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By Strathmore R. B. Cooke, Iwao Iwasaki, C. S. Chang

PYRRHOTITE has long been considered a gangue mineral to be eliminated as tailing in the treatment of various sulphide ores. However, in recent years the world-wide lack of sulphur resources has called attention to this mineral as a potential source of both sulphur and iron. Its importance as an economic mineral, however, has not been particularly emphasized. For this reason very little is known about its response to flotation, except that it can be depressed easily in alkaline circuit, by long aeration,1,2 addition of oxidizing agents3 or by starch.4 The object of this work was to study the floatability of pyrrhotite. This includes the effect of oxidation by aeration, of copper activation, and of change in pH.

Jan 2, 1954

By Allen Garrison

A PREVIOUS paper1 reviewed some of the properties of clays and shales and presented some data on the nature of the gelling phenomenon. It included a brief discussion of origin of clays and shales, their com-position, structure, retention of water, ionization, base exchange, and the nature of the gelling of water suspensions, Other publications of the Institute2-8 have discussed the properties of clays and their relations to drilling-fluid behavior and control. It is the purpose of this article to present some new data obtained and arranged in a different manner and making possible a better understanding of the chemical reactions involved in the control of drilling-fluid characteristics during the normal drilling operations. EXPERIMENTAL PROCEDURE The difficulties involved in the measurements of the flow character-istics of plastic fluids are too familiar to recite, The possible applications of some of the well-known instruments to this problem have been ade-quately discussed by Hobson9 and he has given an excellent bibliography. Although there are many viscosimeters of varied design, none of them appear to fulfill the most obvious demands of accuracy in the measure-ment of clay or shale suspensions, Since the fluid characteristics are dependent on the rate of flow of the fluid, and the viscosity usually falls off very rapidly as the rate is increased, it is clear that the first require-ment is that the instrument shall be capable of a wide variety of speeds. The viscosity of the fluid at any fixed and constant rate of flow is also a function of time, so that the second demand is that the instrument shall be capable of a constant and continuous motion for a prolonged period of time.

Jan 1, 1939

Discussion of the paper of Robert R. Abbott, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2389 to 2400. ALBERT SAUVEUR, Cambridge, Mass.:-Mr. Abbott has certainly made a strenuous effort to ascertain the influence of the various elements on the absorption of carbon by steel-a subject of great importance to those dealing with the case hardening of that metal. Because of the extensive and careful character of Mr. Abbott's experiments, one is all the more disappointed that his results, as he himself recognizes, are not more satisfactory; for, indeed they leave us just about where we were,-still entertaining uncertain views in regard to the carbon-absorbing power of various alloy steels. It might be asked whether Mr. Abbott's method of estimating the amount of carbon absorbed-namely, by weighing the specimens before and after the carburizing treatment-was the best one to select. Are not serious sources of error. inherent to such procedure because of the difficulty of satisfactorily removing the earburizing material attached to the specimen ? The method of least squares has certainly failed to solve the problem satisfactorily. By manipulating Mr. Abbott's results in a different manner I have obtained the following expression: P = 100 - 50 C - 7 Ni + 20 Cr, in which P represents the carbon-absorbing power; C, the percentage of carbon; Ni, that of nickel; and Cr, that of chromium. It is assumed that the carbon-absorbing power of pure iron, or what might be called its carburizability, is represented by 100. Applying the formula, for instance, to a steel containing 0.15 per cent. C, 3 per cent. nickel, and 0.50 per cent. chromium, its carbon-absorbing power would be 100-50X0.15-7X3+20X0.50=81.50; that is, 81.50 per cent. of the carbon-absorbing power of pure iron.

