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By E. J. Bonet, P. B. Crawford

It is fairly common practice to reinject water into the aquifer near the oil-water interface in water-drive reservoirs. There have been many studies of aquifer behavior without reinjection,l-5 but apparently no analytical studies have been made to indicate performance when injection wells are present in the aquifer. The diffusivity equation may be used to describe the pressure behavior in an aquifer. When sources are present it can be written as A general solution of Eq. 1 may be obtained as the sum of two solutions. One is a general solution of the homogeneous equation, obtained by dropping the source term in Eq. 1 and still satisfying the required boundary conditions. Another is a general solution of Eq. 1 satisfying homogeneous boundary conditions.1° The first solution, which corresponds to the aquifer without reinjection, has been given quantitative and qualitative treatment in the literature.l-5,8,9 The latter solution will be treated here. Solutions with variable injection rates are obtained by superimposing solutions with constant rates, so we have considered only the latter. Five cases have been treated here: 1. A linear aquifer of finite width and extent. Water is injected into the aquifer at point xo, yo at constant rate. The pressure along the line x = 0 is maintained at zero pressure. (See Fig. 1.) Equations showing the pressure distribution, rates, velocity and cumulative influx have been developed. Certain numerical results are shown. 2. A linear aquifer of finite width and extent. Water is injected into the aquifer at point xo, yo at constant rate. The rate of production along the oil-water water contact is maintained constant. Equations showing the pressure distribution inside the aquifer are presented. 3. A linear aquifer of finite width and extent. Constant pressures are maintained at opposite ends of the aquifer. Water is injected at constant rates at point xo, yo. Equations showing the pressure distribution are shown. 4. A linear aquifer of finite width and infinite extent. The pressure is maintained constant at the oil-water contact. Water is injected at a constant rate at point xo, YO. 5. A linear aquifer of finite width and finite extent. The pressure at the oil-water contact is maintained constant. Water is injected at constant rate per unit length along a line x,. The Linear Aquifer The linear closed aquifer, performing at constant terminal pressure was selected as the first case to be analyzed. The development of the equations is based on uniform injection per unit of thickness, and gravity effects are neglected. In practical application this condition is probably most closely achieved when the

Jan 1, 1970

By A. T. Yu

The energy crisis and the resurgence of mining activities highlighted 1972-73. Added to the impetus for more effective materials handling systems has been the continued upward trend of inflation and labor costs. The need for addressing the fundamentals has led to the trend toward an overall systems approach to materials handling problems.1 The decision to move forward with large mining ventures such as the $150 million Hibbing taconite comple2 and the immense Carajas iron project must base themselves on indepth studies of a host of factors viewed in the context of an integral mine-transport-market system. What's important is that each ton of pellet or ore must be an economical commodity at the end users' furnace. The project can still be viaable even if certain components in the entire network appear to be individually costly.

Jan 2, 1974

Jan 1, 1886

Bailey, Lewis Newton, Master Engineer, Senior Grade, 4th Regiment, U. S. Engineers, Headquarters Company, died of pneumonia at Camp Merritt, N. J., on April 30, 1918. Baird, Louis, Lieut., Royal Field Artillery, British Army, died on the battlefield in 1915. Cobeldick, William Morley, Royal Engineers, died from gas poisoning on October 7, 1915. Dougall, Ralph, killed in action. Evans, Alfred Winter, Lieut.-Col., New Zealand Rifle Brigade, D. S. 0., D. C. M., killed in action on October 12, 1917. Gorman, Thomas C., Lieut., Canadian Engineers, killed in France, Mar. 18, 1918. Hague, William, 1st Lieut., Engineer Officers' Reserve Corps, died in active service. Hall, William T., Capt., Royal Flying Corps, killed in action. Heine, Bernhardt E., Lieut., Aviation Service, killed at Fort Sill, Okla., Aug. 10, 1918. Irving, John Duer, Capt., 11th Engineers, A. E. F., died while on active service in France on July 26, 1918.

