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By A. Kenneth Schellinger

DURING the comminution of a brittle material in the presence of dry air, no known phase change or chemical reaction takes place. The energy changes associated with the comminution are those of the transformation of kinetic energy into heat energy and the energy absorption represented by the actual rupture of molecular and/or ionic bonds. The random nature of the actual grinding process in a tumbling-mill often precludes the effective application of a rupture force on each individual particle of brittle mineral present. The result must be a great deal of useless vibration on an atomic scale in both the brittle mineral and the grinding medium below the elastic limit, which vibration is eventually manifested as heat energy in the mill. The actual rupture of molecular, or ionic, bonds creates new surface on the brittle minerals; each square centimeter of this new surface then must possess a number of potential bonds, each of which could reform theoretically with the release of energy. The sum total of this potential energy of bonding per unit of new surface, minus bond satiation effects of the enclosing gas or liquid, must be the surface energy of the mineral. If the comminution of the brittle mineral were carried out within the chamber of a calorimeter, the energy released as heat could be determined rather accurately. Moreover, the total kinetic energy input to the comminuting mass (mineral and medium) conceivably could be derived by a suitable torquemeter and revolution counter if the whole calorimeter were revolved. The difference between these two energy figures should then represent the net energy (gross energy input-heat energy output) used in creating

Jan 6, 1951

By B. B. A. Luzzat

ALUMINUM is today the most widely used of the nonferrous metals. The technical literature on the aluminum smelting process is, nevertheless, very meager, so that anyone interested in the subject cannot rely on more than a couple of dozen publications.' The patent literature is equally scarce; most patents refer to the production of alumina from aluminum-bearing ores, while not more than a few score significant patents deal with the electrolytic reduction of alumina, which is the real core of the aluminum smelting industry. The "reduction phase" is, from a technical and a scientific point of view, much more interesting than the "alumina phase", which, in effect, is only a combination of such well-known chemical operations as dissolving, precipitating, filtering, drying, and calcining. The electrolytic reduction of alumina, on the other hand, has features which do not appear in any other metal smelting operation. Some of them are of great technical and scientific interest even for those not directly engaged in the production of aluminum. The purpose of this paper is to describe in some detail the basic facts and developments of the reduction phase of aluminum smelting. Two Aspects of the Electrolytic Process The raw material for the reduction process is alumina (Al2O3) . Its purity in general runs as high as 99.50 pct or more. Small differences in the chemical composition generally do not affect the reduction process.* Of more importance are the physical prop- erties of the alumina, since they affect not only its rate of solution in the molten bath but also its heat insulating power.† In the following pages, un- less otherwise stated, it is assumed that a standard "Bayer" alumina is used. The reduction process, by which alumina is broken down into its components, may be roughly defined as its electrolysis in molten cryolite. The oxygen separates at the anode, and the aluminum at the cathode, which forms the bottom of the electrolytic cell. The electrolytic cell (or pot) where the process is carried out is a strongly reinforced steel box. The

Jan 1, 1951

By W. J. McConnell

OBSERVATIONS on man exposed to unusual temperatures and humidities, and studies conducted under accurately controlled environmental conditions, have supplied information regarding the physiological responses of the human body which may occur incident to such exposure. These investigations also indicate the relative importance of temperature, humidity and air motion-the three physical air factors that affect human comfort. Many and diverse were the conclusions of early investigators who associated the discomfort observed in crowded and ill-ventilated spaces with changes in the chemical constituents of the air resulting from presumably poisonous exhalations from the body. These are of interest today only because, as a recent editorial in the British Medical Journal1 states, there is still an inclination to believe in the old view that there is some injurious quality of the air in ill-ventilated and crowded rooms, quite apart from dust, microbic infection and heat stagnation. There is a tendency to fly to some mysterious unknown agent such as "deionization," which even certain American engineers are now discussing. This editorial denies the existence of the least proof of any subtle poison being exhaled by human beings or of the ionization of the air having any influence in making open-window ventilation better and more stimulating than mechanical methods which propel heated and conditioned air through ducts. Until proof is forthcoming that certain changes, with which we are not now familiar, occur in the transmission of air from the exterior to the interior of enclosures, the responsible known factors which initiate the physiological responses in human beings are limited to the combined conditions of temperature, humidity and velocity of the air. While some mention was made as far back as 1880 that high temperatures and humidities were undesirable, Hermans,2 of Amsterdam, is credited with suggesting in 1883 that the harmful effects noted in ill-ventilated rooms were due to the fact that the increased temperature and moisture of the air prevented the body from maintaining a proper thermal balance.

