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By C. M. Weld

In the course of my professional work in China during the fall of 1907, I had an opportunity to visit the iron-ore mines at Ta-yeh in Hu-pei province (long. 114O 50t E., lat. 30' 20t N.). It occurs to me that a rescript and discussion of my notes taken at that time should be of interest, particularly as supplementing the exceedingly interesting recent paper of Thomas T. Read on The Mineral Production and Resources of China.' Ta-yeh is situated near the right bank of the Yangtze river. The mines are at an average distance of about 16 miles from the river-port Shi-hui-yao, which in turn is some 70 miles SE. of Hankom. The ores are shipped to the works of the Han-Yeh-P'ing Iron & Coal Co. at Hanyang, as also very largely to the Japanese government iron- and steel-works at Wakamatsu, Japan. Smaller qnantities have been exported to the Pacific coast of the United States. These ore-deposits have been briefly noticed in a number of publications, but, so far as I know, Mr. Read's description, in his chapter or1 the iron-ores of the Chinese Empire,2 contains the first attempt to define their geological character. In his more recent paper Mr. Read follows very closely the text of his earlier description. To quote briefly from the recent paper, he says : " The iron-ores at Ta-yeh .... lie along the contact between a marble and an intrusive body of a dark-gray syenitic rock." He refers to a figure which exhibits in plan, but not in section, the relative positions of the syenite, ore-bodies, and limestone. The contact is seen to trend approximately E-W., with the syenite on the north and the limestone on the south. " The syenite lies to the north of the marble, and a few miles farther north the marble again appears, iron-ore again being present along the contact." No litho-

Jan 1, 1913

By H. J. Wasson

WITH the close of 1932 and the third year of the depression, the activity of oil production presents, amidst the general wreckage and chaos of industrial society, a somewhat unique picture of rationalized economic effort. East Texas still dominates the contemporary horizon, but it has become, at least for the time being, a definitely known factor. With its 9500 wells it is approximately 90 per cent drilled up. So long as production control obtains, it is merely one important factor of the national oil reserve. Each succeeding month of stabilized production tends to lull the industry's fears and the menace, both actual and psychological, of this giant field becomes ever more remote.