Jan 9, 1918

By A. E. Chute

The shortage of sulfur is not only continuing but appears to be worsening, attended by steadily rising prices. At the same time emphasis on air-pollution abatement is also increasing. These two factors, a rising market and the growth of environmental attention, have encouraged producers to carefully review all possible sulfur sources. As a result, production of sulfur from hydrogen sulfide occurring in petroleum is receiving greater attention than ever before. Until about a decade ago, the practice of recovering sulfur from hydrogen sulfide separated from gases (either found naturally or generated in desulfurization of liquid petroleum) was wide1y recognized but contributed little to total free-world sulfur production. However, during the past ten years, the production of sulfur from this source has increased so rapidly that it now accounts for a substantial portion of total production. This trend shows no signs of slackening, and current forecasts predict that recovered sulfur may become the dominant source of supply within ten years, exceeding mined sulfur production. This paper is intended to list sulfur sources and relationships, and to discuss the potential of producing sulfur from petroleum. The processing involved, in addition to product storage and transportation will also be discussed along with important economic aspects of sulfur recovered from hydrogen sulfide. For many years, most of the world's elemental sulfur has been produced from salt domes, predominantly by the Frasch process. During the past decade, however, another production source has developed so quickly that it is expected to surpass the Frasch production sources within a short time. This new source lies in the petroleum gases and liquids from which dramatically increasing quantities of elemental sulfur are being recovered. In the phraseology of the trade, the sulfur so obtained is know as "recovered sulfur," a term which does not, as one might expect, include sulfur recovered from other sources such as smelter gases. The growth rate of recovered sulfur compared to that of Frasch sulfur, total elemental sulfur, and total Free World sulfur in all forms is shown in Fig. 1 Since 1963, sulfur consumption has exceeded production,with the natural result that the price of sulfurhas continually increased. The posted price reported for f.o.b. Port Sulphur, La., has risen from as low as $18 per ton in 1962 to $32.50 per ton in mid-1967. With freight and other charges, delivered prices have of course run much higher, amounting to $45 or $46 per ton on the east and west coasts. In some cases, spot sales for as much as $60 have been reported. Although it is playing an ever-increasing role in the sulfur market, recovered sulfur was originally a by-product of the removal of hydrogen sulfide from natural and petroleum refinery gases. Today, however, it is often the most valuable product of a multi-product processing facility. Since there are two major sources of recovered sulfur—production and refining processes —natural gas is included with liquid petroleum for purposes of this discussion. Sulfur from these sources is produced in the form of gaseous hydrogen sulfide which is removed from a gas stream and converted to elemental sulfur. Gases in which hydrogen sulfide occurs naturally are natural gas and the gas produced from a high=pres-sure crude=oil or condensate field.

Jan 1, 1969

By T. E. Watkins, M. D. Nelson

A method of determining the lime content of drilling muds proposed by Battle and Chaney* has been examined both in the Field Research Laboratories of Magnolia Petroleum Co. and in field drilling operations. This proposed analytical method is condensed as follows: Titrate one ml of mud and one ml of mud filtrate, each with 0.02 N H2SO4, to the end point with phenolphthalein. The volume of acid in ml required for the mud titration is recorded as Pm and that of the mud filtrate titration as Pf Calculation of the lb lime/bbl mud is accomplished by use of the formula, lb lime/bbl mud = 0.6 (Pm - 1.3Pf) - 0.6 The analytical procedure outlined by Battle and Chaney was found to be quite satisfactory when reasonable precautions are used in mud sampling technique. Calculation of lime concentration by the method proposed in the above publication, however, has given values that varied as much as 100 per cent from the known lime content, for muds of either high or low solids concentration. By use of a formula, lb lime/bbl mud = 0.26 (Pm-F1.Pf), based on chemical equivalents of acid required for titration, both laboratory and field data have been satisfactorily correlated with the known amounts of lime present in the muds. In this formula a correction, F1, or volume fraction of liquid in the mud, is made for the solid content of the mud. Pm and Pf * Paper on "Lime Base Muds," presented by J. L. Battle (Humble Oil and Refining Co., Houston, Tex., and P. E. Chaney (Sun Oil Co., Beaumont Tex.), at the 1949 Spring Meeting of the Southwestern District API Division of Production, Dallas, Tex. The analytical procedure has also had wide distribution in a trade journal, Kembreak, published by the Accuracy Rig and Tool Co., Houston, Tex, †Derivation of equation lb/bbl — grams/350 ml 1 ml 0,02 N acid = 0.000741 grams of lime 1 ml 0.02 N acid/ml lime suspension = 0.26 lb of lime bbl lb of lime/bbl = 0.26 (Pm -F1, Pf ) have the same significance as in the Battle and Chaney equation. Table I shows typical data employing both formulas in calculating the lime content of various lime muds. This suggested procedure ignores lime which is in solution in the mud. The solubility of lime in water, normally about 0.5 lb per bbl, is greatly decreased by the addition of caustic soda, and, in a lime mud, it is probable that the concentration of dissolved lime is of the order of 0.1 lb per bbl. Such an amount of lime can be ignored, since it is within the range of accuracy of the method.