Jan 1, 1930

By Frederick T. Williams

THE purpose of this paper is to discuss the relative merits of the large 31/8 in. machine and the small 21/4-in. tappett machine in driving development-headings ; and although the . data here presented were obtained from cross-cut headings alone, experience has shown that the results are equally true in drifting, raising and winning. Recently we drove two parallel cross-cuts through the same formation, using a 3k-in. machine at the breast of one cross-cut., and a 2k-in. machine of the same make at the breast of the other. The results of this work afforded an ideal comparison, since in both cases the headings were advanced through rock practically of the same hardness and breaking-properties ; the amount of sludging was equal, and there was no difference in the condition of the steel or the machines, in the air-pressure or in the experience of the operating-crews. Some operators in the Cripple Creek district contend that there is ground which cannot be handled with the small machine, the holes being too small to contain enough powder to pull the ground, etc. The results obtained in working the property of the Portland Gold Mining Co., however, show that the ground worked by them does not fall in this class. During a period of two years there have been driven, with the small machine, 4 miles and 308 ft. of development-headings, through a diversity of ground, including Pike's Peak granite (a coarsely porphyritic type of granite), highly indurated, andesitic or phonolytic breccia, true massive andesite, trachytic phonolyte, tuffas, and along dikes of decomposed basalt and hard phonolyte; in every instance a satisfactory record was made. The headings here described were driven through highly indurated, andesitic breccia, having a hardness of from 5.2 to 7.2

Mar 1, 1906

By Zay Jeffries

HOSTILITIES in Europe, Asia, and northern Africa were responsible for dislocations in rare-metal supplies during 1940. Although the consumption of some of the rare metals is small the dislocations may be relatively large. In some cases these are advantageous to North America and in others they are disadvantageous. Specific instances will be cited later. Barium T HIN films of barium metal on special steel balls greatly improve the life and reduce the friction of rotating anodes in highly evacuated small X-ray tubes and make possible the operation of these anodes at relatively high temperatures. These remarkable results are described in an article by Atlee, Wilson, and Filmer in the Journal of Applied Physics for September, 1940. Oil could not be used because of the high temperatures on the one hand and its volatility on the other. Fig. 3 shows diagramatically the rotating anode and the method of coating the steel balls with barium. The letters K.I.C. refer to "Kemet Iron Clad." The K.I.C. wire was mounted so that the barium could be evaporated by direct passage of the electric current. At high temperatures the barium dif-

