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By Olav Mellgren

Part I. The interaction between potassium ethyl xanthate and lead salts has been studied thermo-chemically. It is shown that ethyl xanthate reacts with lead carbonate, basic carbonate, thiosulfate and sulfate according to principles of simple chemistry, whereas reactions with lead sulfite, metasulfite, basic thiosulfate and hydroxide at high pH are associated with secondary reactions. A new compound "xanthogen thiosulfate" is postulated. Part 11. Adsorption of ethyl xanthate on galena has been studied quantitatively and thennochemi-cally. It is shown that an ion-exchange mechanism governs the adsorption process and that the heat of adsorption of xanthate on galena is equivalent to the heat of reaction of ethyl xanthate with bulk lead salts. It is concluded that the entropy content of the surface "compound" on galena is different from that of a corresponding bulk lead salt. Alkali depression is in part shown to be due to the instability of the xanthate-galena system at high pH and to the formation of basic lead salts. Sulfate and carbonate ions are shown to have a stabilizing effect on the xanthate-galena system. PARTI. THERMOCHEMISTRY OF ETHYL XANTHATE AND OF ITS REACTION WITH LEAD SALTS In the past little attention has been paid to the chemistry of lead xanthate. It is known that xan-thates form slightly soluble compounds with lead and that suspensions of lead xanthates in alkaline solution decompose rather readily.' The solubility of lead ethyl xanthate is of the order of 2.6 x 10-6 moles per 1. At increasing pH the xanthate concentration of a saturated solution contains more xanthate. Thus at pH 11 this xanthate content is about 100-fold larger than at pH 7.1 Xanthates are known to be consumed when added to a suspension of slightly soluble lead salts such as lead sulfate and lead carbonate. It is unknown to what extent this xanthate consumption is due to a simple chemical reaction because, frequently, observations are made which reveal secondary reaction products in such reactions. Thermochemical study of the reaction between xanthate and lead salts offers a means to clarify the significance of these reactions as the enthalpy changes can be accurately predicted from heat of formation of lead salts in pure solution reactions. In the present work the heats of formation of lead ethyl xanthate from potassium ethyl xanthate and lead salts are determined and some thermochemical aspects of xanthate in solution are studied. The results of these investigations are presented in Part I. In Part II the heat of adsorption of ethyl xanthate on galena surfaces is presented. All enthalpy changes were measured directly in a microcalorimeter. Calorimeter: The calorimeter used for measuring enthalpy changes was similar to that used by Redinha and Kitchener2 which was based on a description by Derbyshire and Marshall.3 Other useful references4,5 are listed. A sketch of the calorimeter

Jan 1, 1967

By M. Prats

Most of the information available on the heat efficiency of hot fluid injection processes, both water and steam, has been obtained from calculated temperature distributions in the pay zone and adjacent formations. The usual approach has been to write the heat balance equations in terms of the temperatures, and then to introduce whatever simplifications are necessary to help obtain an analytical or a numerical solution. In either case, the assumption has often been made that the vertical thermal conductivity in the flooded interval is infinite, so that the temperatures within the flooded interval are then independent of vertical position. Because it was first made by Lauwerier,l and has been used extensively since, this assumption will be referred to as the Lauwerier assumption. Excellent reviews of the literature on the heat efficiency of hot fluid injection processes have been given by Spillette,2 Flock et al.,3 and Ramney.4 Of course, the most significant contributions take into account the effect of a finite vertical thermal conductivity on the vertical temperature profile. The most general analytic expression for the heat efficiency of a hot fluid injection process is that of Antimirov5 who considers injection of a heated incompressible fluid into a reservoir through an arbitrary number of wells. The rate of heat injection into the reservoir, as well as the injection temperature, is an arbitrary function of time. The geometry of the horizontal flow is arbitrary, although the reservoir is considered to be of uniform thickness and properties and to be of infinite areal extent. Heat transfer within the reservoir is by horizontal convection and conduc- tion, and by vertical conduction. In the formations adjacent to the flooded interval, heat transfer is by conduction in any direction. Thus, the available expression for the heat efficiency due to hot water injection has been developed for rather general conditions. This degree of applicability has not been obtained for other thermal recovery processes. By making the Lauwerier assumption we have been able to obtain expressions for the heat efficiency that are essentially independent of the thermal recovery process, be it steam, hot-water, or underground combustion. Clearly, then, the approach followed here is more restrictive than that of Antimirov5 in that it uses the Lauwerier assumption. At the same time less restrictive assumptions are made about the horizontal heat transfer mechanisms, either in the flooded interval or in the formations adjacent to it. The main difference between our approach and that of other investigators is that the heat balance in the pay zone is expressed for the pay zone as a whole rather than for a volume element within it. The Lauwerier assumption is introduced after the problem is developed along these lines as far as possible. The details of the development of the heat efficiency are given in the Appendix, while the main features of the model are discussed in the next section. Results and their implications are discussed later in a separate section. The Model Certain assumptions have been made to determine

