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By W. E. Robinson

Samples of raw oil shale and kerogen concentrates were oxidized by alkaline potassium permanganate, air, nitric acid, oxygen, and ozone to obtain information about the chemical structure of organic kerogen in oil shale. In one test, oil shale and oil-shale products were oxidized exhaustively with alkaline potassium permanganate, and the distribution of the organic carbon in the final oxidation products was determined. Comparing results of this oxidation with those obtained from other carbonaceous materials and known compounds gave information about the structure of kerogen. Alkaline potassium permanganate oxidation also was used partly to degrade kerogen into soluble products for characterization purposes. Structures present in these degradation products were indicative of type structures originally present in the kerogen. Nitric acid, oxygen, and ozone were used also for partly degrading kerogen to soluble oxidation products. Carbon-balance oxidation tests using alkaline potassium permanganate showed that Colorado oil-shale kerogen differs from many other carbonaceous materials such as coal and kerogens from other areas. Composition of the degradation products indicated that Colorado oil-shale kerogen is predominantly cycloparaffinic and saturated heterocyclic structures with some long-chain paraffinic and aromatic structures present. The ring systems may be connected through short carbon chains or bridges containing oxygen, nitrogen, and sulfur.

Jan 1, 1963

There is an alternative theory of the high grade orebodies of the Middleback Group, based on the primary nature of the high grade ores in an area of carbonate deposition, with lesser amounts of siliceous and aluminous sediments. The environment is thought to have been unstable, possibly volcanic, and to have been a subsiding basin, substantially isolated from the open sea.Jaspilites, iron bearing talc rocks and iron bearing carbonate rocks were derived from the primary sediments by metasomatic alteration after metamorphism.The metasomatic agents were carbon dioxide and water vapour which were mobilized from the primary dolomite and reacted with a metamorphically produced group of iron bearing and iron free amphiboles, forming talc and progressively releasing silica and iron oxides from the iron amphiboles.The talc rocks in turn released silica which reconstituted jaspilites into their present 200 ft thick crust or zone.The theory accounts for the present disposition of a jaspilite zone over a talc zone which in turn overlies a carbonate zone, and accounts for the down dip changes found in bores which penetrate these zones.INTRODUCTIONIron Duke (Fig. 1) lies some 34 miles south west of WhyalIa in South Australia, and is the most southerly ore body in the Middleback Ranges.The Middleback Ranges are divided into a northern range and a southern range meridionally disposed and separated by an erosion gap called Kimba Gap.The South Middleback Range contains four orebodies;Iron Duke at the southern extremity, Iron Duchess north of Iron Duke and on the same ridge, Iron Knight also on the same ridge, which has been breached by erosion between theDuchess and Knight orebodies, and north east of Iron Knight, the Iron Chieftain.Cook's Range is the eastern range of the South Middleback Range and no large orebodies are known to occur there.

Jan 1, 1963

The CSIRO acid alumina employs the essential steps of digestion, hydrolysis and calcination to produce pure alumina from ores too high in silica or too low in grade for the Bayer process. The two latter stages have been described in some detail previously but the digestion stage requires separate dis-cussion since ores vary widely in composition and reactivity. Kaolinitic clays require. roasting to 8000C to render the alumina soluble in the 11 per cent sulphuric acid used in the process while some ferruginous laterites require roasting to reduce the reactivity of iron minerals. The iron content of pregnant solutions is kept at a low figure by digesting at temperatures where the solubilities of ferric oxide or basic ferric sulphates are small. A.two-stage, counter-current digestion is necessary to extract a high percentage of alumina from the ores and to pro-duce a basic pregnant liquor, with an S03:Al203 ratio of 1. 9 suitable for high temperature hydrolysis. The second stage of digestion, called the modification stage, treats slightly acid liquors with exces's of ore in the temperature range 1200- 1400C. The first stage operates at 1700-190 C to extract further alumina from modification residues, using recycled acid obtained from later steps of the process. Both temperature ranges are critical for economic operation and for proper con-trol of the iron content of solutions. In batch experiments, thirty minutes is regarded as a suitable retention time for digestion and modification; ores which require much longer than this are less suitable for the process. Impurities. such assilica, titanium and vanadium oxides are discarded in the residue along with iron oxide and do not contaminate the final product. Bivalent metallic sulphates such as MgSO4 can build up in the circuit to a very considerable degree without affecting. product purity.Comparison with other processes shows that the C. S. I. R. O. process is superior for control of contamination by iron, which is the major problem in acid processes. The pure intermediate product (3 A1203. 4 S03. 9 H2O) is also more convenient for cal-cination to alumina than the hydrated aluminium sulphate usually recovered in other processes. Detailed cost comparisons must await pilot-plant evaluation of the C. S. I. R. O. process.