Jan 1, 1933

By A. B. Cook

Gas cycling is generally considered a much less efficient oil recovery mechanism than water flooding. HOWever, recoveries from some fields have been exceptionally high as a result of gas cycling. Recovery from the Pick-ton field, for example, was calculated to be 73.5 perceni of the stock-tank oil originally in place. In evaluating pressure maintenance projects, determining how much of the recovery is due to displacement by gas and determining how much is due to vaporization of the imrnohile oil in the flow path of the cycled gas is very difficrilt. Even though most of the oil is recovered by displacetr~ent, the success of a project may depend on the amount of oil vaporized. A limited number of experiments have heen performed with a rotating model oil reservoir that simulates gas cycling operations and allows a separation of the oil from, tile free gas flowing into the laboratory wellbore at reservoir conditions, thus revealing which is displaced oil and which is vaporized oil. It Iras been determined that the amount of varporizatio'n is .significant if proper conditions exist These experiments show that oil vaporization depends on pressure, temperature, volatility of the oil and amount of gas cycled. Increases in each of these conditions increase the volume of oil vaporized. Data from six experiments affecting vaporization are presented to illustrate reservoir condition that range from favorable to unfavorable. 111 these eaperitnenis recovery by vaporization ranged from 73.6 to 15.3 percent of /he immobile oil (oil not produced by gas displacerrlt). INTRODUCTION Between 1930 and 1950, gas cycling was a popular. oil recovery practice. especially for the deeper reservoirs. Later, with many case history-type studies published for both gas cycling and waterflooding, it was generally believed that waterflooding was far superior to gas cycling, even when gas cycling was conducted as a primary production procedure by complete pressure maintenance. A good example illustrating the advantage of water-flooding over gas cycling is given in a paper by Matthews' on the South Burbank unit where gas injection was followed by waterflooding. The author concluded in part that "Early application of water injection, without the intervening period of gas injection, would have recovered as much total oil as ultimately will be recovered by waterflooding following the gas injection, and total operating life would have been shortened". This appears to be a logical conclusion. However, it should not be applied to all fields. Pressure maintenance with gas in the Pickton field, as reported by McGraw and Lohec;' will result in a much larger percentage of oil recovery than was obtained in the South Burbank unit. The great success in the Pickton field resulted partly from vaporization of the immobile oil in the flow path of the cycled gas. The amount of vaporization is related to the following conditions: volatility of the oil as reflected by the APT gravity of the stock-tank oil; reservoir temperature; reservoir pressure during gas cycling; and the amount of gas cycled. Therefore, the U. S. Bureau of Mines is investigating these effects on vaporization in a research project using a model oil reservoir. Three different stock-tank oils having 22, 35 and 45" API gravities are being used as base stock to synthesize reservoir oils. Experiments are being performcd to determine vaporization at 100, 175 and 250F and at 1,100, 2,600 and 4,100 psia. This is a progress report showing the results from six experiments. Other Bureau of Mines reports"- concerning vaporization are listed. LABORATORY EQUIPMENT AND PROCEDURES The equipment ' consists of an internally chromium-plated steel tube packed with finely sifted Wilcox sand. The tube is approximately 44 in. long and has an ID of 13/4 in. The sand section contains approximately 570 ml of voids, has a porosity of 32 percent, and a permeability to air of 4.3 darcies. A unique feature of the laboratory reservoir (Fig. 1) permits the tube part to rotate at 1 rpm while the outlet and inlet heads are held stationary. The outlet end contains diametrically opposed windows to permit observatlon of the flowing fluids, and two valves, one on the top and the other at the bottom. Oil and free gas. when being produced simultaneously, can be separated by manipulating the two valves to keep a gas-oil interface in view through the windows. Thus, only gas is produced through the top valve and only oil flows through the bottom valve. The laboratory equipment was designed to study vaporization. Therefore, a uniform reservoir was made using dry sifted sand as opposcd to using a consolidated sand core with interstitial water. Furthermore. the reservoir was tilted to minimize fingering of gas. This tilting also in-

By H. S. Drinker

THE first discovery of zinc 011 the property now worked by this company was made by the celebrated mineralogist, Prof. William Theodore Rapper, in 1845. Different claimants kept the property in continual litigation till 1861, when everything was satisfactorily settled by the purchase of the land by the company, who have worked it ever since. The mines are situated in a valley, four miles south of Bethlehem, Pa., in Lehigh County. The valley is from two to three miles broad, and is bounded 011 the north and south by syenitic hills. Syenite underlies the valley, and upon this is deposited the Potsdam sandstone, then a layer of slate, and, finally, a dolomitic limestone, belonging to the Chazy or Black River formation, in which the zinc deposits are inclosed. The rocks occur in folds, and have evidently been subjected to tremendous pressure from below, the zinc deposit being found in an anticlinal axis, in nearly vertical veins. I t is supposed that the zinc was originally disseminated through the

By D. A. Dahlstrom

Although the liquid-solid cyclone is a relatively recent innovation in the field of coal preparation, various authors have already indicated three distinct applications to operations encountered in the modern tipple. Driessen's articles and work at the Dutch State Mines exhibited its possibilities in the beneficiation of fine coal with apparently high efficiencies down to the 200-mesh fraction. 1 2 3 4 Other publications point out its use as a recoverer, thickener, and preliminary dewatering agent of fine coal which in too many cases is being wasted due largely to former high operating cost limitations 5 6. Finally, certain authors have emphasized the practicability of applying the cyclone to the elimination of coarse and fine solids from water slurries in the tipple in order to produce a water suitable for recycle purposes containing only minute particles far below the 200-mesh size.6 This would result in a closed water system for many cases, with its accompanying economic and operating advantages to locations where water quantity and quality problems are severe; better operation of washing equipment using a consistent water devoid of injurious fine particles; lowered maintenance costs due to the lesser abrasion resulting when the fine abraiding particles are removed; and the greater ease of disposing of refuse streams of reduced volume containing greater percentages of solids.

