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By B. W. Howlett, M. B. Bever, Somnath Misra

The heats oj- formation at 0°C of the compounds AuSn,, AuSn2, AuSn, and the £ phase were measured in a metal -solution calorimeter with liquid tin or a liquid Sn-Bi alloy as solvent. The melting point, heat of fusion, and heat capacities near the melting point of- the compound AuSn in the solid and liquid state were measured in a constant temperature gradient calorimeter. The free energy and entropy of formation of the compound AuSn at its melting point and at 298 °K were calculated from the experimental results and published data. The heats of formation are discussed in relation to the nature of the compounds. The heat capacity below the melting point, heat of fusion, and entropy of fusion of AuSn are interpreted in terms of processes oc-curring before melting. The atomic arrangement in liquid Au-Sn alloys and the bonding in the intermediate phases of. the Au-Sn system are discussed in the light of the measured thermodynamic properties. THE available thermodynamic information on the intermediate phases in the Au-Sn system consists of the heats of formation of the compounds AuSn4, AuSn2, and AuSnly2 and of one composition of the < phase2 besides values of the heat content of the compound AuSn from 0" to 635".&apos; However, the heats of formation refer to different temperatures ringing from 90" to 450°C. Also, the reported error limits of some of the values are large and several inconsistencies are apparent. In the investigation reported here the heats of formation of the compounds AuS-, AuSnz, and AuSn and of three compositions of the < phase were determined for a single reference temperature of 0°C by liquid metal-solution calorimetry. The compound AuSn, which is the only congruently melting intermediate phase in this system, was further investigated in a constant temperature gradient calorimeter by measuring its heat of fusion, melting point, and heat capacity in the solid and liquid states near the melting point. From these data and published free energies of the liquid of composition Au~n,&apos; the free energies of formation of the compound AuSn at the melting point and at 298°K were calculated. The results shed light on the solid-liquid transition of AuSn and on the atomic bonding and state of association of gold and tin in the solid and liquid phases. 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Samples. Stoichiometric amounts of gold and tin, each 99.99+ pct pure, were melted in evacuated Vycor capsules (12 mm ID). The melts were maintained approximately 150°C above the liquidus for about 12 hr and shaken repeatedly. Samples of the compound AuSn were cooled slowly to room temperature. Melts of the other phases, all of which solidify by peritectic reactions, were transferred to the narrow end (5 mm ID) of the capsule, which was then quenched into iced brine. The solidified samples were annealed in the unopened capsules for 10 days at 30" to 50° C below the respective solidus temperatures. The absence of microsegregation and second phases was confirmed by metallographic examination. At least two batches of each composition were prepared. 1.2) Solution Calorimetry. The heats of formation were determined by liquid metal-solution calorimetry. In this technique, the difference between the heat effects on dissolution in a liquid metal, or alloy bath, of the compound and a mechanical mixture of its annealed components, adjusted for changes in composition of the bath, is the heat of formation of the compound at the temperature from which the samples are added. Details of the equipment and technique have been described."&apos; A tin bath at 300" or 350°C was used with the compounds AuSn,, AuSnz, and AuSn. The high gold content of the £ phase would have caused it to dissolve with an appreciable exothermic heat effect. In order to achieve thermal compensation, the samples were added from 0°C to a bath at 350°C consisting of 66.2 wt pct Bi (99.999+ pct pure), balance Sn (99.99+ pct pure). This solvent gives thermal compensation because gold dissolves exothermically in tin and endothermically in bismuth. The calorimeter was calibrated by adding from 0°C approximately 0.015 g-atom of the solvent.

Jan 1, 1965

E. D. Peters, Jr., Dorchester, Mass.: This paper of Mr. Keller&apos;s seems to me a step in a direction that has been very little exploited, and iff likely to lead to valuable practical re-