Jan 1, 1963

By A. H. Daane, B. J. Beaudry

The Sc-Y and Sc-Zr systems were studied by thermal and X-ray methods. Both systems are characterized by complete solid solubility in the low temperature hexagonal form and in the high temperature bcc form. In the Sc-Y system, there is a minimum in the solidus at 50 at. pct and 1365°C, while the solidus in the Sc-Zr system follows a nearly straight line relationship between the melting point of scandium and zirconium. There is a minimum in the temperature of transition from hexagonal to bcc in the Sc-Y system at 43 at. pct Y and 1175°C; while the temperature of transition is raised in the Sc-Zr system to a maximum of 1415 °C at 30 at. pct Zr. INTEREST in the metals of the first transition series has usually stemmed from their useful properties; however, there is now a great deal of interest in determining the fundamental nature of these metals. Since scandium is the first of these transition metals, a study of the preparation and Properties1 and the alloying behavior of scandium2 was initiated. In a continuing study of the alloying behavior of scandium, the systems of scandium with zirconium and yttrium have been established. Extensive solid solubility in both the Sc-Zr and Sc-Y systems was expected from application of the classical rules of Hume-Rothery. Also, the modified Darken and Gurry plot as suggested by Gschneid-ner3 showed ideal conditions for solubility in the Sc-Zr system with less favorable conditions in the Sc-Y system. The effect of scandium on the transformation temperature of zirconium and yttrium was of interest, since a recent empirical observation by Uly and Burr4 predicted that the solute scandium would raise the transformation temperature of zirconium and lower the yttrium transformation. In addition to noting the validity of the above predictions, the SC-Y and Sc-Zr systems were established. EXPERIMENTAL METHODS Materials. The metals employed in this investigation were crystal bar zirconium, distilled scandium prepared by the method described by Spedding, et al.1 and yttrium prepared by the method described by Carlson, et a1.5 The major impurities present in these metals are listed in Table I in ppm. Alloy Preparation. All the alloys examined were initially formed by comelting the two metals in a nonconsumable electrode arc-melting furnace under an atmosphere of purified helium or argon. The buttons were inverted at least five times and re-melted each time to ensure homogeneity. During preparation of Sc-Zr alloys, approximately 1 wt pct was lost which was attributed entirely to the loss of scandium by distillation. When preparing Sc-Y alloys, approximately 1.5 wt pct was lost, but it was assumed that the intended composition was maintained, since the relative weight lost when arc melting the component metals was nearly the same. Samples weighing 15 to 20 g were prepared for time-temperature thermal analysis, while only 1- to 2-g samples were prepared for the optical pyrometer and X-ray diffraction studies. Thermal Methods. The solidus and the melting points of the metals were determined by an optical pyrometer method described previously.2 The temperatures at which the transformation from hexagonal to bcc occurs were determined by differential thermal analysis. Several points on the solidus and liquidus in the Sc-Y system were also determined by this method and are in good agreement with those obtained by the optical pyrometer method. The procedure followed in the preparation of samples for thermal analysis and the furnace used have been described elsewhere.2'6 Since a limited quantity of scandium was available, most of the alloys were not melted during thermal analysis, thus avoiding contamination by the crucible. The alloy could then be reused and the composition changed by adding the desired quantity of solute to obtain the next alloy. Heat Treatment and X-Ray Methods. In order to ensure homogeneity, the "as arc-melted" alloys Were wrapped in tantalum foil, sealed in quartz capsules and heated at 1100°C for 15 hr and then cooled at a rate of 8 deg per min. Samples for X-ray diffraction were filed from these heat-treated alloys, sealed in 1/8 in. by 1/2 in. tantalum capsules under

Jan 1, 1963

By Pablo Hadzeriga

There are two places in the world where potash, trade name for potassium chloride, is economically recovered from naturally occuring brines by solar evaporation. One is at the Dead Sea and the other at Wendover, Utah. American Potash and Chemical at Trona, California recovers potash from natural brines, but uses fuel to accomplish evaporation. Under proper meteorological conditions the use of solar evaporation might be desirable from the economical standpoint. Of course, this may not be true when, if by artificial evaporation, a group of very valuable salts are recovered. This is the case of the American Potash operation at Trona. Solar evaporation has its limits. The working temperature is low. We may say, just to cover most areas of the world where solar evaporation may be practical, that it will take place between 18°C and perhaps around 45°C. In most cases the average working temperature expected will be around 25°C.