Jan 1, 1941

By J. B. Wagstaff, R. A. Buchanan, J. F. Elliott

High speed photography through blast-furnace tuyeres showed coke particles moving rapidly. Model studies showed a raceway was formed and gave quantitative results which were correlated with actual blast furnaces. Another study showed the similarity between hanging and the flooding of a packed column. This was explored by models. THE combustion zone before the tuyere in an iron blast furnace is a vital region because here are generated: 1—most of the gases on which the furnace depends to carry out its basic operation of reducing iron ore to the metallic state, and 2—the major fraction of the heat required in the nearby regions of the furnace for the various reduction reactions, the fusion of the slag, and the melting of the iron. Since the greater part of the coke is consumed in this region, the descent of the burden must be greatly affected by the characteristics of the tuyere zone. This region then would seem to be a profitable field for study. Fortunately, a view into this important zone is available to the operator through the tuyere peep sight. Here he sees relatively dark pieces of coke "dancing" in the blast. What he sees is of considerable help in interpreting the behavior of the furnace at a given time but the very rapidly moving particles and the intense radiation obscures what is happening very deep in the zone. This investigation was initiated in the hope that a better understanding of the combustion region could be obtained by using a high speed camera with a maximum speed of 3000 frames per sec. It seemed the best practical method of "slowing down" this characteristically violent action within the highly luminous field. Model studies and tuyere probing also have been used to aid in explaining the observed phenomena. Above the combustion zone, but below the fusion zone, there is probably a region in which the coke is comparatively stationary. Here are zones in which the gases must flow up through the granular bed counter to descending liquid slag and metal. There is no easy way to observe this zone in a blast furnace, but model studies have been of some help in explaining the nature of the zone and the laws governing the flow of the fluids involved. The whole problem is difficult and involved and any approach to a complete solution may require long investigation. This preliminary report has been written, therefore, because it is believed that appreciable progress has already been made that would be of interest to others. Tuyere Studies, Chemistry and Kinetics It is well known from the early work of Kinney and coworkers1,2 that combustion of carbon before the tuyeres appears to occur in two zones: Zone A: C + O, = CO2; AH77°F. = — 14,108 Btu per lb of carbon [I] Zone B: CO2 + C = 2CO; H77°F = + 6,183 Btu per lb of carbon [2] Zone A (Fig. 1) is close to the tip of the tuyere and zone B is somewhat farther back; there being a transition region in which both reactions occur. It is interesting to estimate the rate at which coke is burned before a tuyere with a wind rate of 90,000 cfm in a modern furnace having 18 tuyeres. Approximately 0.55 lb of carbon is consumed by eq 1 per tuyere per sec. A like amount disappears by eq 2 for a total consumption of 1.11 Ib per sec per tuyere. Assuming the coke is 85 pct C and has a bulk density of 30 lb per cu ft, this figure can be converted to a total of 1.30 lb of coke with a bulk volume of 0.043 cu ft disappearing per sec per tuyere. At the temperatures prevailing in the combustion zone (according to Kozlovich,³ he maximum is about 3400°F), the rate at which carbon is con-

Jan 1, 1953

By Richard Moldenke

One of the gravest problems of the iron foundry today is the accumulation of sulfur in commercial scrap and its effect on the castings made therewith. The ordinary jobbing castings today show a sulfur content of 0.18 per cent;, and occasionally as high as 0.22 per cent. The product of the foundry during the war is undoubtedly to blame for this rapid increase and conditions will become worse as the millions of tons of gray-iron castings of the war period return to the foundry in the form of commercial scrap. In the ordinary cupola remelting of pig and scrap, at least 0.02 per cent. sulfur is taken up; often double that amount. The high cost and difficulty of obtaining pig iron during the war period compelled the use of considerable scrap in the mixtures; frequently charges containing 90 per cent. of bought scrap were melted. Naturally the sulfur content of the castings increased. Until the advent of the basic-hearth electric furnace, the only method of holding the sulfur within reasonable limits was to use high percentages of pig in the foundry mixtures. Pig iron seldom contains over 0.05 per cent. sulfur, if well made. With pig iron forming 60 per cent. of the charge and the gates, runners, rejections, and bought scrap the other 40 per cent., the sulfur content of the castings can easily be held down to 0.10 per cent. Pig iron, however, costs more than scrap even when melting loss differences are considered, hence as small a percentage as possible will be used. The recent advance in knowledge of rational melting and the consequent reduction in losses directly due to oxidation of the metal and cold iron, has permitted the acceptance of castings with a much higher sulfur content than formerly. The steel industry also is seeking to determine how high sulfur may go with safety. In the iron foundry, however, there is the danger of a low cupola bed or an unduly retarded air-furnace heat, with the consequent raising of the freezing point of the metal and segregation effects resulting from high sulfur with insufficient manganese. The iron foundryman must, therefore, have a means of correcting his