Jan 1, 1949

Discussion of the paper of WALTER 0. SNELLING, presented at the New York meeting, February, 1915, and printed in Bulletin No. 100, April, 1915, pp. 695 to 704. A. F. LUCAS, Washington, D. C.-Are the results of the experiments in practical operation? WALTER 0. SNELLING.-There have been no large-scale operations up to the present. The necessary conditions of temperature are easily arranged for, but the required condition of pressure, 800 lb., is not so simple a matter. The company has been working on this problem, and at the refinery in Oklahoma work of this kind is now being carried on. The way in which an ordinary still will leak at 50 lb., and more at 100 lb., leaves some doubt in the mind of many as to what can be clone at a continuous working pressure of 800 lb. On the other hand, the fact that they are making ammonia abroad by a method which employs higher pressures and temperatures than anything involved in this method, leads me to believe that the difficulties, which will undoubtedly arise when this is attempted on a commercial scale, can be overcome. WILLIAM N. BEST, New York, N. Y.-Is there any change in the calorific value of these oils?

Jan 5, 1915

By B. E. Sundquist

The various methods based on solution models for obtaining free energies of mixing from miscibility-gap data have been applied to a number of binary-alloy systems. For nine of these systems there exist experimental thermodynamic data that permit a comparison of the results to experiment. It was found that the method of van der Toorn and Tiedema almost invariably leads to results that are physically unacceptable and that vary drastically with small changes in the miscibility-gap parameters. The subregular solution model is found in all cases, except the Al-Zn, Fe-Cr, and Cu-Pb systems, to exaggerate the free energy of mixing by 30 pct or more. The model developed by Lumsden is found to give results that are often in excellent agreement with experiment and which exaggerate the free energy of mixing by no more than 30 pct. These results and others give evidence that the Lumsden treatment of the effect of unequal atomic sizes and of imperfect configurational randomness due to deviations of AB bond energies from the mean of AA and BB bond energies is adequate for most systems. ANALYTIC expressions are frequently proposed for the dependence on composition of the activities of the components of a solution. Because the development of solution theory is incomplete, these expressions contain parameters which must be determined by experiment. The measurement of activities is often difficult and consequently such measurements are less readily available than are measurements of phase equilibria which, under certain conditions, can also be used to evaluate these parameters. For example, suppose it is known that two structurally dissimilar phases, each of known composition, in an n-com-ponent system are at equilibrium at a given temperature and pressure. n equations can be set up in terms of these parameters expressing the equality of the chemical potential of each component in the two phases. In addition, one can write the Gibbs-Duhem equation for each phase that also contains these parameters. Thus, if these n + 2 equations contain n + 2 parameters, these parameters can be determined (at the temperature in question) from the phase diagram alone. If the average number of parameters in each expression for the activity of a given component in a given phase is V then there will be 2nV parameters involved. Equating 2nV to n + 2 shows that, for n + 2, V = 1. If the temperature dependence of each parameter were to be expressed in some explicit form one could use equilibrium conditions at a number of temperatures to increase V. The situation is much improved when the two phases in equilibrium are structurally similar. It can then be assumed that, stably or metastably, two phases will become one at higher temperatures. Thus the number of parameters involved becomes nV instead of 2nV. Hence, V = 2 for n = 2 using only one temperature. (It is implied here that the activity expressions used are valid over the entire composition range.) In this investigation only the equilibrium of two structurally similar, two-component phases (miscibility-gap systems) will be considered. The various proposed solution models will be applied to a number of these systems and the results compared with available experimental results. All of the analytic expressions that have been proposed for the free energy of mixing of a two-component system are of the form where ?Gmix is the free energy of mixing per mole of solution, N1 and N2 are the mole fractions of components 1 and 2, respectively, and f(Ni, T) is some function of composition and temperature. In the "ideal" solution model f = 0. In the "regular" solution model f = a constant. Since these two models permit only a symmetric equilibrium diagram they will not be considered further here. The simplest model that permits a nonsymmetric miscibility envelope is the so-called "subregular" solution model proposed by Hardy.1 This model gives where the Ci(T) are functions of temperature only. The same expression for f is obtained from the "linear a function" model proposed by Darken and Gurry2 and applied to miscibility-gap systems by Wriedt.3 This model requires that the a function defined by be a linear function of composition (yi is the activity coefficient of component i). This model is not purely hypothetical for it has been found2 to hold true for a number of systems. It is readily shown3 that the f(Nl, T) obtained from this model is of the form given in Eq. [2]. It will be noted that the subregular solution model contains only two parameters and hence both of them can be determined at any desired temperature below the critical temperature, Tc, for a miscibility-gap systems in the manner described previously. At T, the two constants can be determined by equating the second and third derivatives of ?Cmix with composition to zero. Another two-parameter model was proposed by Lumsden4 who set