Jan 1, 1963

This paper deals briefly with the geology and mineralisation of the Ediacara Mineral Field, which is located about 300 miles north of Adelaide in the Mount James Range.The field was discovered sane time prior to 1872. Total recorded production for the field amounts to a few hundred tons of lead and 36 tons of copper. Re-listing of the field during 1961-62 led to its classification as a Mississippi Valley type deposit. Diamond drilling has partly outlined the spread of mineralisation and confirmed its stratiform distribution,Sources for the metals are suggested and various possible mechanisms. of deposition are described.

Jan 1, 1963

By Wilson G. L, Lord J. H

A detailed analysis of faulting indicatcs that blocks of "greenstone" have been thrust beneath the southern end of the Mt. Isa orebodies.This "greenstone" basement is considered to be a major structural control in the localization of these orebodies.INTRODUCTIONThis paper is based on exploration carried out by Mining Corporation (Aust.) N.L. from 1956 to 1960 in the area immediately south of Mt. Isa, Queensland. During this period over 20,000 ft of diamond drilling was completed together with costeaning and geochemical exploration.Early in 1959, it became apparent that diamond drill information could not be correlated with the current geological concepts of this area and a detailed geological appraisal became necessary. In all, sixty square miles were mapped at a scale of 1 in. to 500 ft, using enlarged aerial photographs. All drill core was logged and sections re-interpreted.Professor K. C. Dunham of the University of Durham consulted on this project and contributed through valuable discussion. Dr. A. Day of the University of Sydney carried out a gravity survey in February 1960 and Dr. H. Wilshire of the same University undertook microscopic examination of rocks from the area. Certain sections of the area were investigated geochemically by Mr. K. K. Hughes of New Consolidated Gold Fields (Asia) Pty. Limited in 1960.In outlining a theory of ore genesis in the area the writers have drawn heavily on the invaluable data published by many previous workers on the Mt. Isa field, in particular...

Jan 1, 1963

By C. D. Allman

Specifications for coal at the Grand Lake thermal electric station read in part: "Coal will be Rom Minto Bituminous (strip operation). Maximum lump 3x3x4 ft. Very corrosive, abrasive and when damp, sticky. Coal may consist of frozen lumps of coal, snow and ice." To maintain quality control it was necessary to develop an automatic sampling system capable of: 1) sampling from one 10-ton truckload every 1½ min; 2) permitting an operator to automatically take a sample from each truckload; 3) depositing the sample in a pre-selected container, one of a possible 10; and 4) performing the sampling operations in accordance with latest ASTM specifications for sampling coal with an ash content of 35%. This paper tells how these and other problems were resolved and describes the equipment used. The New Brunswick Electric Power Commission issued detailed specification No. 5351-5009 outlining the scope of work and general requirements for a mechanical coal handling system to be installed at the Commissions Grand Lake Generating Station. The thermal station is located at Newcastle Creek, some 40 miles east of Fredericton, N.B. Canada, on the shore of Grand Lake. This particular location is immediately adjacent to the Minto strip mining coal area of New Brunswick. Contained in the specifications, but not detailed specifically was an automatic coal sampling system. The system outlined, was to be designed and specified by the individual equipment tenderers. In conjunction with the Hardinge Co., the Barber-Greene Co. designed a sampling system which was contained in the general contract proposal. The system as designed originally, however, presented certain limitations to a continuous coal handling system and was ultimately changed. However, it was only through preliminary study and design that problems created by the specifications were determined, and these problems discussed and finally negotiated with the NBEPC engineering staff created the subsequent sampling system now being installed by Barber-Greene. It must be considered that where the original specifications did not detail the mechanical equipment, it was necessary to present a system which would correspond to the intent of specification and for which Barber-Greene would be responsible as to function, but remain in a competitive position with regard to the tender considered primarily on a price basis. The system now being installed, contains basically all the components which were detailed originally, with the exception of the holding bin arrangement, which was changed to allow a continuous operation of the entire coal handling system. SPECIFICATIONS The specifications covering the sampling system follow. 4.5 Sampler: An automatic sampling system shall be installed capable of sampling one-truck load of coal every 1½ min. When the coal is dumped into the receiving hopper, the operator shall push a button and the sampler shall automatically take a sample of that particular coal when it reaches the sampler. Then the sample taken shall be crushed and reduced in quantity to a workable sample and deposited in a pre-selected container, one of a possible ten. All samples and sampling operations shall be in accordance with the latest edition of ASTM designation 492 for sampling coal with an ash content of 35%. The coal for the initial sample shall have maximum sized lumps of about 3/4 in. and the final sample shall be adjustable from 2 to 5 lb per sample and capable of passing through a sieve with 1/8-in. diam openings. It should be noted that, because of the time delay between the time the sample is requested and when it is actually taken, the operator may call for one or two additional samples from different coal before the first sample is completely refined and in the final sample can. Coal is received from a number of different suppliers on the same day, therefore, the system shall be designed so that there is no possibility of mixing or contaminating the coal from the different suppliers. All coal rejected from the sample shall be returned to the main conveyor. All chutes, hoppers, etc. shall be designed in accordance with Section 4.6 of these specifications. 4.6 Chutes, Hoppers, etc. All chutes and hoppers