Jan 1, 1970

By Scott Turner

GOLD AND SILVER, the monetary metals, have presented in the last year a striking contrast; gold has experienced unusual prosperity, while silver has been depressed more severely than ever before. Gold mining has been hailed as the only basic industry that is able to thrive on depression; the new gold produced is thought by many to be the most important material for the reconstruction of prosperity. Silver production, meanwhile, has been sinking to its level of 40 years ago, and its price to a level never before recorded. These factors have reduced the value of silver produced in 1932 to about the value of the average annual production more than a century ago, that of the decade 1801-1810. No other major commodity in world trade appears to have suffered a greater decline during the present depression.

Jan 1, 1933

By R. W. Stahl

Employees and dollars are necessary to all enterprises and any force, such as fire, which destroys either, can bring very serious consequences, including business failure. Since everyone acknowledges the necessity of conserving human life, we will devote most of our paper to the economic factors involved. A coal-mine fire is considerably more difficult to combat than a fire in a surface building because of the combustible surroundings in the mine, the explosive gases emitted from the coal, the suspension of explosive dust when mine timbers burn and the unsupported roof falls, the limited space in which approach to the fire can be made, and the limited avenues of escape. A survey of coal-mine-fire protection indicated that a rather low value was being placed on property and equipment. This prompted comparison with other industries. The comments made in this comparison are not intended as an indictment of the coal industry, since we do have mines that are well protected against fire, but the comments on conditions at the mines visited are factual and may help others to improve similar conditions. SURVEY PROCEDURES Plants of the steel, aluminum, rubber, chemical, and petroleum industries were surveyed, and all facets of the fire-protection scheme were covered. The industrial plant invariably had four times as much water readily available for instant use than the mine. In many mines where water is available, no equipment for applying it is provided, such as hose, nozzles, and adapters, so that time is lost in collecting this equipment. (See Table I.) EXTINGUISHERS Many more and generally larger portable extinpishers are available at the plant as compared to the mine. The extinguishers are generally placed nearer to sources of danger. In addition, respiratory protective equipment is always available at strategic points in plants but only in a few mines. (See Figs. 1 and Table 11) INSPECTING AND TESTING EQUIPMENT Plant water facilities are checked weekly and flushed at 6-month intervals, and hose is pressure-tested at least yearly; some mines check water yearly, but hose is not tested unless used. Fire extinguishers are inspected weekly in plants and completely overhauled yearly; one mine had monthly checks and overhauls only after use. FIRE BRIGADES AND TRAINING Every plant had designated fire-fighters and some complete full-time brigades; at one mine a chief mechanic was designated as being in charge of fires, and other depended entirely upon officials who might not be familiar with the equipment. COST OF FIRES AND PERCENTAGE OF CAPITAL INVESTMENT IN FIRE PROTECTION The direct cost of recent mine fires ranged from $128,000 to $240,000; indirect costs, such as lost tonnage, idled equipment, lost orders, and the like might run the cost to over $500,000. (See Figs. 2 and 3).

Jan 1, 1961

By S. M. M. Safvi, A. Jowett

Small-scale continuous flotation tests are described in which the influence of 1) pulp density and 2) feed rate on the rate of flotation are investigated. The results provide further evidence of first-order kinetics for flotation and indicate that tests at different feed rates provide a particularly simple method of determining rate constants. Flotation kinetics are discussed in general terms. Over a period of many years numerous research workers have studied the rate of recovery of valuable materials from flotation pulps with a view to deter-mining the mechanism of the froth flotation process. Froth flo ation is fundamentally a collision process involviug at some stage collision and then mutual attachment between air bubbles and mineral particles. It is possible to draw analogies therefore between the flotation process involving mainly macroscopic particles and the ordinary processes of chemical reaction kinetics involving collisions between atoms, molecules and ions. By adopting this analogy we may postulate a general equation representing the kinetics of the flotation process: -dC/dt =K.CC ,Aa (1) The rate constant, K, will be a complex function involving reagent concentrations, particle and bubble sizes, induction times and no doubt flotation cell design. However, these are factors which can be kept constant in any series of experiments, permitting investigation of the exponents a and c, which determine the order of the reaction occurring in flotation. The various research investigations carried out so far have all aimed at evaluating a and c and in the majority of cases only since the concentration of air has usually been kept constant in a series of tests, so that a relationship of the following type has been investigated: -dC/dt = K1 Cc (2) The techniques of both batch testing and continuous testing have been used to investigate this relationship. The technique of continuous testing, in which steady-state conditions are established, permits direct investigation of the above equation. In the case of batch testing, C is decreasing continuously