Jan 1, 1967

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1935 are available at Institute headquarters, unless otherwise noted. They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS. Copies of the TECHNICAL PUBLICATIONS have been mailed to members of the Institute that are registered in the different classes: A-Metal Mining; B-Milling and Concentration; C-Iron and Steel Division; D-Nonferrous Metallurgy; E-Institute of Metals Division; F-Coal Division; G-Petroleum Division; H-Industrial Minerals Division (Nonmetallics); I-Mining Geology; J-Mineral Industry Education Division; K-Mining Administration; I-Geophysical Prospecting. Other members may obtain copies by writing to the Secretary. Copies of CONTRIBUTIONS may also be obtained from the Secretary's office. Additional copies are sold at the rate of 1 cent per page; minimum charge, 25 cents. Nonmembers may purchase the papers at the prices mentioned. [ ]

Jan 1, 1936

By R. J. Wasilewski

THERMAL expansion of rhenium data have been reported by Agte et al.,&apos; and Medoff and cadoff,&apos; respectively, while the linear expansion coefficient was determined by Sims et Al.3 Denoting expansion coefficients parallel and at right angle to c axis by all and Al respectively, their weighted mean should be equal to dilatometric linear coefficient of a random polycrystalline specimen. The values reported for these coefficients are tabulated below: Since these values are in poor agreement, and because of anomalous expansion behavior observed in titanium 4 and chromium, a rede termination of the axial expansion was carried out. A Unicam 19-cm-diam high-temperature camera was used, with unfiltered CuK radiation. Camera calibration was carried out using at Pt wire standarde at temperatures up to 1100oC, the variation between indicated and true temperature being within the experimental error (estimated at <3oC) above 750o C. Rhenium Johnson Matthey spectrographic standard) was vacuum annealed at 1000 oC prior to X-ray diffraction experiments. Lattice parameters were obtained by least-squares solution using the reflec- tions (1232), (1015), (2024), and (3030) for all the patterns, and the additional reflection (2133) for higher temperature (400°C and above) patterns. The relative expansion data obtained are shown in Fig. 1, lengths of the vertical bars indicating the spread in the parameter values obtained by using various combinations of three spacings from the four or five measured. The data calculated from the equation of Ref. 2 are included for comparison purposes. Several specimens were used to obtain the above data, neither of them showing a significant parameter change after completion of the high temperature runs. Some parameter data and the corresponding expansion coefficients between 25 oC and the measurement temperature are tabulated below. The comparison of the present data with those previously reported shows reasonable agreement with the results of Medoff and cadoff2 within the temperature range covered by them (up to 1000 oC). The a values are appreciably higher throughout most of the investigated temperature range. The basal expansion is—in agreement with their findings—appreciably higher than that in the direction of hexagonal axis. The expansion coefficient, al, however, decreases rather more slowly with temperature than previously reported. The expansion along the c axis up to nearly 1000°C appears in excellent agreement. However, at higher temperatures there is a marked deviation towards higher expansion, reproducible between different specimens. Furthermore, there seems to be some irregularity in the variation of all with temperature, the apparent local minimum and maximum values at 510o and 1024o C, Table II, being well outside the experimental error limits. It must be stressed that the apparent discontinuity in the c parameter expansion is still insufficient to account for the expansion value reported by Agte et al.&apos; since a total expansion of close to 2 pct would