Jan 12, 1913

By L. S. Panyity

The inception of this paper may be traced directly to the various discussions of another paper by the writer1 wherein certain indefinite beliefs and opinions were emphasized as to the relative importance of total sand porosity and the actual size of the openings between the grains. Since publication of that paper it has been possible to study various methods of sand analyses and results that have been obtained under different conditions and actual operations in the field. The purpose of this paper is to indicate the value of screen analysis, especially in areas where repressuring by means of water-flood, air or gas is being used in the partly depleted fields. Sand samples have been analyzed for porosity, saturation and grain size. They are mainly from the Bradford water-flood area, where a great reliance has been put upon such analyses, and where many data are available, A few sand studies are included from fields other than the water-flood area, in order to indicate the possibilities of screen analysis in any field. Examples of various conditions are given in Figs. 1 to 7, which show the porosity, saturation and grain-size analyses of submitted cores or drill cuttings. The generally accepted methods of delineating such sand studies on cross-section paper, known as "core charts" has been employed; with the exception that a method of representing grain size has been evolved which is believed to be the best adapted for this purpose. It differs from the block diagrams generally used, in the employment of a linear section. Percentage of grain-size is represented by the subdivision of a given distance, where the total length represents the whole sample of rock chunk, while the subdivisions indicate the percentages of grains of the different sizes that will pass through the various sieves, through which the samples of crushed sand are sorted to determine the size and amount of the components that make up the aggregate. Thus, on Fig. 1, under the heading of Grain Size, the first samples are composed of grains of the following sizes: 16 per cent. through 120-mesh sieve; 33 per cent. through 150-mesh; 25 per cent. through 180-mesh; 26 per cent, through 200 mesh; a total of 100 per cent. A minus sign is placed before

Jan 1, 1931

By J. W. Marx, R. H. Langenheim

The injection of heat-bearing fluids may offer a wider application to secondary and tertiary recovery from conventional oil reservoirs than inderground combustion since the process is more easily controlled and the reservoir requirements, in general, are less critical. In all cares, conduction heat losses to overburden and un-derburden will impose an economic limit upon the size of the area which can be swept out from any one injection point for any given set of conditions. The present report describes a method for c.rtin~ating thermal invasion rates, cumulative heated area, and theoretical economic limits for sustained hot-fluid injection at a constant rate into an idealized reservoir. Full allow-ance is made for non-productive reservoir heat losses. Required solutions can be obtained directly from the numerical tables given here, as soon as all operating conditions are specified, withou extensive mathematica1 ~nanipulation on the part of the user. The injection of a heat-bearing fluid into a reservoir is frequently proposed as a means of secondary or tertiary oil production. This form of thermal recovery may offer a wider application to conventional oil reservoirs than underground combustion since the process is more easily controlled and the reservoir requirements, in general, are less critical. Because of its large gross heat capacity, steam appears to be the most efficient heat injection medium, although mixtures of steam and other gases, hot water, hot oil and hot non-condensable gases also have been employed. Whatever the nature of the injection medium, economic evaluation of such thermal recovery processes will depend upon thermal invasion rates, or rates of productive reservoir heating, at any given time after the start of heat injection. In all cases, conduction heat losses to overburden and underburden will impose an economic limit upon the size of the area which can be swept out from any one injection point, for a given set of reservoir conditions, at any given heat injection rate. The present report describes a method for estimating thermal invasion rates, cumulative heated area and theoretical economic limits for sustained heat injection at a constant rate into an idealized reservoir, making full allowance for non-productive reservoir heat losses. Required solutions can be obtained directly from the nu- merical tables given here, as soon as all operating conditions are specified, without extensive mathematical manipulation. It should be noted that ordinary water flooding may be used to move an annular-heated zone outward, even though the economic areal limit for straight heat injection has been reached. Thus well spacing need not be confined to the areal limits as determined here. However, the present calculations do not cover such supplementary heat scavenging programs. The operating element consists of a radial flow system, concentric about the point of injection, with the idealized step function temperature profile illustrated by the dashed line in Fig. 1. The solid curve shown in Fig. 1 gives a qualitative picture of the true radial temperature distribution. It will be shown later that the expressions given below, which are derived from the simplifying step idealization (dashed line in Fig. I), also can be interpreted in terms of the more realistic temperature distribution shown in Fig. 2. For this case, the thermal invasion radius is simply redefined as the distance from injection well to the mid-point of the temperature distribution.

