard Klein

Reduction of oxygen-containing copper has always heretofore been brought about with wood poles. This paper reveals the first successful, economical, and Practical substitute for poles: a gaseous reductant, of which the production and plant use are detailed herein. THE art of fire refining of copper, consisting of melting, oxidation, slag removal, and finally reduction with wood poles, has been practiced for many centuries. An authentic record, discussed in detail in De Re Metallica,* mentions that as early as 1200 A.D. workers in this field of metallurgy were already acquainted with and practiced the basic principles of copper purification. Undoubtedly, the art was well developed marly centuries before the first written records began to appear. Notwithstanding the many advantages gained by application of mechanical con. trivances and by the tremendous increase in size of operations over the centuries, the reduction phase of the process has persisted essentially the same to the present time except for a very recent breakthrough. Numerous articles have been published and many patents have been issued on the subject of substitutes for wood poling in the past half century. They have dealt with a variety of gaseous, solid, and liquid reducing agents. But to the knowledge of the writer, no procedure has ever been prosecuted to a complete success on a large operating plant scale with the single exception of gaseous reduction of oxygen-containing copper revealed in detail herein. A natural gas-air reformer with ample capacity for

Jan 1, 1962

By L. J. Ingvalson, Roy H. Miller

IN 1948, as part of a program to expand the copper tube mill facilities of the American Brass Co. plant at Kenosha, Wisconsin, plans were formulated to convert the 100 ton capacity anode casting furnace at the Great Falls, Montana plant of the Anaconda Co. to the production of 3 in. phosphor -ized billets. The furnace was rebuilt completely and construction was started on an addition to the building. Members of the Great Falls staff visited various billet casting plants to draw upon the experience of other producers of this type of casting. Many features of other plants were incorporated into the Great Falls plant but, in addition, many new designs were made and perfected to make the plant the most advanced of its type. Construction was begun in 1949, with the intention of having the plant in production in the early part of 1951. In January 1951, as the plant was being rushed to completion, the government placed restrictions on the production of copper tubing. As a result, work was halted and the plant lay idle for two years. Interest was reactivated in May 1953 with the lifting of restrictions on copper. Plans were laid to go into production in July and the first charge was taken out July 1, 1953. Basically the plant is designed to produce from cathode copper a 3 in. diam billet, 50 in. long. weighing 110 lb, and containing 0.013 to 0.036 pct P, at a rate of 150,000 Ib per operating day. These billets are to be pierced and drawn into tubing. Furnace The furnace is a 100 ton capacity reverberatory type, gas fired furnace; 21 ft long and 9 ft wide. Gas is introduced to the furnace through two 38 hole Mettler gas burners. These burners are of chrome nickel alloy with four jets per hole. The furnace is charged with cathodes from the Electrolytic Copper Refinery plus return scrap from the casting operation by means of a Wellman Seaver Morgan Co. 7,000 lb capacity charging machine. The charge crane has a 20 ft boom and fork peel provided with an air ram to push material off the peel. The machine travels on overhead tracks and can be moved in any direction. The boom can be raised and lowered and swung through an arc of 180". With well stacked units of 6,000 lb, an experienced operator can put the first charge into the furnace in 40 min. After charging, the steel framed silica brick charge door is put in place and sealed with clay. After melting and skimming off the slag, the copper is blown until an oxygen content of 0.40 pct is reached. The metal is then heated to 2180°F, covered with coke, and poled. Poling is continued until a 3 in. diam test billet, 8 in. long, shows a flat set. The oxygen content is usually 0.030 pct at this time. At the end of poling, a temperature of 2160" to 2180°F is desired. In the side of the furnace opposite the charging door is the taphole slot, extending 36 in. upward from the bottom of the furnace. It is 4½ in. wide at the outside face and widens to 9 in. at the inside face of the furnace. It is filled with a wet mixture of sand, fireclay, and crushed coal. Flow of metal