Jan 1, 1899

By Frank Robertson Van Horn

In June, 1911, the writer spent a few days in studying the economic geology of the vicinity of Park City. During this rather hurried visit a number of specimens of ore were collected, which have since been examind. The results of these investigations show that bournonite (PbCu-SbSa) is present in the ores in greater or less quantity. This fact has never before been reported, as far as can be learned. The failure to recognize this mineral is due to its similarity to tetrahedrite, with which it has probably been confused during a long period of years. Jamesonite (Pb2sb2s6) has been reported from the region in a rather doubtful manner, but the writer has seen it in notable amounts from several mines, and can offer the first analysis of this mineral from the district. Calamine (HzZn2SiO5) was found at one mine and has never been ecognized and reported from the district. Geogbaphy and Geology Park City, Utah, is located at an elevation of about 7,000 ft. above sea level on the eastern slope of the Wasatch mountains. It is situated approximately 25 miles southeast of Salt Lake City. &apos; The geology and ore deposits have been described in detail by Bout well and Woolsey.&apos; The mines visited are situated south-southeast from the town. The Silver King Coalition mine is located in Woodside gulch about 1 mile southeast of Park City, at an altitude of about 8,100 ft. The other mines visited were the Daly West and Quincy, which are in Empire canyon about 2 miles sontheast of the town, at elevations of 8,300 to 8,500 ft. respectively. The Daly Judge tunnel goes into the mountain from Empire canyon about 1 mile south of the city, at an altitude of 7,700ft.

Jan 1, 1915

By R. E. Radabaugh, J. M. Brown, J. S. Merchant

The Gilman district is on the northeast flank of the Sawatch Range in central Colorado. It has yielded a total of 10,000,000 tons of ore having a value of over $250,000,000. Paleozoic sediments intruded by a Tertiary quartz latite sill and unconformably overlying Precambrian intrusives and metasediments comprise the country rock of the area. The sediments strike northwesterly and dip 8° to 12° northeasterly. Structures in the Precambrian are related to the Homestake shear zone of the Colorado mineral belt. Only minor folding and faulting occur in the sediments. The principal ore bodies are massive sulfide replacement deposits in carbonate rocks. They consist of long, pipe-like mantos in the completely dolomitized Mississippian Leadville Limestone and funnel-shaped chimneys of copper- silver ore cutting across the Mississippian and Devonian strata. Mineralization is continuous from the chimneys into the mantos. The principal ore bodies are roughly in the shape of a four-tined fork which points up dip. Smaller manto deposits occur in the Cambrian Sawatch Quartzite, and fissure veins are present in the Precambrian rocks. The principal minerals in the mantos are marmatite and galena in a gangue of pyrite and manganosiderite. The chimneys consist of a central core of pyrite with erratically distributed chalcopyrite, tetrahedrite, freibergite, and occasional galena with a shell of zinc ore on the outer margin. Both the chimneys and the mantos are surrounded by imperfect shells of manganosiderite and sanded dolomite. The mineralization is of Laramide age. Hydrothermal alteration affects all rock units to varying degrees. Clay mineral alteration halos occur around the ore bodies. Hydrothermal solutions have developed sanded rock, rubble filled channels, and banded zebra textures, principally in the Leadville Limestone. Structural control of the ore bodies is not well defined. Both the location of the district and the chimneys are probably related to basement structures. The mantos are largely controlled by stratigraphic factors and a pre-Pennsylvanian karst topography in the Leadville Limestone, which were modified by hydrothermal activity, and by weak zones of northeasterly trending faults.