Jan 1, 1963

By M. J. deBastiani

The uranium producing division of Denison Mines Limited operates a 6,000-ton-per-day integrated mining unit in the Algoma area of Ontario. The property is located approximately one and one-half miles from Highway I 08, eight miles north of the town of Elliot Lake. The property was staked in 1953, diamond-drilled in ?late 1954 and 1955, and put into production in 1957. Since that date, the operation has produced $250,000,000 worth of uranium oxide from approximately 11,000,000 tons of ore milled, and paid $18,000,000 in dividends to its shareholders. The operation employs about I000 people, and monthly operating costs are approximately one million dollars. From these figures alone, it is obvious that it was necessary to develop and institute an adequate set ?of controls for effective management at all levels of supervision over a period of four years, a system of production and cost control was developed that enables us to effectively measure the pulse of the various phases of the operation at any given time.

Jan 1, 1963

Geochemical data on Australian granites and pegmatites9 and the.,mineral.components of these rocks, is presented and compared with that obtained in similar studies in.the U.S.òS.R and:.elsewhere.The petrochemical character of tin granites and the trace.-chemistry of their component minerals, particularly biotites, have some significance as ore guides in prospectingfor tin.The primary geochemical dispersion of tin can be readily tested both in the laboratory and field by colourimetric methods, after volatilization with ammonium iodide, using modifications of.the method described by Wood (1958).Secondary dispersions of tin in residual soils or.alluvia can likewise be readily tested by rapid colourimetric methods in the field, but simple hydraulic methods,.handling larger-. sample volumes, give reliable outlines of dispersion patterns.

Jan 1, 1963

By LeRoy A. Thorssen

The use of lightweight aggregate as a constituent of concrete is not a recent development. Pumice was used by the early Romans, in pozzolana cement concretes, in the construction of many of their works. However, the recent development of manufactured lightweight aggregates, such as the expanded shales, vermiculite and perlite, has created a possible use for a whole new group of Portland cement concretes. Concrete can now be produced with unit weights ranging from 30 to 150 pounds per cubic foot and with various insulating, fireproofing, acoustical and structural properties. The tonnage of such materials being used has increased considerably in each of the past ten years, and can be expected to increase for the next several years as availability of the aggregates becomes more widespread and the properties of such concretes become more thoroughly investigated and more generally known. LIGHTWEIGHT aggregates of many types have become avail-able to the construction industry in most localities on this continent

Jan 1, 1963

By H. L. Riley

This report describes the methods and equipment used by the Watauga Stone Co. to drill und blast limestone in a two-level quarry, and to crush, screen, blend, and load this stone. Power requirements per ton of stone produced are reported. The personnel requirements for individual phases of the operation are tabulated in man-hours per ton of stone produced.