Jan 1, 1950

By Herbert Hoover

I HAVE been greatly honored as your unanimous choice for President of this. Institute, with which I have been associated during my entire professional life. It is customary for your new President, on these occasions, to make some observation on matters of general interest from the engineer's standpoint. The profession of engineering in the United States comprises not alone scientific advisers on industry but, in great majority, is comprised of the men in administrative positions. In such positions, they stand midway between capital and labor. The character of your training and experience leads you to exact and quantitative thought. This basis of training in a great group of Americans furnished a wonderful' recruiting ground for service in these last years of tribulation. Many thousands of engineers were called into the army, the navy, and civilian service for the Government. Thousands of high offices were discharged by them with credit to the profession and the nation. We have in. this country, probably, one hundred thousand professional engineers. The events of the past few years have greatly stirred their interest in national problems.' This has taken practical. form in the maintenance of joint committees for discussion of these problems and support to a free advisory bureau in ,Washington. The engineers want nothing for themselves from Congress.. They want efficiency in government, and you contribute to the maintenance of this bureau out of sheer idealism. This organization for consideration of national problems has had many subjects before it, and I propose to touch on some of them this evening.

Jan 1, 1920

Jan 1, 1969

Jan 1, 1969

Organization Place Date 1919 American Society of Civil Engineers..: Twin Cities, Minn. June 17-20 American Society of Mechanical Engineers Detroit, Mich. June 17-20 American Institute of Chemical Engineers Boston, Mass. June 18-21 American Drop. Forge Association Pittsburgh, Pa June 19-21 American Institute of Electrical Engineers Lake Placid, N. Y. June 24-27 American Society for Testing Materials Atlantic City, N. J. June 24-27 Society for Prom. of Engng. Education Baltimore, Md. June 25-28 American Chemical Society Philadelpia, Pa. Sept. 2-6 National Assn. of Stationary Engineers Huntington, W. Va. Sept. 8 American Peat Society.. Minneapolis, Minn. Sept. 22-24 American Iron; Steel Electrical Engineers St. Louis, Mo. Sept. 22-26 American Institute of Min. and Met. Engineers, Chicago, Ill. Sept. 22-27

Jan 6, 1919

By F. Lynwood Garrison

Except in the old Catalan forge, or its modifications, attempts to make iron and steel directly from ore in a practical and economical manner have failed so frequently and completely that such schemes are looked upon with justifiable distrust. Without exception, all have failed from one cause or another, although in some instances every indication of a practical success was manifest in the beginning. It is, therefore, necessary to carefully examine and consider every detail affecting the process, or more properly, furnace, under consideration. This I have done to the best of my ability during a long visit to Russia last summer, and after satisfactorily observing the practical success of the furnace in the iron works of Count Stroganoff at Dobriansky in the Government of Perm, I decided to investigate as completely as possible the history of similar furnaces in Finland and Russia. These data, sifted and verified with the greatest possible care, form the substance of the present paper.* An illustration on page 321 of Percy's Iron and Steel shows the old type of Osmundssmide or harkugnar, which has been in use in Northern Europe since pagan times. Fig. 1 shows a furnace of this kind. It should, perhaps, more properly be called a high-bloomary furnace or forge, the Swedish word hark meaning bloom or loupe. It was with this type of furnace that Mr. Husgafvel began his experiments at Porsaskoski in 1875. Attempts to obtain better results with larger furnaces of this type were failures, as every bloom or loupe obtained necessitated blowing out the furnace with a consequent large waste of fuel. A larger furnace of course increased this waste with no corresponding advantage. A movable hearth of threeeighth inch iron, lined with a mixture of clay, quartz and lime, was next tried, but in consequence of the frequent repairs of this lining,