Jan 1, 1962

By J. L. Huiatt, D. G. Foot

The Bureau of Mines devised a direct flotation method for treating low-grade carnallite (KCl*MgC12*6H20) and sylvinite (a mixture of KC1 and NaCl) ores characterized by a high content of water-insoluble impurities. The procedure consists of flocculation-depression of the insoluble slimes; decomposition leach (carnallite only); potash rougher, cleaner, and recleaner flotation; and final product leaching. The technique eliminates the necessity of removing the water-insoluble slimes by mechanical or flotation desliming. Laboratory results demonstrated that the direct flotation procedure, when compared with conventional techniques, yielded equivalent or improved flotation results with equal or less reagent consumptions. The direct flotation method recovered 81.6% of the solid phase KC1 from camallite ore and 79.7% of the KCl from sylvinite ore in final products containing 60.5 and 60.9% K2O, respectively. A flowsheet incorporating the described flotation procedure is presented.

Jan 1, 1983

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria &apos;Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1934 are available at Institute headquarters, unless otherwise noted They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS Copies of the TECHNICAL PUBLICATIONS have been mailed to those members of the Institute who are registered in the different classes A-Metal Mining, B-Milling and Concentration; C-Iron and Steel Division; D-Nonferrous Metallurgy; E-Insti¬tute of Metals Division; F-Coal Division; G-Petroleum Division; H-Nonmetallic Minerals; I-Mining Geology; J-Mineral Industry Education Division; K-Mining Administration; L-Geophysical Prospecting Other members may obtain copies by writing to the Secretary Copies of CONTRIBUTIONS may also be obtained from the Secretary&apos;s office Additional copies are sold at the rate of 1 cent per page, minimum charge, 25 cents Nonmembers may purchase the papers at the prices mentioned

Jan 1, 1935

Edgar Archibald Collins was born at Truro, Cornwall, Nov. 16; 1877. He was the fifth (and youngest) son of J. H. Collins, a well known Cornish geologist and engineer, who died in 1916. Edgar Collins spent part of his childhood at Rio Tinto, in Spain, and after returning to England was educated at Alleyne&apos;s School at Dulwich, near London. His technical training was acquired by practical experience in Cornwall, supplemented by private study and by his father&apos;s teaching. This method of training for the work of a mining engineer was preferred by his father to that of the technical schools then available, and judging by its result, was not unsuccessful. It is,-however, noteworthy that all members of the Collins family who were products of this system later sent, or planned to send, their own sons to technical schools. Edgar Collins came to Gilpin County, Colorado, in 1894, and returned there in 1898, after several intermediate years spent in Cornwall. In Colorado he worked, under his brother Arthur, in the California and other mines of the Gilpin County district, and thereby gained a practical skill and experience as a working miner, and a habit of minute observation of vein phenomena, which proved of the greatest value in later years. In 1899 he went to the Smuggler-Union it Telluride, as general assistant to his brother Arthur, and stood the brunt of 3 years of struggle with the Western Federation, gaining a reputation, for quiet courage and sound work under the most difficult conditions. After Arthur Collins&apos; assassination in the Smuggler-Union office, in November, 1902, Edgar left Telluride, and shortly thereafter entered the employment of a syndicate headed by Arthur Winslow, of Boston, to search for and develop new mines. While so engaged he spent several unsuccessful months near Parral, in Mexico, and later visited and sampled the- newly discovered district of Grandpa, afterward known as Goldfield, in Nevada. This led to the acquisition by the Winslow syndicate of the Combination mine, at first under lease and option; and Edgar Collins was placed in charge. The Combination was really the starting point of Goldfield. It was a profitable mine before the discoveries at the Jumbo were made; and while the Combination, being a "Company-account" mine, controlled by a few responsible men, never attracted the publicity that centered around the sensationally profitable leases on the Jumbo and Mohawk, which publicity was used to further the feverish stock-dealings that characterized the new district. The Combination was really the pioneer mine, made the first shipments of rich ore, constructed the first water-line, and built the first mill (designed by F. L. Bosqui, an old friend and associate); and while it pursued a quiet and unobtrusive. career up to the time of its sale to and incorporation with the Goldfield Consolidated, was probably, in ;proportion to the amount of money risked, the most profitable bonanza in the recent history of gold mining.