Jan 1, 1957

By J. B. Cohen, B. W. Howlett, M. B. Bever

The partial molar heats of solution at infinite dilution in tin of aluminum at 300° and 350°C and of gallium, indium, and thallium at 240°, 300°, and 350°C have been measured by tin solution calori-metry. Aluminum, gallium, and thallium are endo-thermic on solution; indium is exothermic. Any temperature dependence of the heats of solution lies within the experimental scatter. Over the dilute ranges investigated, only aluminum has a measurable change in its heat of solution with composition. HEATS of solution of one element in another reflect the interaction between them. The investigation of partial molar heats of solution in dilute alloys is of particular interest as the properties of the solvent are altered to only a limited extent by the presence of the solute and also as the interaction between solute atoms is small. When the heats of solution of a related series of elements in a solvent are known, a systematic comparison may be made. In the investigation reported here, the partial molar heats of solution of the Group III elements aluminum, gallium, indium, and thallium in dilute solution in tin were measured. This work follows an investigation of the heats of solution in tin of the Group IB elements.&apos; EXPERIMENTAL PROCEDURES Materials. Samples of gallium, indium, and thallium were obtained from Johnson, Mathey and Co., Ltd. Indium and thallium were supplied as wire, 1.6 mm in diam; gallium was in the form of irregular pieces. The supplier reported the following minimum purities: gallium—99.95 pct; indium—99.99 pct; thallium—99.99 pct. The aluminum, obtained from Alcoa Research Laboratories, was reported to be 99.995 pct pure. The tin was supplied by Baker and Co., Inc.; the reported analysis indicated a tin content of at least 99.96 pct with lead as principal impurity. Calorimeter. this description will cover only the essential features of the calorimeter with special attention to modifications made since an earlier description was published.&apos; A Dewar flask containing the tin bath was held in a constant-temperature bath of a near-eutectic mixture of lithium, sodium, and potassium nitrates. This bath, which was stirred vigorously, was heated by a primary resistance winding in the container wall and by a secondary winding immersed in the salt. The voltage supplied to both windings was stabilized. The temperature of the salt bath was controlled by means of a platinum resistance thermometer in one arm of a Wheatstone bridge. The light from a mirror galvanometer in the bridge circuit fell on a photocell which controlled the current in a saturable reactor in series with the secondary winding. In this manner, the temperature of the salt bath was controlled to ±0.003°C and that of the tin bath to at least ±0.002°C. Each of these temperatures was measured by two iron-constantan thermocouples in series, coiled in a helix to minimize heat loss and immersed in the salt and tin baths in protective sheaths. The temperature of the laboratory was kept constant to ± 1°C during a run. Specimens were dropped into the tin bath from an addition arm held at O°C which was part of the cal-orimetric system. The system was evacuated to about 0.02 1 to minimize oxidation and to reduce transfer of heat. The bath was stirred by a glass stirrer introduced through a double Wilson seal. The samples were scraped clean before weighing, which was carried out as rapidly as possible. Each sample was immediately placed in the evacuated addition arm to minimize contamination. These precautions were especially necessary with aluminum. After the runs with gallium and thallium at all temperatures and with indium at 240° and 350°C (Series I) were completed and before the runs with indium at 300°C and aluminum at 300° and 350°C (Series 11) were begun the following changes were made. The shape of the Dewar flask was changed so as to result in a lower surface to volume ratio of the bath and at the same time the amount of tin was reduced from 500 to 400 g. The paddle type stirrer was replaced by a helical screw and the rate of stirring was increased to about 150 to 200 rpm.

Jan 1, 1962

By L. B. Ticknor, M. B. Bever

An isothermal calorimeter suitable for measurements of heats of solution in liquid tin as solvent is described. Measurements of the heats of solution of gold, silver, copper, and a gold-silver alloy are reported. The heat of formation of this gold-silver alloy is also reported. HEATS of solution in liquids can be determined directly, but few such data have been published for metals as solvents. Knowledge of heats of solution is desirable because it contributes to the general understanding of energy relations in metallic solutions. Thermochemical measurements of this type also furnish answers to specific problems: For example, from the heats of solution of an alloy and of a mixture of its constituent elements in a given solvent, the heat of formation of the alloy may be found. Similarly, differences in the energy content of samples of the same metal in two different states, such as the annealed and cold worked states, may be determined. In the work reported here, gold, silver, and an alloy of gold and silver were dissolved in liquid tin at 240°C and gold, silver, and copper were dissolved in tin at 300 °C. The experiments yielded the heats of solution of these metals in tin. The heat of formation of the gold-silver alloy was also determined. The same calorimetric method is being used to measure the energy stored in metals during cold working and preliminary results have been published.&apos; Equipment and Experimental Procedure The isothermal calorimeter used in this work, Fig. 1, consisted of a Dewar flask completely immersed in a constant-temperature salt bath. A long neck provided space for thermocouple leads and a stirrer shaft and permitted the injection of solute samples. The metal bath in the calorimeter flask was stirred at about 100 rpm by a small glass impeller driven by a constant-speed motor. The shaft of the stirrer passed through a Wilson vacuum seal.2 All measurements were made under vacuum in order to eliminate temperature disturbances resulting from gas convection and to prevent the oxidation of tin. The calorimeter flask was joined by an all-glass connecting line to a gas-control system which made possible the use of a protective atmosphere of deoxidized and dried hydrogen. At the operating temperature of the calorimeter tin oxide was not reduced by hydrogen, presumably because the reaction rate was too slow. Part of the closed system was a removable side tube through which the solute sample could be introduced and in which it was held at a temperature of 0°C prior to injection into the metal bath. The salt bath containing a mixture of sodium, lithium, and potassium nitrates was similar to that described by Beattie3 and was equipped with a stir-

Jan 1, 1953

By M. J. Pool, C. E. Lundin

THE relative partial molar enthalpies of aluminum, gallium, and indium in liquid tin have been measured at 750°K by liquid-metal solution calorimetry. The measured heat effects and the calculated relative partial molar heats of solutions at infinite dilution are listed in Table I along with the relative heat contents of the solutes calculated from the data of Kelley. All of the values are referred to 750°K even though the calorimeter temperature fluctuated by +1°K during the entire series of experiments. The effect of this small temperature variation on the experimental values should be less than the experimental error. The limits of error given in Table I represent the standard deviations of all values from the mean. In no case was the experimental deviation greater than the listed error limits. The reported error estimates only apply to the estimated precision of experimental values and not to their accuracy. Systematic errors could be present in the calorimeter which would affect the absolute values given. Moreover the heat-content data used could also be in error and this would affect the end results. The relative enthalpies used were listed in Table I so that future corrections could be made if necessary. The relative partial molar heats of solutions of aluminum in liquid tin and dilute A1-Sn liquid solutions are large and positive. The value at infinite dilution is given in Table I. In the dilute-solution region investigated the relative partial molar heat of solution was a linear function of composition. A least-squares analysis of the data gave the following expression at 750°K: Atf^ = 6195 - 12,160 A:A1(cal/g-atom) where XA1 is the mole fraction of aluminum in the alloy. This can be compared with the data of Cohen, Howlett, and ever&apos; who obtained the expression: 1SM = 6075 - 10,750 XM at 573°K Apparently both the partial molar heat of solution at infinite dilution and the concentration dependence increase with increasing temperature. This same

Jan 1, 1964