Jan 1, 1888

By E. Martinez

The effect of ultrasonic energy transmitted through a liquid on chrysotile asbestos was investigated. Ultrasonic energy was effective in fiberization of chrysotile crudes as well as standard grades of milled asbestos fibers. Treated samples of several grades of milled fibers had increased wet bulk volumes and decreased settling and filtration rates compared to untreated fibers. Ultrasonics may be a method for fiberization of chrysotile without decreasing length or use of chemical additives that alter surface properties. Cavitation of the liquid on the surface of fiber bundles is believed to be the cause of the fiberization. It was found that ultrasonic energy greatly increased the rate of precipitation of latex on asbestos. When chrysotile asbestos fibers require additional opening or fiberization, the usual method employed is some type of high speed impact or grinding to open the fibers and produce a larger surface area. These methods always cause some degradation in length due to breaking of fibers. In addition, the efficiency of mechanical methods decreases as the diameter of fiber bundles decreases. Chemical methods have been proposed and it is claimed that fiberization down to individual fibers of 200-300 A diam is possible with some wetting agents. However, large amounts of reagent are required, approximately EDWARD MARTINEZ is with Central Research Laboratories, American Smelting and Refining Co., South Plain-field, N.J. TP 63H226. Manuscript, Aug. 12, 1963. Discussion of this paper, submitted in duplicate prior to Mar. 15, 1964, will appear in SME Transactions, September 1964, and AIME Transactions, 1964, vol. 229. 50 pct of the weight of fiber treated, and some of the wetting agent remains on the surface of the chrysotile and cannot be removed by any solvent which does not destroy the asbestos.' This investigation was directed at determining whether ultrasonic energy transmitted through a liquid would be effective in fiberizing chrysotile asbestos. Samples of asbestos crudes and commercially milled fibers were treated; settling and filtration rates of treated and untreated milled fibers were obtained. EQUIPMENT A Westinghouse Corp. ultrasonic cleaning system WEHH was used in this investigation. See Table I for a breakdown of this ultrasonic unit. RESULTS AND DISCUSSION Fiberization of Chrysotile Crudes: Samples of chrysotile crudes were pulled apart with tweezers so that coarse bundles of fiber approximately 1/16 in. in diam were obtained. The bundles were put into a bottle with 200 ml of methanol and the mixture placed into the ultrasonic tank for 30 min at a power output of 1200 w. The test was repeated using water instead of methanol. During the irradiation it was noted that the surfaces of the bundles were being fiberized. The liquid eventually became cloudy with dispersed solids. Fig. 1 is an electron micrograph of the fibers, some reduced to unit dimensions, and a fine material released by the ultrasonic energy. The platy particles in Fig. 1 were identified by electron diffraction and differential thermal analysis as brucite, Mg(OH)2, which must have been intergrown in the chrysotile crudes. Electron micrographs of bulk specimens of chrysotile have shown a fine material filling the interstices between tubular fibers.2,3 Electron diffraction patterns of the fine material collected after ultrasonic treatment indicate that it is amorphous. After decanting the solution, bundles of chrysotile remained somewhat decreased in diameter. Continuing the ultrasonic irradiation of the remaining material resulted in additional fiberization. The opening of the fibers occurred in both methanol and water. Cavitation of the liquid by the ultrasonic energy is undoubtedly responsible for the fiberization. When sound waves are transmitted through a liquid at a

Jan 1, 1963

By Thomas T. Read

AT this time of the year, engineering schools are releasing a group of young men who probably are, on the average, in much the same attitude of mind as a person arriving at the terminal station of a railway journey; namely, of having a general idea of his objective, but having to make a decision as to just where he is going and how best to get there. The man leaving the train can at first follow the crowd, but it soon breaks up, as one goes one way and one another, until he has to choose his own course. The recent graduate may do the equivalent of following the crowd by accepting the first position offered, but this only postpones a decision as to where he is going and how best to get there. So many young engineers ask for advice as to what to do that the following statement has been prepared as an attempt to make a general answer to such queries. The engineer taking his first job should realize two fundamental relations. The first is that in electing to be an engineer he has elected to be a hired man. A consulting engineer has more freedom than a man on a regular pay roll, but he is also a hired man; hired for briefer periods at a relatively high rate, but under the necessity of simultaneously doing his consulting work and developing new retainers. There is nothing derogatory in being a hired man (all doctors, lawyers and clergymen are hired men), but the tardy realization that he is one seems to give many an engineer a mental jolt that can be avoided if he accepts it from the beginning.