Jan 11, 1918

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who registered at Institute headquarters during the period Nov. 10 to Dec. 10, 1915: F. Lynwood Garrison, Philadelphia, Pa. E. Fleming l&apos;engle, Costa Rico, C. A. William J. Lakeland, Burma, India. Fred Maccoy, El Oro, Mexico. Dwight E. Woodbridge, Duluth, Minn. 0. N. Scott, Toronto, Ont., Canada. Chester A. Fulton, Yonkers, N. Y. K. P. Swenson, Tokyo, Japan. Willet G. Miller, Toronto, Canada. - H. L. Mead, New York, N. Y. L. G. Huntley, Pittsburgh, Pa. E. DeGolyer, Norman, Okla. L. E. Howard, Lockport, N. Y. J. S. Lane, New York, N. Y. H. W. DuBois, Philadelphia, Pa. T. V. Nonactre, Argentina. Howard R. Stewart, London, England. N. H. Darton, of the U. S. Geological Survey, has returned to Washington after a long season of field work in New Mexico investigating the prospects of finding potash deposits in the Red beds.

Jan 1, 1916

By AIME AIME

MESSRS. BURT and Shockley and others have been for three years urging upon the Institute the matter of simplified spelling. The Institute endeavors to be progressive in the matter of spelling and. is in cooperation with the national body which has this in hand and which has its principal office in New York. Our spellings are changed as fast as-good usage will permit (so it seems to the Board of Directors) and the national body, which is the real representative of the simplified spelling interests, deems that the Institute is making real progress, although not quite as fast as extremists would wish. In January, 1919, Mr. Shockley sent out letter ballots which created a misconception in the minds of many members, who received the impression that the communications came from the Institute instead of from a small group of members. As a result of this propaganda 163 proposal-ballots were sent in to the Institute divided as follows: Yes ?114 No ?20 Negative letters ?9 Split ballots ?20 Total ?163 The total membership at this time was about 7200. The disgusted members would not vote.

Jan 1, 1920

By L. A. Bromley, R. L. McKisson

A high temperature calorimeter designed for use up to 1500°K is described and the theory of its operation presented. This calorimeter was used to measure the heats of formation of Na-Sn alloys ranging in composition from tin to Na2Sn. The values tend to support those reported by Kubaschewski and Seith. ONE method of obtaining the heat of formation of an alloy is to measure the heat of mixing of the elements at high temperature. The principal advantage of this method is that the desired quantity is measured directly, while in conventional room temperature methods the differences of the heats of solution of the elements and the alloy in a suitable solvent are measured. A method of improving the accuracy of the high temperature measurements, when the precision of the measurement is lower than that of the heat capacity values for the elements, is to add one component at room temperature to the other at the high temperature, so that part of the heat of reaction is dissipated in heating the cold component to the high temperature. Thus, only a fraction of the heat of reaction is measured, and a result of higher precision is obtained. The limitations of the high temperature technique are that volatile systems cannot be studied, and that many alloys melt at temperatures higher than those at which the calorimetric apparatus operates readily. Nevertheless, a calorimeter operating at 1500°K would be useful in investigating many of the lower melting alloy systems and the low melting mixed oxide systems. A unit designed for these applications was built and is described here. The Na-Sn system was chosen for investigation because the temperature involved, 880°K, would adequately test the operation of the calorimeter. Further, the data reported in the literature for the various alloys of sodium and tin differ markedly, and it was hoped that this investigation would help to fix the values of the heats of formation in this system. Design of Apparatus A detailed discussion of the considerations involved in the calorimeter design is given by Mc-Kisson and Bromley,&apos; and a brief summary follows. Fig. 1 shows a sectional view of the calorimeter. The inner graphite chamber is maintained at constant temperature by means of the circulating molten tin bath in which it is submerged. The tin is contained in a graphite vat. This unit comprises a thermostat whose heat capacity is about 7000 cal per "C. The main heating element consists of a machined graphite spiral with a room temperature resistance of about 1/2 ohm. These parts are separated from the powdered carbon external insulation by the cage, a cylindrical graphite chamber. The electrical insulators and separators, the auxiliary heater spool, and the loading tube liner are made of sintered alumina. The tin vat stirrers, the sample stir-rer, the melt thermocouple well, and the power leads are made of molybdenum. The auxiliary heater is wound with molybdenum wire and serves to compensate for the heat loss up the loading tube. All of the individual components in the high temperature region of the calorimeter will withstand at least 2000°K, and the various contacting materials should easily withstand 1500°K. The external container for the insulating carbon powder is a copper shell upon which copper tubes are soldered to serve as cooling coils.