Jan 1, 1961

By J. C. Borland, J. H. Rogerson

Jan 1, 1963

By Henry Rawdon

THE following note describing the behavior of copper under rather unusual conditions is offered here for its suggestiveness rather than as a complete study of the question. The examinations described were made because of a request for information concerning the embrittlement of copper when heated in a molten salt bath (sodium chloride) for the purpose of cleaning it, as well as for softening it. It is well known that metals may be rendered very brittle by electrolytic action, in aqueous solutions, in all probability by the action of nascent hydrogen, and it was suspected that perhaps the embrittlement of the copper by means of the molten salt was produced in a somewhat similar manner. It was found that the copper was in contact with iron (or steel) while immersed in the molten salt, through the occasional use of an iron stirring rod, iron forceps for handling the pieces, and an iron pot for containing the fused salt. In the electrochemical potential series iron and copper stand some distance apart, copper being electronegative to the iron. Assuming that the two metals bear a similar relation to each other, when immersed in a bath of molten salt, as they do in an aqueous solution, they would be expected to form a galvanic couple, the copper being the cathode. By this means the copper might be embrittled, as often happens in aqueous solutions, by the action of the liberated hydrogen. In this case, however, the embrittlement must be attributed to some other agent than hydrogen. To demonstrate how copper may be embrittled under these conditions, two small rods, one of copper and the other of mild steel, approximately 3/8 in. (9.5 mm.) in diameter, were immersed in a bath of sodium chloride that had been heated somewhat above its fusion point (melting point of sodium chloride is 819° C.) and an electromotive force of approximately 6 volts from a storage battery was impressed upon the system. The copper was made the cathode and the action was continued for

Jan 2, 1920

By C. E. Melbye

A serious problem confronted the city of Gunnison early in 1958 in that, for a few months during each spring runoff, the water supply derived from the Gunnison River became polluted to an unsafe point. The city management had the choice of building a new filter plant to replace the old unworkable one or drilling wells to develop a ground water supply. The cost of a new filter plant was estimated at $180,000 compared to $50,000 for 6 wells, pumps, and additional water lines, hence their decision to attempt the development of sufficient ground water. Six wells at 300 gpm per well were estimated as necessary to handle the peak usage of 1800 gpm, compared to only 600 gpm winter usage. Although the water table is only about 7 feet below the surface, existing private wells drilled at random locations were producing much less than 300 gpm. The problem was to find sufficient quantities from about 6 wells. Since the presence of an ancient bedrock channel was suspected, which would be expected to localize greater quantities of water, the city of Gunnison authorized a resistivity survey to investigate bedrock topography below unconsolidated gravels. Survey results were highly satisfactory and led to the preparation of a fairly detailed bedrock contour map, Fig. 1. This map was used in selection of all well sites. The city of Gunnison is situated in a flat, broad, Quaternary gravel-filled valley (terrain dips south at 20 feet per mile) at the junction of the Gunnison River and Tomichi Creek. The valley, about 2-4 miles wide, is bordered by hills of Tertiary volcanics to the northwest, Cretaceous and Jurassic sediments to the north and northeast, and pre-Cambrian granite and gneiss to the south. One previous deep test well at the west end of the city hit pre-Cambrian granite at 496 feet, which, allowing for 40 feet of surface gravels, makes the older sedimentary section 456 feet thick. This section is probably all Jurassic Morrison formation, consisting of the Saltwash sandstone overlain by the much thicker section of Brushy Basin shales and mudstones. According to the driller's logs, each well was bottomed in what is believed to be Brushy Basin shale. FIELD PROCEDURE A standard Gish-Rooney type of resistivity apparatus was employed, which used 45-volt dry batteries as a direct-current power source. Applied voltages could be selected from 45 volts to a 270-volt maximum. Copper-coated steel stakes were employed as current electrodes and porous porcelain pots as potential electrodes to avoid possible polarization effects with direct current. The expanding Wenner electrode configuration was utilized for this investigation and measurements were made at 20 40, 60, 80, and 100-foot spacings,