Jan 1, 1922

By Richard Moldenke

One of the gravest problems of the iron foundry today is the accumulation of sulfur in commercial scrap and its effect on the castings made therewith. The ordinary jobbing castings today show a sulfur content of 0.18 per cent;, and occasionally as high as 0.22 per cent. The product of the foundry during the war is undoubtedly to blame for this rapid increase and conditions will become worse as the millions of tons of gray-iron castings of the war period return to the foundry in the form of commercial scrap. In the ordinary cupola remelting of pig and scrap, at least 0.02 per cent. sulfur is taken up; often double that amount. The high cost and difficulty of obtaining pig iron during the war period compelled the use of considerable scrap in the mixtures; frequently charges containing 90 per cent. of bought scrap were melted. Naturally the sulfur content of the castings increased. Until the advent of the basic-hearth electric furnace, the only method of holding the sulfur within reasonable limits was to use high percentages of pig in the foundry mixtures. Pig iron seldom contains over 0.05 per cent. sulfur, if well made. With pig iron forming 60 per cent. of the charge and the gates, runners, rejections, and bought scrap the other 40 per cent., the sulfur content of the castings can easily be held down to 0.10 per cent. Pig iron, however, costs more than scrap even when melting loss differences are considered, hence as small a percentage as possible will be used. The recent advance in knowledge of rational melting and the consequent reduction in losses directly due to oxidation of the metal and cold iron, has permitted the acceptance of castings with a much higher sulfur content than formerly. The steel industry also is seeking to determine how high sulfur may go with safety. In the iron foundry, however, there is the danger of a low cupola bed or an unduly retarded air-furnace heat, with the consequent raising of the freezing point of the metal and segregation effects resulting from high sulfur with insufficient manganese. The iron foundryman must, therefore, have a means of correcting his

Jan 1, 1922

By M. J. Coolbaugh

Mining of potash more than 3000 ft beneath the water-bearing sediments in Saskatchewan presented the unique challenge of designing stable mine workings and assuring protection from overhead water in a material that was believed to flow plastically, but whose behavior as a plastic material was not sufficiently known. Under the stress conditions ordinarily encountered in mining most rocks behave as elastic materials; that is, they compress slightly under pressure, and rebound when the pressure is released. Salt and potash, however, are different. Even under the relatively low pressures encountered at shallow depths, these materials become slightly plastic and yield to stress by flowing.* The plastic properties become more pronounced at greater depth and pressure, and the question arises as to whether or not the plastic flow will be rapid enough and exert enough pressure to destroy underground structures or interrupt the mining process.

Jan 5, 1967

By L. A. White

IN this paper it is proposed to follow the developments in the design of the lead blast furnace at Port Pirie from the time The Broken Hill Associated Smelters Pty. assumed control in 1915 to the present time, with special reference to the development of the system using two superimposed rows of tuyeres as is now in operation. Lead smelting operations first commenced in 1889, when the British Broken Hill Pty. Ltd. started its first furnace. This was followed by installing two more furnaces during the same year and another the following year. In 1892, Broken Hill Proprietary Co. Ltd. acquired the smelting works and combined operations with those at Broken Hill, New South Wales; by 1897, the whole of the smelting operations had been transferred to Port Pirie and thirteen blast furnaces were built to treat the Broken Hill ore production. In 1915, The Broken Hill Associated Smelters Pty. Ltd. took over from the Broken Hill Proprietary and have carried out operations since that time. From its inception, the present company started on a long range program of reconstruction, in which the development of the lead blast furnace has played a prominent part. A definite trend in plant development has been towards the simplification of plant control by a reduction in the number of operating units. The great advantages of technical control which resulted from the very simplified flowsheet established in the continuous refining process stimulated the desire to extend the principle to the smelting operation. Thus in the sequence of furnaces described here, it will be noted that the trend has been towards larger and, of course, fewer units. With each such development it is significant that the operating conditions and metallurgical results have shown steady improvement. Standard Furnace In 1920 there were seven furnaces operating, five of a type subsequently called the standard furnace and two of the original thirteen smaller furnaces, the latter type being used for the treatment of drosses, etc. produced from the refinery section, while the standard type carried out the main, lead-smelting operations. The standard furnace (figs. 1 and 2) had the dimensions given in table I.

Jan 1, 1951

By Zdzislaw Specht

THIS paper discusses elementary laws pertaining to seismic reflection methods and presents a general and simple criterion for determining the direction of dipping of a reflection horizon from observational data of distance and time. The important development of practical geophysics and the successful results obtained in America, Germany, and other countries, caused introduction of geophysical methods of prospecting in Poland. Of all methods, seismic prospecting has proved most successful in the area of the Carpathian foreland, where new oil reserves are to be expected. Because of the great depth of the sedimentary column in that area, rang-ing sometimes over 2000 meters, it was obvious that only the seismic reflection method could give reliable information regarding the structural features of these strata at such a depth. During the experimental surveys it appeared that the complicated geological conditions of that area do not always allow prediction of the depth and the angle of dipping of reflecting horizons, and for that reason information about the inclination of a given horizon has great importance in the determination of subsurface structure. Therefore the problem arises of obtaining from seismic reflection data reliable information as to the direction of dipping of reflecting strata, without any previous knowledge of the average velocity and depth of geologic horizons under consideration.