Jan 1, 1953

Meeting of May 22, 1914.-President Thayer. announced the appointment of the following Committee on Arrangements for the San Francisco meeting of 1915: Charles W. Merrill, Chairman; F. W. Bradley, Abbot A. Hanks, S. B. Christy, and H. C. Hoover. President Thayer announced the appointment of the following Committee on Organization for the Utah-Nevada Local Section: R. C. Gemmell, Chairman; C. D. Blood, Lafayette Hanchett, Ernest Gayford; Duncan MacVichie, and George W. Riter. The President of the Institute offered $100, to be known as the "President&apos;s Prize," to be used as prizes for the best papers submitted by members of the Affiliated Student Societies, to be divided as follows: First Prize, $50; Second Prize, $30; Third Prize, $20. A committee, consisting of J. F. Kemp, Chairman; W. L. Saunders, and T. T. Read, was appointed to report on the conditions to govern the award. The President announced the appointment of the Committee on Mining and Milling Methods, the personnel of which is shown on a subsequent page of this Bulletin. The following were appointed on the Advisory Committee to the U. S. Bureau of Standards, to represent the manufacture of the various non-ferrous metals as indicated: Copper, F. L. Antisell; Nickel, David H. Browne; Lead, H. O. Hofman; Aluminum, J. W. Richards; Zinc, G. C. Stone. It was voted to hold a meeting of the Institute under the auspices of, the Iron and Steel Committee, the Committee on Petroleum and Gas, and the Committee on Coal and Coke, in Pittsburg, Pa., Oct. 8, 9, and. 10, 1914.

Jan 7, 1914

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.&apos; Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2&apos;4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy&apos;s equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.&apos; were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By J. E. Sherborne, P. H. Jones, E. C. Babson

A study of the Chapman zone in the Richfield field, Orange County, California, indicates that the quantity of oil recovered by present methods will be only a small portion of the oil originally in place. Since the volume of residual oil is believed to be of large magnitude, an experimental water-flooding operation has been initiated in order to determine whether water-flooding offers promise as an economical method of recovering some of this residual oil. A single injection well was drilled between old producing wells, and a water-treating plant using alum flocculation and chlorination was designed and built. Water has been injected into the input well for six months at rates in excess of 100 bbl. per day. Production from one of the neighboring wells has increased materially, the oil production having risen from 7 to 30 bbl. and the water From I to 40 bbl. per day. While definite conclusions regarding the economic success of water-flooding in the Chapman zone are not justified at this time, it has been demonstrated that water can be injected into the zone on a sustained basis and that this water will displace appreciable quantities of oil from the sand. Introduction As a result of an investigation of subsurface conditions in the Chapman zone of the Richfield field, it was concluded that ultimate oil recovery from this zone would probably be low and that natural water encroachment was so localized as to be of little importance from a recovery stand- point. Furthermore, it was found that in many portions of the zone the wells were approaching an unprofitable level of production. When these data were presented to the management of the Union Oil Co.; their reaction was that an attempt should be made to develop methods of recovering at least a portion of the large quantity of oil remaining in this zone. After some investigation, it was decided that wafer-flooding offered the most likely means of accomplishing this end, but reservoir conditions in the Chapman zone differ so widely from those encountered in any of the flooding projects described in the literature that it was difficult to evaluate the probability of success. Despite encouraging results from laboratory tests, it was not even certain that water would displace an appreciable volume of oil from the Chapman sand under reservoir conditions. Therefore, it was decided to initiate a small-scale project, for two purposes: first, to determine whether water would displace oil from the Chapmall sand and, second, to obtain information and experience for future operations if water-flooding appeared to be a promising method of secondary recovery. Reservoir Data The Chapman zone is the upper of the two producing zones in the Richfield field, being found at depths from 3000 to 3700 fi.. The productive portion of the zolle consists of a large irregularly shaped sand body, which is more than 400 ft. thick at the top of the structure. As the margin of the field is approached, the sand is replaced