Jan 1, 1961

By M. W. BERNEWITZ

ALL live producers and manufacturers of metals and alloys are investigating new uses for their products. The tin and tin-plate industry is no exception. One-third of all the new tin mined and refined is consumed in making tin plate. Several billions of cans are each year made from tin plate for the preservation of nearly 200 kinds of food. There are more than 500 tin-plate mills or individual stacks in the United States, which country makes more tin plate than all other countries combined and exports large quantities. As much as 1,800,000 tons of till plate has been made in a year in this country, and 28.000 tons of tin has been used in this period for this purpose. In sonic years a third of the till is so consumed; in 1933 it was half of the supply.

Jan 1, 1935

By D. R. Cook

This paper is a case history of an exploration venture for base metals, begun by the Rocky Mountain District of Bear Creek Mining Company in 1952 and completed in 1954. The project was based on the idea of W. S. Burbank, U. S. Geological Survey, that commercial deposits of base metals might occur in Paleozoic sediments beneath hydrothermally altered volcanic rocks in the Southern Bonanza mining district, Colorado. Here, an area of andesitic rocks, four square miles in extent, has been argillized, pyritized, chloritized and silicified. Geological, geophysical and geochemical studies were followed by the diamond drilling of three holes totalling 6,220 feet. Further alteration ang geochemical studies were made on the cores from these holes. A brief review of the alteration and geologic mapping, colored aerial photograph interpretation, geochemical soil and rock sampling, magnetic, gravity and radio-metric surveys are presented together with some conclusions regarding this work. This paper is a case history of an exploration venture for base metals, begun by the Rocky Mountain District of Bear Creek Mining Company in 1952 and completed in 1954. Important contributions were made to the project by personnel of the Rocky Mountain District and the Geophysics Division. Individual acknowledgements to these people are made at the end of the paper. BASIS FOR THE PROJECT The project was based on the idea of W. S. Burbank (1947, p. 444) that commercial deposits of base metals might occur in Paleozoic sediments beneath hydrothermally altered volcanic rocks in the Southern Bonanza mining district, Colorado. Paleozoic sedimentary rocks, including the favorable Leadville limestone, are exposed three miles south of the altered area, and reason exists to believe that they might underlie it within a reasonable depth. Alteration of pre-mineral volcanic rocks has been used successfully as a guide to concealed orebodies in the Main Tintic and East Tin tic mining districts, Utah (Bill-ingsley, 1933, p. 120-122; Lovering et al, 1949; Howd, 1957, p. 124-134; Cook, 1957, p. 73) and could be a useful guide here. GENERAL GEOLOGY AND STRUCTURE The Northern and Southern Bonanza mining districts are northwest of the San Luis Valley in southern Colorado, just within the northeastern edge of the San Juan volcanic province. The districts are1ocated on the southern extension of the Sawatch uplift, a prorninent northwest-trending structural high. The highly productive mining camp. of Leadville, Gilman and Aspen are on the northeastern and northwestern flanks of this uplift where Paleozoic limestones have

Jan 1, 1961

By Felix Edgar Wormser

JUST as the ancients used the products of their crude mining endeavors to fashion tools with which to make digging easier, so today mining enterprises are dependent upon the very metals they mine for the efficient conduct of mining and metallurgical operations. In fact, the outlet afforded by the production of minerals in the United States is no mean market for the nonferrous metals. I believe that mine managers frequently lose sight of the opportunity they have to select from competitive products those which will help the market for their own metal output. For example, some years ago a large lead mine used storage-battery locomotives for its haulage, common practice, of course, throughout the United States. These particular locomotives, however, were powered not with the ordinary lead storage battery but by a competitive battery product made from an imported metal. After studying this situation, the manager saw how he could help himself by purchasing a product made from his own mineral output, and in his next order turned tip the use of the lead storage battery.

Jan 1, 1935

By E. L. Oliver

IN OFFERING a few comments and suggestions on trends in mining practice, and the methods and tools of tomorrow's mining, perhaps it will be appropriate to start with the subject of education. Charles Kettering, one of the best-known scientists and experimentalists in the automotive industry once said, in effect, that tech- 111ca1 schools have to be carefid not to teach a lot of hard and fast rules that may have been true once, but aren't so any more, or won't be presently. Possibly the mining school of the future will concern itself less with what has happened and more with what is going to happen. It will be built about or around problems. Such a school will be judged, not by the number of its students but by the quality of its improvements. To such a school the industry will send for men to solve particular problems. The industry will doubtless at some time sup- port such a school financially though a lot of hard work will be required to organize miners to undertake such financing, primarily because the mining industry, other than that concerned with iron and steel, is too loosely knit. Each company tends to its own knitting too closely for its own good. Wouldn't it be splendid if the mining industry would finance a "problem school" as suggested by Mr. Kettering and others.