New York Meets first Wednesday after first Tuesday of each month. DAVID H. BROWNE, Chairman. PERCY E. BARBOUR, Vice-Chairman A. D. BEERS, Secretary, 55 Wall St., New York, N. Y. C. A. BOHN, Treasurer. JOHN V. N. DORR, LEWIS W. FRANCIS. Boston Meets first Monday of each winter month. W. E. C. EUSTIS, Chairman. R. L. AGASSIZ, Vice-Chairman. E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Boston, Mass. ALBERT SAUVEUR, H. L. SMYTH. Columbia Holds four sessions during year. Annual meeting in September or October. W. H. LINNEY, Chairman. OSCAR LACHMUND, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON, S. SHEDD.

Jan 3, 1917

New York Meets first Wednesday after first Tuesday of each month. J. E. JOHNSON, JR., Chairman EDGAR RICKARD, Vice-Chairman D. M LIDDELL, Secretary, 7 Wall St., New. York, N. Y C. A. BOHN, Treasurer JOHN V. N. DORR _ LEWIS W FRANCIS Boston Meets first Monday of each winter month. R. L. AGASSIZ, Chairman - JAMES G. CARLETON, Vice-Chairman E. E. BUGBEE Secretary-Treasurer, Mass. Inst. of Technology, Cambridge, Mass. W. E. C. EUSTIS G. A. PACKARD Columbia Holds four sessions during year. Annual meeting in September or October. S. S. FOWLER, Chairman J. C. HAAS, Vice-Chairman LYNDON K. ARMSTRONG, Secretary-Treasurer. P. O. Drawer 2154, Spokane, Wash. W. H. LINNEY

Jan 2, 1918

New York Meets first Wednesday after first Tuesday of each month. DAVID H. BROWNS, Chairman. PERCY E. BARBOUR, Vice-Chairman A. D. BEERS, Secretary, 55 Wall St., New York, N. Y. C. A. BOHN, Treasurer. JOHN V. N. DORR, LEWIS W. FRANCIS. Boston Meets first Monday of each winter month. W. E. C. EUSTIS, Chairman. R. L. AGASSIZ, Vice-Chairman: E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Boston, Mass. ALBERT SAUVEUR, H. L. SMYTH. Columbia Holds four sessions during year. Annual meeting in September or October. W. H. LINNEY, Chairman. OSCAR LACHMUND, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON, S. SHEDD.

Jan 2, 1917

New York Meets first Wednesday after first Tuesday of each month. DAVID H. BROWNE, Chairman: PERCY E. BARBOUR, Vice-Chairman. A. D. BEERS, Secretary, 55. Wall St., New York, N. Y. C. A. BOHN, Treasurer. JOHN V. N. DORR, LEWIS W. FRANCIS. Boston Meets first Monday of each winter month. W. E. C. EUSTIS, Chairman. R. L. AGASSIZ, Vice-Chairman. E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Boston, Mass. ALBERT SAUVEUR, H. L. SMYTH. Columbia Holds four sessions during year. Annual meeting in September or October. W. H. LINNEY, Chairman. OSCAR LACHMUND, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane; Wash. STANLY A. EASTON, S. SHEDD.

Jan 1, 1917

By L. C. Graton

Civilization did not begin until metals became the material of tools, implements and machines. - RICKARD, Man and Metals. HISTORY is no more an end in itself than is a backsight the sum total of a survey. This Institute may view with satisfaction the remarkable development of the mineral industry since its founding three score and fifteen years ago, its own enlarging service to that industry, and the contribution thus made toward the enhanced welfare, opportunity and mutual understanding now in greater or less degree reaching and benefiting all peoples of the globe. But neither this professional society nor the dynamic mining industry as a whole wishes on this anniversary to direct its gaze chiefly toward the past. The foremost purpose of historical review should be to throw into clear perspective the strong points and the defects in the forward march thus far, primarily as the basis for conceiving and designing a still sounder progress henceonward. At various times since the Institute's founding, the theories of ore deposition have been considered from the historical view point.l-7 For the present occasion it seems fitting to lay prime emphasis on the practice and utilization of geology in its varied relations to the problems of the mining industry. It is hoped that the reader will understand and accept the degree to which the whole is sampled by parts familiar to the present writer, and the disproportionate attention to thought and achievement within the United

Jan 1, 1947

US 4,195,426-Manganese nodules are recovered from relatively great depths on the ocean floor using a self- propelled remote-controlled vehicle having a V-shaped tubular structure with a system of crawlers at its apexes. Underneath each side of the V-shaped structure is a scraping system for gathering nodules and directing them into a tubular conveying system for elevation to the surface ship. A given area of sea bed is fully mined in a single pass of the vehicle. V. Banzoli, V. Di Tella, and P Vielmo, assigned to Tecnomare, SPA. Apr. 1, 1980. 5 pp. 137-60) Filed. 3-31-78 (892,197). Priority: Italy, 4-1-77 (84119A/77).