Jan 1, 1945

By Larry Kaufman, Martin Schatz

The effect of pressure on the extension of the ? loop in the FeSi system has been determined by means of metallogvaphic studies and hardness measurements performed on a series of high-purity Fe-Si alloys containing 7.5, 11.0, and 13.9 at. pct Si, respectively. These mensurements, performed at 42 kbar and temperatures up to 1200oC, indicate that the ? loop is expanded to about 10 at. pct Si at 42 kbar as opposed to a maximum extension of 4 at. pct Si at 1 atm. Comparison of the experimental results with thermodynamic predictions of the pressure shifts yields satisfnctory results. DURING the past few years, several studies have been performed in our laboratory1-&apos; in order to determine the effect of high pressure on phase equilibrium in pure iron and iron-base alloys. The purpose of these studies has been to elucidate the effects of high pressure experimentally and to compare the observed results with predicted pressure effects derived on the basis of known thermody-namic and volumetric data at 1 atm. These studies have included work on pure iron2,5,7 as well as Fe-Ni,1,5 Fe-cr,l,5 and Fe-c4-6 alloys. In addition, Tanner and Kulin3 have reported results of pressure studies on two Fe-Si alloys containing 2.0 and 6.25 at. pct Si. At the time of this latter study, no detailed information was available concerning the difference in volume between the a (bcc) and ? (fcc) phases in the Fe-Si system as a function of silicon content. In order to compare their observations with calculated pressure shifts, Tanner and Kulin were forced to assume that silicon had no effect on the difference in volume between a and ? iron. The resulting discrepancy between their calculation of the a/? phase boundary at 42 kbar and the observed results led them to the conclusion that silicon additions probably decrease the difference in volume between a and ? iron. Recently: Cockett and Davis8,9 have reported de- tailed studies of the lattice parameters of a series of Fe-Si alloys at temperatures ranging from 20" to 1150°C. These measurements, performed on alloys in the bcc and fcc range, show that silicon does indeed decrease the difference in volume between a and ? iron. By correcting the calculations of Tanner and Kulin in line with the observed effect of silicon they were able to show improved agreement between computed and observed pressure shifts.&apos; The present measurements were undertaken to provide additional corroboration of this effect, by extending the range of composition, in addition to exploring a situation where large extensions of a ? loop could result in impingement of the ? field with an ordered bcc phase (based on Feo.75Sio.25). I) EXPERIMENTAL PROCEDURES AND RESULTS The alloys investigated were obtained from Dr. F. Kayser of M.I.T. They were prepared at the Ford Scientific Laboratory by vacuum melting electrolytic iron and high-purity silicon. The melts were poured under an argon atmosphere into hot-topped steel molds. Subsequently the ingots were hot-worked down to 1/2-in.-diam rods. Three alloys containing 7.5, 11.0, and 13.9 pct Si were studied. Carbon, regarded as the principal impurity, analyzed at, or below, 0.001 wt pct for all of the alloys. Prior to pressure-temperature treatment, the rod was annealed for 24 hr in vacuum at 1000°C, water-quenched, and subsequently machined into 0.100-in.-diam by 0.100-in.-long specimens. Subsequent to machining, the specimens were again annealed and then examined metallographically. They were found to exhibit a clear coarse-grained ferrite similar to Figs. 10 and 110 of Ref. 1 and Fig. 2 of Ref. 3. Subsequently, specimens of each alloy were equilibrated at 42 kbar at various temperatures in supported piston apparatus.1,3,4,6 Three specimens, one of each alloy, were wrapped in platinum and exposed simultaneously. The pressure-temperature cycle consisted of increasing the pressure from ambient to 42 kbar at 25oC, heating rapidly to the desired temperature, holding for 15 min, and quenching to 100°C, followed by slower cooling to 25°C and pressure release. The temperature was measured with a Pt/Pt-13 pct Rh thermocouple which was not corrected for pressure effects. Subsequently, specimens were examined metallographically and by

Jan 1, 1964