Jan 1, 1940

By Eugene McAuliffe

AS anthracite is no longer used to a marked extent by the rail- ways of the United States (1,513,000 tons in 1933), that portion of the mining industry engaged in the production of bituminous coal is, and will continue to be, the one chiefly concerned with the future use of its product by the railways. In a period such as the present, when all enter- prise is unsettled, when fundamental principles of industrial management and control are being swept aside or else changed overnight, it is difficult to predict what will happen. The relation between the total production of bituminous coal and the volume consumed by the steam rail- ways of the United States, Classes I,

Jan 1, 1936

By G. E. McElroy

MUCH attention has been directed to mine-air flow in recent years, more especially in Great Britian where there is frequent reference to a theory of fluid flow developed by English engineers. Briefly stated, this theory is that for similar passages of the same relative roughness, in which fluid flow occurs, the conditions of flow are exactly the same for equal values of the product W D V/ µ, where W = density of the fluid, D = diameter of the passage through which flow occurs, V = mean velocity of flow, and µ = absolute viscosity of the fluid flowing. This, the "Reynolds Criterion" of fluid flow, had its origin in the work of Prof. Osborne Reynolds' more than 40 years ago. Later, Lord Rayleigh amplified the theory2 which has been conclusively proved for small pipes by the experiments of Stanton and Pannel3 over a large flow range, and by Lacey4 over a somewhat more limited range. Concordant results on small pipes have also been obtained by numerous other investigators with single fluids over more or less limited ranges of flow. According to this theory results in one medium, such as water, are immediately applicable to another, such as air; and experimental results on models are (theoretically, at least) applicable to full-scale designs. This is of great importance in aeronautics and can be of considerable value in mine ventilation research. Hodgson, in a recent paper,5 has outlined the application of this theory to mine-air flow and recent English experiments" on the resistance of a timbered mine airway have been expressed in this form.

Jan 10, 1926

By Edward Halse

The tin-deposits of Durango, Mexico, have been ably described by Mr. W. R. Ingalls in a paper published in our Transactions in 1895.* While the occurrellces of tin-ore in other parts of the Republic are similar in many resperts to those in Durango, there are noteworthy local differences which, it is hoped, ma? lend interest to the present paper. The deposits examined by me in May, 1895, are found in the Serrania de Chacuaco, Municipality of Sain Alto, District of Sombrerete. The workings are situated in a range of mountains having a general northwest to southeast trend between Sombrerete and Fresnillo; the most northerly claim (La Desparranlada) being about six leagues southeast of the former town. El Refugio lies about four leagues to the southwest, and El Calabrote eight leagues to the west, of Fresnillo. The claims are from about 8425 to 8775 feet above sea-level, and from 1500 to 1800 feet above Sain Alto, the position of which town is marked in the map printed in Mr. Ingalls's paper. In order to reach the claims, one uses the carriage-road from Sain Alto to the small tin-colony of Las Cuevas; from the latter place to the mines there is only a rough mule-track. The mountain range consists of a rugged, weathered, gray granite rock, remarkable for large grains of quartz, and is flanked by masses of rhyolite and rhyolite-tuff of upper Tertiary age. The whole formation is broken up by narrow and steep willding arroyos and deep barrancas, mainly the result of denudation, and it appears to be a southeasterlj extension of the tin-bearing belt of rocks north of Durango City. Here and

Jan 1, 1900

By AIME AIME

ENGINEERS in the past have been largely associated with private enterprise and there has been a considerable tendency on the part of some members of our profession to depreciate government service for engineers. We engineers must change our mental attitude about employment in government service, particularly in view of the present most friendly attitude of the U. S. Civil Service Commission toward engineers for major posts in our Government. We must also take a much more active interest in public affairs. It must be realized that the national-defense program, which we are now organizing, will require for its effectiveness large numbers of engineers skilled in a wide range of technical and administrative services. In fact, the success of this undertaking will depend largely upon the extent to which our Government can command expert engineering talent to serve during the emergency. There is an acute shortage of technical and supervisory engineering personnel not only in the industries concerned with national defense but also in the Army, Navy, and other defense agencies of the Government. By an Act of Congress, approved on Oct. 9. 1940. $9,000.- 000 was turned over to the U. S. Office of Education, the regular defense agency of the Government which has co-operated with higher education for