Jan 1, 1982

New York Meets first Wednesday after first Tuesday of each month. J. E. JOHNSON, JR., Chairman EDGAR RICKARD, Vice-Chairman D. M. LIDDELL, Secretary, 7 Wall St., New York, N. Y. JOHN V. N. DORR C. A. BOHN, Treasurer LEWIS W. FRANCIS Boston Meets first Monday of each winter month. R. L. AGASSIZ, Chairman JAMES G. CARLETON, Vice-Chairman E. E. BUGBEE Secretary-Treasurer, Mass. Inst. of Technology, Cambridge, Mass. W. E. C. EUSTIS G. A. PACKARD Columbia Holds four sessions during year. Annual meeting in September or October. W. H. LINNEY, Chairman OSCAR LACHMUND, Vice-Chairman LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON S. SHEDD

Jan 9, 1917

New York Meets first Wednesday after first Tuesday of each month. J. E. JOHNSON, Jr., Chairman EDGAR RICKARD; Vice-Chairman D. M LIDDELL, Secretary, 7 Wall St., New York, N. Y. C. A. BORN, Treasurer JOHN V. N. DORR - LEWIS W. FRANCIS Boston Meets first Monday of each winter month. R. L. AGASSIZ, Chairman JAMES G. CARLETON, Vice-Chairman E. E. BUGBEE Secretary-Treasurer, -Mass. Inst. of Technology. Cambridge, Mass. W. E. C. EUSTIS G. A. PACKARD Columbia Holds four sessions during year. Annual meeting in September or October. W. H. LINNEY, Chairman OSCAR LACHMUND. Vice-Chairman LYNDON K. ARMSTRONG, Secretary-Treasurer, P. 0. Drawer 2154, Spokane, Wash. STANLY A. EASTON S. SHEDD

Jan 1, 1918

New York Meets first Wednesday after first Tuesday of each month. J. E. JOHNSON, JR., Chairman EDGAR RICKARD, Vice-Chairman D. MI. LIDDELL, Secretary, 7 Wall St., New York, N. Y. C. A. BOHN, Treasurer JOHN V. N. DORR LEWIS W. FRANCIS Boston Meets first Monday of each winter month. R. L. AGASSIZ, Chairman JAMES G. CARLETON, Vice-Chairman E. E. BUGBEE Secretary-Treasurer, Mass. Inst. of Technology. Cambridge, Mass. W. E. C. EUSTIS G. A. PACKARD Columbia Holds four sessions during year. Annual meeting in September or October. W. H. LINNEY, Chairman OSCAR LACHMUND, Vice-Chairman LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON S. SHEDD

Jan 8, 1917

By Edgar S. Cook

Portions of this paper repeat in substance the statements made by me in an address before the meeting of the American Society for Testing Materials, held in June, 1903, at Delaware Water Gap, Pa. The views I then expressed, I still hold and believe to be pertinent to the present discussion of this subject. In doing my part, therefore, at the request of our Secretary, towards the further consideration by the Institute of the Physics of Cast-lron from a commercial as well as a theoretical standpoint,—a theme which received interesting treatment in our meeting some years ago, but has been somewhat neglected recently,—I make no apology for reiterating the views I have expressed elsewhere. Indications all point to the substitution of classifying pig-iron by chemical analysis for the old-time method of grading by fracture. Commencing with the larger users, and the makers of specialties, who require more positive information as to the composition than is afforded by the fracture; the use of pig-iron, guided by analysis, has spread with much greater rapidity to all classes of foundry-work than the most sanguine expected. Grading by fracture, as guided by experience with any particular brand of iron, has some points in its favor. The fact that, for so many years, castings of multitudinous forms, and for an endless variety of uses, were made in a fairly satisfactory