Jan 1, 1926

By Scott Tzcrner

WITHIN recent years people have begun to realize the importance and significance of the mining and allied industries. The leading part the engineer plays in civilization is becoming recognized. However accurate quantitative knowledge of the industrial importance of mining is still seldom possessed except by those close to this business. It is true that there are a few who go to the extreme and represent the whole progress of civilization as a reflection of man's gradual mastery of mineral utilization, but on the whole, the magnitude of the-industry is underestimated. In this paper I shall call attention briefly to the importance of mining in the United States, in Canada, and in the world. Ordinarily, the annual primary mineral production of the United States is about $5,500,000,000. The average for the last 5 years has been a little over that, but last year, sadly enough, it was less than 31/4 billion. Just now, we are on the decline, and have been for the last two years. In Canada, the 5-year average was about $268,000,000, and last year it was 227 million. Due in part to gold mines (in 1930, for the first time, Canada's gold production exceeded that of the United States), the Canadian average is holding up better than ours. Average world mineral production over the last -5 years has been estimated at about $12,000,000;000 whereas in 1931 it was less than than 8 billion.

Jan 1, 1932

By William B. Plank

A NEW record-a quarter million students in the engineering schools of the United States and Canada-has resulted from the great demand for engineers following World War II. The figures released by the American Society for Engineering Education and which appeared in detail in the Journal of Engineering Education for January 1948, show that, on Nov. 1, 1947, 252,250 students were studying engineering in 149 engineering schools of both countries. There are 244,390 in the 143 schools canvassed in the United States, and 7860 in six schools in Canada. These figures include both undergraduate and graduate students and are therefore comparable with the figures in previous presentations on this subject. This unprecedented engineering student body

Jan 1, 1948

By B. Wilshire, P. W. Davis

It has been shown that grain-boundary migration during high-temperature creep can reduce or even prevent the formation of intercrystalline voids, giving a considerable increase in ductility.' A similar observation has been made in a recent investigation of the creep properties of various grades of nickel and nickel alloys. The results can be illustrated by the observations made on: a) Pure vacuum-cast nickel (99.993 pct Ni) b) Impure vacuum-cast nickel (99.97 pct Ni) c) Pure nickel containing internal voids (produced by a process of intering). d) A substitutional solid solution alloy of pure nickel containing 1.16 pct Sn. All the materials were given a high-temperature anneal (>850°C) to produce a stable grain size of 7 to 10 grains per linear mm. The apparatus and techniques used to obtain the present results have been described elsewhere.' In this series, grain growth was observed only in the highest-purity, vacuum-cast metal. Thus we may consider that in the other materials grain-boundary migration was prevented by either preexisting voids or solute atoms. The effect of migration on the creep ductility of the above materials can be seen from Fig. 1, which

Jan 1, 1962

By J. Greenspan

The anisotropy of fracture and slip, that is, the brittleness and ductility of the beryllium single crystal, is characteristic also of po1ycrystalline beryllium in which the grains are oriented in a preferred manner. Beryllium with grain orientations resulting from hot working either unidirectionally or bidirectionally is ductile or brittle in directions given by the anisotropy and orientation of the grains. Textures developed from various hot-working sequences are given, and tensile results are correlated with textures. Not only texture, but fine grain size is necessary for obtaining high tensile elongation. Ultimate tensile strength and elongation are both correlated with grain diameter. Of particular interest is the case in which unusually high tensile elongations of 30 to 40 pct are obtained when basal planes are oriented to carry THE beryllium crystal (of nominal purity) is probably unique among metals with respect to its unusually acute anisotropy of slip and fracture. While extensive slip can occur on the system (1010) [ll20] starting at about 19,000 psi, the (0001) plane is particularly vulnerable to fracture at 4500 psi or less. Fracture occurs also on the (11zo) plane at about 26,000 psi.1"3 Further, there seems to be no other slip System which contributes significantly to