Jan 1, 1941

By R. C. Weed

LEACHING in place at Cananea began in the 1920's on a limited scale. The first plants were small wooden boxes located underground in the Capote and Oversight mines, and output was low. Scrap iron was used as precipitant. Later several other small plants were started up. Leaching was limited entirely to underground areas, and production remained low. The Veta precipitating plant, the first on a larger scale, was put into operation in the late 1920's. After a period of intermittent service it was rebuilt in 1946 and has since been running continuously. In 1943 work on the Colorada open pit was started. This produced 40 million tons of waste, which averaged 0.20 pct capper. When these dumps had aged a few years it was decided to leach them on a large scale, and after considerable research and investigation a leaching system of pumps and pipelines was laid out and installed. At the same time the Ron-quillo precipitation plant was built to treat the copper solutions from the pit dumps. This plant started operation in March 1953. Leaching areas consist of the Colorada pit dumps and various mined out and caved underground stopes. The principal mineral, chalcocite, leaches readily in a weak sulfuric acid solution containing ferric iron. Enough pyrite is contained in the areas to produce an acid-ferric iron solution strong enough to dissolve the copper. Each area is studied to determine the best method of distributing the water over it and the best method of collecting the copper-bearing solutions after leaching has taken place. Water is generally distributed by means of ponds, ditches, and sprays. Spraying has proved the best method of spreading the water evenly; however, in a dry climate some water is lost through evaporation. After passing through the leachable material the solution is collected underground by dams and bulkheads and on surface by dams. An effort is made to give the maximum storage capacity practicable.

Jan 1, 1957

By Thomas T., Read

IT will be recalled that the first professor of metallurgy in the United States, appointed in 1855, never really gave any instruction in metallurgy and gradually turned into a professor of mineralogy. Metallurgy was included with. mining in the early curricula, two students who took the B.S. in mining engineering from the Polytechnic College of Pennsylvania in 1862 wrote their graduation theses on the metallurgy of copper and zinc, respectively. Even after Columbia School of Mines established, in 1868, a separate curriculum leading to the Ph.B. degree in metallurgy, very few students elected it,* preferring to take the mining degree, since they received in its curriculum nearly all the metallurgical instruction they would have in the metallurgical curriculum. For many years a large proportion of the men who attained prominence in metallurgical enterprises had taken mining rather than metallurgical degrees. METALLURGY Clifton Sorby's study of thin sections of rocks under the micro¬scope, beginning in 1850, and its subsequent development by Zirkel and others, had made microscopic petrography a recog¬nized department of geological research as early as 1873. . It was inevitable that the idea of studying polished metal surfaces-¬under the microscope by reflected instead of transmitted light would occur to investigators. Sorby himself did it in 1864, and Adolph Martens and Floris Osmond may -be especially named among the many European workers who, by the late eighties, had so developed the, necessary techniques that they were able to photograph polished metal surfaces at magnifications as high

Jan 1, 1941

By B. Prof. Silliman

THE occurrence of diamonds of some size in the gold-fields of California is by no means uncommon, and was noticed by me in a communication, to the California Academy of Science in 1867, when specimens of this gem, from at least five different localities, were exhibited. I then suggested that a more attentive examination of the heavy sands left in the sluices of hydraulic washings would in all probability detect diamonds, mingled with other rare species not commonly believed to have occurred in these sands. Mr. George A. Treadwell, of San Francisco, has lately sent me a small package of these sands, collected by him from the sluices of the "Spring Valley Gravel Mining Claim," Cherokee, Butte County, California. A microscopic examination shows these sands to abound in beautiful colorless zircons (hyacinths), of the form well known in the hyacinths of Expailly (France), associated with crystals of topaz, quartz in fragments, rounded grains 'of chromic and titanic iron, and