Jan 1, 1905

By E. J. Rapperport, E. D. Levine

The boundaries of the (a +ß) field in the Al-Li system were determined between 150°and 550°C utilizing quantitative metallography and lattice-parameter measurements. The solubility of lithium in aluminum decreases from 12.0at. pct Li at 550°C to 5.5 at. pct Li at 150°C. P Al-Li is saturated with aluminum at 45.8 at. pct Li and has this boundary value constant over the temperature range 150°to 550°C. THE solid solubility of lithium in aluminum has been determined by several investigators, 1-6 but, as shown in Fig. 1, there is little agreement among the various determinations. The earliest investiga-tions'-' are suspect because of the use of impure materials. Although high-purity materials were employed in more recent work,4'5 the experimental techniques may have led to contamination of the specimens. Probably the best work has been that of Costas and Marshall,6 who obtained close agreement between results obtained by two independent phase-boundary techniques: electrical resistivity and mi-crohardness. No detailed studies of the solubility of aluminum in the bcc ß phase, Al-Li, have been reported. Cursory investigations1,2,6 have indicated only that the (a+ß) -p boundary lies between 40 and 50 at. pct Li and is relatively independent of temperature. The present work was undertaken in order to provide an independent check on Costas and Marshall's determination of the solubility of lithium in aluminum, to extend knowledge of this solubility limit to temperatures below 225°C, and to make an accurate determination of the solubility of aluminum in Al-Li. EXPEFUMENTAL Alloy Preparation. In view of the difficulties encountered in previous investigations of the A1-Li system, close attention was paid to the use of methods of alloy preparation and treatment that would minimize contamination. Aluminum sheet (99.99 + pct Al) was vacuum-induction melted in a beryllia crucible to remove hydrogen. Lithium (99.9 pct Li) was charged with pre-melted aluminum into a beryllia crucible, in a helium-filled drybox. The crucible was sealed in a Vycor tube and transferred from the drybox to an induction furnace. Melting of alloys was performed by induction heating in a helium atmosphere. Solidification was accomplished by means of a suction apparatus, shown in Fig. 2, in which the alloy was forced by changes of pressure into a 3/16-in. inside diam closed-end beryllia tube. This technique produced rapid solidification of a small portion of the melt, resulting in alloys with a high degree of homogeneity. Typical lithium distributions are presented in Table I. Transverse sections 1/8 in. long were cut from the alloy rods, and each section was split in half longitudinally. One half of each section was analyzed for lithium, and the opposing halves were employed for phase-boundary determinations. Lithium contents were determined by flame photometry with an accuracy of 1 pct of the amount of lithium present. Thermal Treatments. Homogenization and equilibration heat treatments were performed in electrical-resistance furnaces with temperatures controlled to ± 2OC. Calibrated chromel-alumel thermocouples were employed to measure temperature. Homogenization was performed in helium-filled l?yrex tubes for 1 hr at 565°C. The encapsulated specimens were then transferred directly to furnaces maintained at lower temperatures for equilibration. Equilibration times were 2 hr at 550°C, 8 hr at 450°C, 27 hr at 350°c, 90 hr at 250°c, and 285 hr at 150"~. These times were chosen on the basis of conditions employed by previous investigators. Alloys were quenched from the equilibration temperatures by breaking the capsules into a silicone oil bath. By performing all possible operations either in sealed capsules or in a helium-filled drybox, the specimens were given minimum exposure to the atmosphere. Quantitative Metallography. Metallography of Al-Li alloys is difficult because of the atmospheric reactivity of the ß phase. It was found possible, however, to prepare surfaces of good metallographic quality by preventing contact with moisture during preparation. Grinding through 4/0 paper was performed in the drybox. The specimens were then transferred under kerosene to the polishing wheel. Three polishing stages were employed: 25-p alundum with kerosene lubricant on billiard cloth, 1-µ diamond paste on Microcloth, and 1/4-p diamond paste on Microcloth. Between stages the samples were cleaned by rinsing in trichloroethylene and buffing