Jan 1, 1963

By L. G. Marshall

This report presents a cross section of the sand and gravel operations in the Minneapolis-St. Paul area. The study covers individual operations, economic problems peculiar to the industry, glacial geology of the area and its effect upon the grades and types of products, and past, present, and future trends of the expanding population and its effect upon the industry.

Jan 1, 1963

By R. M. Gooding

This paper presents a short history of the production of mineral-energy fuels and energy from waterpower in the United States, with brief discussions of the utilization of each of the fuels and hydropower, and a look at fuels competition and interchangeability. Basic data, in figures and tables, are brought together in this publication for the production of coal in the United States from 1800 to 1960, for crude petroleum, natural gas liquids, and natural gas from 1859 to 1960, and for hydropower since 1900. Production for each segment of the fuels complex in the principal producing States from 1946 to 1960 is shown. Data are not included for consumption as such or for imports and exports.

Jan 1, 1963

By Nichols J. Grant, Bill C. Geissen

In low temperature phase diagrams, liquidus curves below about 1500°C are relatively easily established, e.g., by thermal analysis or separation of coexisting solid and liquid phases, followed by chemical analysis. Experimental difficulties increase considerably at higher temperatures and in systems involving more reactive metals. Although there are now thermocouples available for use from 1600" to 2400°c, as summarized by Caldwell,' the need for frequent calibration, aging, and contamination problems, and unavailability of suitable protection tubes has sharply limited their use at higher temperatures. Many of the high melt- ing metals are found to react with refractory oxides. TO avoid such problems, a frequently used procedure is the diffusion and saturation method, as described by Spedding et a1.' for the system La-C. This technique involves the annealing of one metal or a suitable alloy in a crucible of the other element at a temperature above the melting point, followed by chemical analysis of the center of the melt, after equilibrium is established. Further, if an alloy system is to be investigated employing the electron microbeam probe, and calibration charts have been established, it may be possible to measure the alloy concentration at the center of a cored as-cast structure, and to conclude from this points on the liquidus curve in a manner similar to the one to be described. It is known that in phases with a broad homogeneity range the rapidly cooled, cored, as-cast structure of an alloy presents concentrations having different lattice constants; this spread of lattice constant values contributes to the broadened lines of a powder pattern for the as-cast condition. The region of the crystal which is first to solidify will then correspond to the edge of the lines if the change of the lattice parameters with concentration is monotonous. In the course of the determination of the Ta-Tr phase diagram,3 it became evident that such behavior made it possible to construct the

Jan 1, 1963

By E. Douglas, D. N. Collins, J. R. Stevens

E. Douglas (Dept. of Scientific and lndustrial Re-search, Warren Spring Laboratory, Hertfordshire, England) — The authors are to be congratulated on the considerable improvements they have made in tailoring efficiency and selectivity terms which are generally superior to the alternative forms in current use. However, I feel that their efficiency expression is limited to lower-grade feeds; its accuracy reduces as the feed grade increases. For example, its application to such processes as the beneficiation of glass sands, refractories and clays will invoIve considerable inaccuracies. The reason for this lies in the direct use of recovery, which, with high-grade feeds, biases their empirical expression, R(1 - c/h). With a 90% grade feed, the recovery weighting for the slightest degree of beneficiation, over a zero efficiency sampling operation, will be 90+%+ I disagree with their second basic requirement which states that there can be no fundamental basis for any single quantifying expression. A formula giving a comprehensive representation of concentra- tion efficiency can be derived fundamentally accord-to the procedure outlined in the literature. '' This formula, called the Basic Efficiency formula, is

Jan 1, 1963

By G. P. Contractor

Medium and low carbon steels, modified with uranium, were studied in order to evaluate the influence of uranium on forge ability, mechanical 11roperties, response to heat treatment and microstructure. Uranium contents ranged up to 0.70 per cent. The medium carbon steels are hot short if the uranium content exceeds about 0.35 per cent. More uranium can be tolerated in low carbon steels. The hot shortness is caused by the formation of intergranular phase UFe2. Critical transformation temperatures, Jominy hardenability, and resistance to tempering are not significantly affected by the 11resence of uranium. Similarly, uranium has little or no effect on the tensile properties of carbon steels. The addition of uranium has a favourable effect 11n the stress-rupture characteristics and some beneficial effect on fatigue properties. However, more results are required for verification. In the steels investigated, it seems that most of the uranium carbide combines to form complex inclusions of U (0, C, N) or (C, N), rich in oxygen or nitrogen or both.