Jan 1, 1873

By B. Silliman

THE occurrence of diamonds of some size in the gold-fields of California is by no means uncommon, and was noticed by me in a communication, to the California Academy of Science in 1867, when specimens of this gem, from at least five different localities, were exhibited. I then suggested that a more attentive examination of the heavy sands left in the sluices of hydraulic washings would in all probability detect diamonds, mingled with other rare species not commonly believed to have occurred in these sands. Mr. George A. Treadwell, of San Francisco, has 1at.ely sent me a small package of these sands, collected by him from the sluices of the " Spring Valley Gravel Mining Claim," Cherokee, Butte County, California. A microscopic examination shows these sands to abound in beautiful colorless zircons (hyacinths), of the form well known in the hyacinths of Expailly (France), associated with crystals of topaz, quartz in fragments, rounded grains 'of chromic and titanic iron, and

By Albert B. Horn, J. J. McKetta, O. L. Culberson

Since water is present in natural gas and petroleum reservoirs, it is of engineering value to have accurate experimental data regarding the behavior of water in hydro-carbon systems. Since experimental data of this nature are so scarce in literature, a program is under way at the University of Texas to obtain experimental data regarding the distribution of water in petroleum hydrocarbons. This initial paper is subdivided into three parts: A. The apparatus and analytical procedure are discussed. B. The equipment has been checked by comparing the experimental data with data of literature on the solubility of methane in water at 77°F and pressures to 10,000 psia. C. Experimental data are presented at 100, 160, 220, 280, and 340°F on the solubility of ethane in water at pressures to 1200 psia. As the temperature is increased the solubility of ethane in water first exhibits a minimum and then a maximum solubility. The range of applicability of Henry's Law is discussed. INTRODUCTION Although considerable experimental data have been published on water-hydrocarbon systems in the hydrate region, the information on these systems in the vapor-liquid and the vapor-liquid- 'References are given at end of paper. Manuscript received at the office of the Petroleum Branch August 31. 1949. liquid regions at elevated pressures is extremely scarce. A survey of the literature on hydrocarbon-water systems at elevated pressures was presented by McKetta and Katz12,13,14 showing the systems and phases investigated. In addition to these existing published data, Poettman and Dean" have reported the water content of propane in the three-phase region (only the propane-rich liquid and the vapor phases were studied) and Michels, et al.15 have reported the solubility of methane in water at pressures to 6800 pounds per square inch at 77°F and at pressures to 1500 psia at temperatures to 300°F. It has been shown12,14 that the presence of water will materially affect the phase equilibrium of hydrocarbon systems. In order to make experimental studies on the quantitative effect of the presence of water in naturally-occurring hydrocarbon systems, it is desirable to have data available on binary hydrocarbon-water systems. A program is underway at this laboratory to determine the phase relations of the hydrocarbon-water systems. Initially the investigation will be limited to binary systems with water as one of the components. Later ternary and complex systems will be investigated and reported. EQUIPMENT AND ANALYTICAL PROCEDURE Apparatus In order to avoid a description of the methods employed in each subsequent paper, a description of the apparatus and the analytical procedure will be given here. The apparatus is shown schematically in Fig. 1. The numbered items in Fig. 1 represent the high pressure valves. The equilibrium cell is of the totally enclosed type, with a volume of 550 cubic centimeters. The cell is mounted in an air bath which in turn is mounted on pillow blocks and connected to a rocking mechanism so that the cell and bath will oscillate approximately 30 degrees above and below the horizontal at 35 oscillations per minute. The air bath is heated by two resistance heaters. The first or primary heater is 250 watts and is controlled by a thermoregulator; the second heater is of 500-watt size and is manually controlled to aid in bringing the cell to equilibrium temperature. Air circulation in the bath is accomplished by means of a fan. the shaft of which is concentric to the heaters. The walls of the bath are insulated with 2-in. thick blocks of 85 per cent magnesia. Temperature observations are made with three calibrated thermocouples. One couple is sealed in a well provided within the equilibrium cell, and is used as the criterion of the cell being at the equilibrium temperature. The other two thermocouples are located on opposite sides of the cell to indicate temperature uniformity within the air bath. The thermoregulator, used in conjunction with a relay, gives a variation in the temperature of the air in the bath of plus or minus one degree Fahrenheit. However, since the equilibrium cell weighs approximately 55 pounds, the

Jan 1, 1950