Jan 1, 1963

By Kent E. McElhattan

Selecting efficient machinery for an underground mining operation is a highly skilled art that still depends largely on human judgment and experience. In a coal mine, for example, there is no better way to predict the results of operating with a cutting machine or a continuous miner than to go underground with a sharp-pointed miner's pick. The trained eye can detect the depth of point penetration, cleavage planes, roof and floor strata, and many other conditions impossible to determine in a laboratory. Even so, however, an entirely new set of conditions may lie unexposed just a few feet behind the solid face. The candid truth of the matter is that practically nothing is known of the phenomenon of extracting a mineral from a solid. Consequently, the selection of mineral extraction machinery and systems must be based on results obtained elsewhere under apparently similar conditions. A recent study of the problem of equipment and system analysis was conducted in the coal mining regions of West Virginia. This state was chosen for study because it afforded representative sampling. The 172 coal mines investigated ecompassed seam heights ranging from less than 30 in. to over 84 in. and covered virtually all known coal mining conditions except two. The exceptions are the extreme pitch of coal seams in the western United States and British Columbia and the "bumps" encountered in the Rocky Mountains. Both of these extreme conditions are worthy of individual study.

Jan 7, 1969

IlAbad, Leopoldo F , Min Engr , Div of Mines, Bureau of Science, Manda, P I '23 ||Abadilla, Quince, A , Cia Minera de Petrolco El Aguila, S A Box 86, Puerto Mexico, Ver , Mexico '20 ||Abarquez, Ramon F , Met , Bureau of Science Manila, P I '24 ||Abbey, Robert Graham, Student, Case School of Applied Science Cleveland, Ohio '21 Abbott, A N , Mines Supt, Mazapil Copper Co , Ltd Concepcion del Oro, Zac , Mexico '23 Abbott, Clarence E , Gen'l Supt , Iron Mines Div , Tenn Coal, Iron & R R Co , 1405 Minnesota Ave , Bessemer, Ala '04 Abbott, Louis Benjamin, Chief Engr , Consolidation Coal Co , Elkhorn Div Jenkins, Ky '15 Abbott, Robert R , Met Engr , Peerless Motor Car Co Cle veland, Ohio '12 ||Abbott, Wells Osborn, Ray Consolidated Copper Co Hayden, Ariz '23 Abeel, George H , Jr, Cons Min Engr 4612 W 17th St, Los Angeles, Cal '18 Abel, Albert E, Asst to Pres, Valley Mould & Iron Corpn Sharpsville, Pa '19 Abernathy, George Elmer, Prof Geol & Min , Kansas State Teachers College Pittsburg, Kans '20 Abey, Hiroshi, Min & Met Engr, Takata & Co , 2 Yeirakucho, Nichome, ICojimachi-ku, - Tokyo, Japan '17 ||Aborn, Robert H 24 Groveland St , Auburndale, Mass '19 Abouchar, Sylvain Sley, Min Engr & Geol , Care of S H Sekaly, 13 Rue El Nimr, Cairo, Egypt '17 ?Abraham, Arthur W 1626 N Alexandria Ave, Los Angeles, Cal '21 Abrahams, Alexander I, Gen'l Mgr, Ricon Electrical Co Slough, London, England '13 ||Abrahamson, C Walter, Min Engr, Brule Min Co Stambaugh, Mich '21 Abrams, Charles Jackson, Mill Supt, Utah Apex Min Co Bingham Canyon, Utah '21 Abrams, David H, Cons Min Engr 182 Worth St, Johnstown, Pa '20 ?Acker, E O'C , Met 128 East Washington Lane, Germantown, Philadelphia, Pa '86

Jan 1, 1923

By J. M. Floyd

The theory, construction and applications of oxygen sensors employing high-temperature electro- chemical cells with solid electrolytes are briefly reviewed. The application of disposable probes to measurement of the oxygen potential in matte and slag baths in tin, copper, and nickel smelting operations is described. Examples discussed include end-point determination in smelting and slag-cleaning operations, pilot-scale investigations of process chemistry to assist in the development of smelting strategies, and measurements in operating smelters to improve the efficiency of operation.

Jan 1, 1984

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;' 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