Jan 1, 1939

By R. N. Edmondson, L. Mair, M. Tenenbaum

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhord Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chipmon, Vice President; T. D. Jones, Treosurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. w. Thornton, Chairman; Dennis Carney, John Chipman, J. C. Fulton I. H. Hollomon H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supenision of the following Publications Committees: Extractive Metallurgy Division: T. 0. King Chairman; S. J. Dickenson, R. P. Hermsdorf R. Schuhmann. Jr.. and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman F. Lincoln Vogel Jr., Vice-chairman, W. A. Baikofen, R. W. Boliuffi J. H. Bechtold M. B. Beyer. R S. Busk, C. G. Gaetzel, Paul Gordon C. D. Groham, Jr., Robert F. Hehe-mann,' R. I. Joffee, F. c. Joumot Jr lrving R. Kramer A. J. Lena Harold Morglin, C. J. McHargue, Russell A: Meussner, J. B. Newkirk H. W. Paxton, G. E. Pellissier, I. S, Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B King, F. C. Langenberg, W. 0.. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining Metallurgical and Petroleum Engineers Inc., 29 West 39th Street, New York 18, N. Y. Telephon: pEnnsvlvanio 6-9220. Subscription 522 Per year for non-AIME members in United States and North South and Central America; $25 foreign;, $5 for AIME members. Single copies, 54.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed In its publications . . . Copyright 1958 by the American lnstltute of Mining Metallurgical and Petroleum Engineers Inc. . . . Registered cable address AIME New York , . . lndexed in Engineering Index Industrial Arts Index and Chemical Abstrats . . . Application for second class mail privileges ii pending at New York, N. Y. Volume 212, Number 4.

Jan 1, 1959

By E. W. Rouse

THE year 1936 has seen rehabilitation of many plants which had been closed or severely curtailed. The Steptoe smelter of the Nevada Consolidated Copper Co. has been transformed by a rearrangement of the flow of material and utilization of mechanical handling to a maximum. The Phelps Dodge Corp. reports the construction of newer and better reverberatories at the Copper Queen smelter, and of particular interest, a single high-pressure waste-heat boiler placed directly over the uptake. There has also been a complete reconstruction of the smelter at the Laurel Hill plant of the Nichols Copper Co.

Jan 1, 1937

By TENNEY C. DeSOLLAR

TRADITION tells us that the earliest use of Alabama iron was to make shoes for the horses of General Andrew Jackson and his men during the first part of the nineteenth century. The first recorded incident in the making of iron was the request of U. S. Indian Agent Benjamin Hawkins "that a crew of blacksmiths be sent to the Creek Nation in the lower Mississippi territory." These frontiersmen made up the first body of pioneer iron makers in the territory. The first known blast furnace was built by Joseph Heslip in 1818 at Russellville, named after Major William Russell, who was General Jackson's chief of scouts. The Tannehill furnace was built in 1830 in what is now Tuscaloosa County and its ruins, as shown above, can be seen today.

Jan 1, 1937

By C. G. Dunn

James, Jones, and Leak (JJL) conclude that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally produced recrystallization textures. I agree. However, it is not clear whether they conclude a) that the orientation dependence of rate of growth of secondaries in (commercial) silicon iron depends on both temperature and a temperature gradient or b) that, in applying rate data obtained in a steep thermal gradient, the isothermal annealing temperature must be close to the temperature for which the rate data apply. Also, it is not clear what tem-

Jan 1, 1967

By R. J. Stokes

S. Floreen (international Nickel Co.)— One fairly simple way to differentiate between em brittle me nt due to surface microcracks or due to a dislocation barrier effect might be to load a brittle rock salt crystal in tension to some stress just below the fracture stress and then immerse the loaded crystal in water. If a surface film is retarding plastic flow then one should observe some plastic deformation of the rock salt as