Jan 1, 1960

By J. D. A. Morrow

TO my mind the National Bituminous Coal Act so far has proved one of the unhappiest experiences that has ever befallen the bituminous coal operators of the United States. Viewed in the light of its ugly consequences everyone should recognize this measure for what it is -a weird thing as unreal as a page from "Alice in Wonderland." Indeed it might be another stanza to the tale of the Walrus and the Carpenter, with the coal operators in the role of the unfortunate oysters who were taken on that memorable ramble. It is time that coal producers open their eyes, jerk themselves out of any lingering hypnotic optimism about the price-fixing provisions of this law, demand the repeal of these corroding clauses, and then set about remedying as best they can the disastrous effects of this retromingent scheme to regulate the coal business.

Jan 1, 1939

By O. M. McRae

The Courtland-Gleeson area is in Cochise County about 15 miles east of Tombstone in southeastern Arizona. Rocks exposed in the area range in age from Pre-cambrian to Quaternary. The Precambrian is repre-sented by the Pinal schist. Paleozoic rocks include the Cambrian Bolsa quartzite and Abrigo limestone, Mississippian Escabrosa limestone, and the Permo-Carboniferous Naco Group limestones. Rocks believed to be of Triassic and/or Jurassic age include the Copper Belle monzonite porphyry, Turquoise granite, and Gleeson quartz monzonite. The Cretaceous is represented by andesitic volcanics and various sedimentary rocks. Tertiary rocks include the intrusive and extrusive Sugarloaf quartz latite porphyry and numerous dikes of various rock types. Quaternary conglomerates cover the northern and eastern part of the area. The geologic structure is extremely complex. All rocks as old as early Tertiary have been involved in either tilting, normal faulting, high angle reverse faulting, imbricate thrusting or folding and overfold-ing. Major deformation was initiated during the first half of the Tertiary. Northeast-southwest compres-sional forces caused thrust plates containing lower Paleozoic rocks to override Cretaceous rocks. Subsequently, two large slide blocks of lower Paleozoic rocks, acting under the influence of gravity, moved eastward. The imbricate structure and the gravity slide blocks were then broken by late Tertiary normal faults. INTRODUCTION The Courtland-Gleeson area, or Turquoise Mining District, has long been recognized as an area of extreme structural complexity. Gilluly 2 referred to the entire district as a "gigantic thrust breccia". In 1962, Bear Creek Mining Company completed a two year program of detailed geologic mapping supported by exploration drilling. The purpose of this paper is to present some of the results of this investigation and to provide a structural interpretation based on these results. The geologic map that accompanies this report is generalized and shows only the major and significant features. The area was initially mapped on aerial photographs on a scale of 1 in. equals approximately 500 ft. These data were transferred to a planimetric base using a vertical sketch master. LOCATION The Courtland-Gleeson area is in central Cochise County, about fifteen miles east of Tombstone, and about twenty-two miles northeast of Bisbee in southeastern Arizona (Fig. 1). The area is readily accessible over graded gravel roads from both Tombstone and Elfrida. GENERAL GEOLOGY Rocks exposed in the area range in age from Pre-cambrian to Quaternary. wilson3 and Gilluly2 have published very detailed descriptions of the principal rock units exposed in the area. Only a summary description is provided in Table I. A great number of previously unmapped narrow Tertiary dikes and small irregular masses of hornblende andesite porphyry, lamprophyre, and aplite intrude the Gleeson quartz monzonite in the western part of the map area. The scale of the map prohibits showing them. The aplite dikes are related to, and bear the same structural relationships as, the Sugarloaf quartz latite dikes found in this area. For that reason, and because both the hornblende andesite porphyry and the lamprophyre are post-mineral and post-thrusting, their omission from the map is not considered significant. Because so many of the contacts in the district are fault contacts, because bedding faults appear to be prevalent but are difficult to recognize and map, and because igneous intrusions are so common throughout the sedimentary section, it is virtually impossible to measure an exact total thickness of any of the sedimentary rock units. Nevertheless, neither the field mapping program nor the diamond drilling provided any basis for suspecting that the thicknesses of the sedimentary units are significantly greater or less than what might be inferred from surrounding districts.

Jan 1, 1967

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957