Jan 1, 1963

By S. E. Bronisz, Dana L. Douglass

a Uranium was deformed by cold rolling, and the effects of this plustic deformation on the microstruc-ture of the metal were observed by the technique of transmission elecbon microscopy. The recrystalli-zation of selected cold-wmked samples was also studied by this method. The samples were prepared for examination by electrolytic thinning in a standard metallographic electrolyte which has not been previously reported as being used in producing thin foils of uranium. The microstructural changes observed in the a uranium were generally similar to those seen by optical microscopy. The changes in the microstructure of a uranium following cold work and recrystallization treatments have been the subjects of several studies employing optical and X-ray techniques.12-19 These studies indicated that twinning was the redominant mode of deformation at room temperature20 and that the regions of high energy associated with the deformation twins were preferred sites for the initiation of recrystallization.15,18, Recently several workers have prepared thin foils of uranium suitable for examination by transmission electron microscopy.'-lo The foils thus prepared have been used to study fission fragment damage; a particular dislocation reaction,' and gas precipitation." At this laboratory the microstructural changes occurring during the cold working and recrystallizing of a uranium samples have been studied by using transmission electron-microscopy techniques. The foils used in this work were electrolytically thinned in a polishing bath not reported previously in the literature as being used for this purpose. EXPERIMENTAL PROCEDURE The uranium used in this investigation was depleted a uranium sheet 4 mils thick. The results of a spectrochemical analysis of this material are shown in Table I. The as-received uranium was cut into strips, 1 in. wide by 5 in. long, and annealed in vacuo at 600°C for 2-1/2 hr. The resulting microstructure consisted of relatively uniform, equiaxed grains having diameters of 10 to 50 p. Cold Working. The cold-worked samples were prepared by rolling several of the annealed uranium strips to various thicknesses. The strips were reduced 3.5 ± 0.5, 6.0 ± 0.6, 10.0 ± 0.5, 19.5 ± 1.0, and 28.5 ± 2.0 pct in thickness. It was not possible to achieve these reductions with a single pass through the rolling mill, so the strips were turned end for end during the rolling procedure. The cold-rolled strips were stored in dry ice until samples from them could be thinned and examined (within 24 hr after rolling). Annealing. The samples used in studying the re-crystallization behavior of a uranium were obtained by annealing sections of the strips which had been reduced 10.0 and 28.5 pct. These samples were sealed in evacuated Pyrex capsules and were annealed in a tube furnace at temperatures from 200" to 600°C and for times from 1/2 to 2 hr, see Table l. Thinning: The samples from the rolling and heat treatments were prepared for examination in the electron microscope by electropolishing in a bath composed of 25 g chromic acid, 133 ml glacial acetic acid, and 25 ml water. This electrolyte has been used and recommended for preparing specimens for optical metallography It was necessary to mask the edges of the sample with a stop-off paint in order to prevent preferential attack in these areas. The paint used was made by dissolving polystyrene in benzene. The electrolytic cell consisted of a cylindrical stainless-steel cathode placed in a beaker containing the electrolyte, with the sample as the anode positioned at the cell axis. The temperature of the electrolyte was held below 15°C by cooling with liquid

Jan 1, 1963

By Leon D. Keller

Hydraulic concentration of minerals has been practiced for a good many years. Until recently, however, the practice has been limited to a multiplicity of small pockets and relatively low tonnages and flows. The adaptation of the SiphonSizer to the concentration and classification of magnetite has changed this concept. Some fifty commercial units are currently in operation on magnetite, varying in size from 16 ft diameter circular unit to a 25 ft by 100 ft rectangular unit. Additional units up to 38 ft diameter are under construction. Depending upon the application in the flowsheet, upgrading-varies from 0.75% to 14% Fe in a single stage. To those not familiar with taconite processing, the importance of the struggle to economically remove as much silica as possible may not be fully appreciated. These figures pertaining only to transportation may be thought-provoking. If a 10,000,000 ton per year plant could reduce the silica content of their concentrate by 17, a savings in boat freight alone would amount to 100,000 tons at $2.00 per ton annually.

Jan 1, 1963

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

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

Jan 1, 1963