Jan 1, 1962

By F. R. Hensel

The present paper describes a number of experiments with fine silver, coin silver, silver-cadmium oxide and silver-nickei-copper compacts, prepared by powder metallurgical methods. The test data are of a preliminary nature, since most of the work was exploratory. Fine Silver Eject of Compacting Pressure on Hardness and Density during Cold and Hot Pressing The cold-welding properties of silver have received considerable attention and the welding characteristics are functions of such variables as: cleanliness of metal particles (impurities and adsorbed gases), chemical nobility of particles, plasticity and hardness, particle assortment, particle shape, particle porosity, apparent density, temperature, pressure, time, recrystalliza-tion characteristics. Chemical nobility, plasticity and low temperature of recrystallization after work-hardening are responsible for the excellent low-temperature bonding properties of silver. Several series of compacts were pressed at pressures of 5, 10, 20, 30, 40, 50, 60 70 and 80 tons per square inch, at temperatures of 32°C. (room temperature), l00°, 2000, 300°, 400°, and 450°C. Silver powder of minus 325-mesh, produced by displacing silver from a nitrate solution by means of copper, was used. The density was calcuiated from accurately measured and weighed compacts. The hardness was measured on the Rockwell F scale. The investigation shows that an increase in pressure promotes a higher density and hardness regardless of pressing temperature, up to a temperature of 400° C. The pressure-density curves at various pressing temperatures are shown in Fig. I, the pressure-hardness curves at various pressing temperatures, in Fig. z. The greatest increase in both hardness and density was obtained in the pressure range of 5 to 20 tons per square inch. A compact from each series was annealed at 300°C. in air, for various lengths of time. The hardness values after annealing are shown in Table I. A minimum hardness was obtained after one hour of annealing. No change in density occurred during annealing. The maximum density was obtained at 80 tons per sq. in., and at this pressure the hardness is equal to that of hard-drawn wrought

Jan 1, 1945

By J. C. Detweiler

THE Jacksonville plant of Humphreys Gold Corp., operating under leases from National Lead Co. and Rutile Mining Co. of Florida, recovers rutile, ilmenite, zircon, and monazite from an ancient beach deposit containing about 2.5 pct of these minerals in combination. The location of the plant is unique, being situated about ten miles from the center of Jacksonville, Fla., surrounded by a thriving suburb. Two four-lane highways pass within 1 ½ miles of the plant. An expressway now under construction will pass over the tailing pile, within 500 ft of the mine office. The elevation at the plant site is approximately 50 ft above sea level. This is one of two mines producing titanium minerals and zircon in Florida. Another mine is also operated by Humphreys at Starke, about 50 miles southeast of Jacksonville. The Jacksonville deposit extends about six miles in a north-south direction, averaging approximately one half mile wide and twenty ft thick. Values begin at the surface over most of its length and ter-

Jan 1, 1952

By J. M. Toguri, K. Grjotheim

It is known 1,2 that the equilibrium between titanium metal, TiCl2 , and TiCl3, in a solvent of molten metal chlorides, is influenced both by the total amount of dissolved titanium and by the type of solvent. Assuming that the trivalent titanium forms the complex ion Ti111 Cl4, the equilibrium reaction may be expressed by the following equation, (Me) TiIII cl4+ 1/2 Ti = 3/2 TiII cl2+ (Me) Cl The ideal ionic equilibrium constant for this reaction is, Where the N's are the molar ionic fractions in the equilibrium melt, and (Me) the different types of cations present in the equilibrium mixture. The following thermodynamic relation is derived between Kand the concentration of cations in the equilibrium melt, mix The N"S are the equivalent ionic fractions, and so forth are constants corresponding to the standard changes in free energy for reactions in melts where only the cation indicated is present, and f (y1) is a function of the activity coefficients in the equilibrium mixture. When this term vanishes, a simplified linear relationship between In Kideal and the concentration is obtained. The simplified relationship has been applied with satisfactory results to the experimental data of Mellgren and pie,' and Kreye and Kellogg.2 MANY existing methods for the production of light metals involve the reduction of their respective metal halides in the presence of salt melts composed of alkali or alkaline earth chlorides. In such a solution phase, the light-metal halide may undergo stepwise reduction from a higher, to a lower valence, and finally to a zero valent state. In this connection, the disproportionation equilibrium is of great interest. In the case where the higher valence is three and the lower valence is two, the disproportionation equilibrium may be written as follows, 3 Me11 = 2 Me111 + Me [I] If this equilibrium occurs in a salt melt containing a large excess of alkali chlorides, a typical ionic melt is obtained. It is then possible to formulate the cation equilibrium: 2 Me+h' + Me = 3 Me++ [II] Reaction [11] is analogous to a cation exchange reaction. It has been shown thermodynamically that the equilibrium constant for such a reaction in 2

Jan 1, 1960