Jan 1, 1968

By G. L. Fisher, R. Maddin

The rate of self-diffusion in silver single crystals during torsional strain was measured over a wide range of tenperatures and strain rates. The torsional strain was applied in a cyclic manner by reversing the divection of twist aftev a certain fraction of the total strain was reached. Surface roughening was substantially reduced in cyclically strained specimens compared with those strained entirely in one direction. Diffusion coefficients were determined using a special sectioning technique whereby slices could be removed parallel to the surface of a strained torsion specimen. The accuracy of the technique was first determined using roughened specinzens statically diffused to various penetration depths. Simultaneous strain-diffusion experiments were then performed over the temperature range 550&apos; to 800 using strain rates of lo-&apos; to 2.2 x 10&apos; sec-&apos;. The increase in silver self-diffusivity during torsional plastic strain was small. In only one case was the enhancement greater than twice the static value of the diffusion coefficzent. The enhancements increased slightly with decreasing tenzperature and increased with increasing strain rate. A dislocation pipe mechanism of enhancement was found to explain the present results satisfactorily. The magnitude of the enhancements and the tenzperatures at which they were observed suggests that a steady-state dislocation density of 10&apos; to 109 dislocations cm-2 existed during the high-tempevature deformation. The diffusion coefficient in an fcc metal can be increased by 1) an excess concentration of point defects and 2) the rapid movement of diffusing atoms along grain boundaries and dislocations. Plastic deformation may be responsible for enhancements by both of these mechanisms. The results of simultaneous strain-diffusion experiments have caused a controversy over the magnitude of the effect of strain upon diffusion. Experiments reporting large enhancements have been criticized for the manner in which the diffusion coefficient was measured. Several of these experiments have been contradicted by other results obtained in a similar manner. No enhancement was reported by two investigators&apos;&apos;&apos; who performed their experiments at high temperatures where strain is expected to have little effect upon diffusion. A recent theoretical analysis3 indicates that strain enhancement by a vacancy mechanism will be small and exist only at low temperatures and rapid strain rates. It is doubtful whether any experiment has yet proven that strain enhancements can occur by an excess vacancy mechanism. In the present research, experiments were performed at extremes of temperature and strain rate in an attempt to measure enhancement of diffusion by strain. Self-diffusion of silver during torsional deformation was chosen since two separate investigations4j5 indicate that at least a small enhancement exists under these conditions. An accurate method of determining the diffusion coefficient, mechanical sectioning, was employed after a technique was devised to apply it to the roughened surface of a strained torsion specimen. First, the accuracy of the technique was determined for different penetrations (2fi). Then diffusion experiments were performed at temperatures between 550" and 800°C at strain rates of 10"" to 10"" per sec. I) EXPERIMENTAL PROCEDURE Preparation of Specimens. The experimental procedure detailing the growth of crystals, their treatment, and the annealing techniques during straining are contained in earlier publications.496 The dimensions and orientations of the torsion specimens are shown in Figs. 1 and 2. licatiin of Torsional Strain. The torsion procedure was changed from that used previously. The specimens were strained in cycles to reduce the gross distortion and surface roughening inherent in twisting to high strains in one direction. For all strains above 0.30, the total surface strain was obtained as follows: the specimen was twisted to 0.10 strain in a clockwise direction; the direction was reversed; the backlash in the torsion apparatus was taken up; and the specimen was twisted in a counterclockwise direction through the initial starting point to 0.20 surface shear strain in the opposite direction. The strain reversal took no more than 1 min to accomplish. The total accumulated surface shear strain was arbitrarily taken as the sum of the 0.10 strain in the clockwise direction plus 0.20 in the counterclockwise direction. Although cyclic torsional strain was beneficial, surface roughening and specimen distortion were not entirely eliminated. The variation in the diameter at various points on the specimen was often much greater than the depth of the diffusion zone. Since serious errors might result if specimens were sectioned in the usual manner, a technique of lathe sectioning was devised to allow sections to be taken parallel to planes of equal concentration.

Jan 1, 1967

Annual Meeting,Wallace, Idaho, Nov. 15-16, 1913. The third annual meeting, which was also the eighth consecutive meeting and the second to be held in the Coeur d&apos;Alène district, was held in Wallace, Idaho, Nov. 15-16, 1913, with side trips to Kellogg-Wardner, Larson, and Mullan, where several mills were visited. The meeting was held jointly with the Montana Section, about 50 members and guests being present. Headquarters were in the Samuels Hotel, sessions being held in the public library. The arrangements and program were in the hands of the following local committee: George W. Roddewig, W. Earl Greenough, H. M. Childs. At 2.30 p.m., Nov. 15, the first session was called to order by Prof. F. A. Thomson, member of the Executive Committee, adjournment being taken to the Mine Rescue car, where Mr. Anderson and his assistant entertained the visitors for nearly two hours by demonstrations of mine-rescue and, first-aid practice, after which the party visited the Hercules mill, mention of which was made in the report of last year when the Section visited the plant. There are, however, several important alterations and additions to the flow-sheet to be noted, such as substitution of Chilean and Hardinge mills for the Huntington mills in the regrinding department; rearrangement of the tables and slimers, with a noticeable addition of the later models of the Franz machines, and the installation of the Wyman flotation process, which has been tried out, or is being tested, with more than ordinary success, on the middlings in several of the mills of the district, the Green Hill Cleveland mill being provided with a 100-ton unit, partly described below

Jan 12, 1913

By J. J. Fritts, J. L. Patrick, T. L. Wright, C. O. Ensign, W. S. White, J. W. Trammell, J. C. Wright, D. J. Hathaway, R. J. Leone

The copper deposit at White Pine, Michigan, from which a little more than 5 per cent of United States primary copper currently is produced, is a large stratiform orebody, 4 to 25 feet thick and several miles across. The present ore column, containing about 1.2 per cent copper as chalcocite and native copper, is confined to the basal beds of the Nonesuch Shale. This upper Keweenawan (Upper Precambrian) formation is a distinctive gray siltstone unit, about 600 feet thick, overlying and overlain by thick red-bed sequences. All these rocks contain abundant volcanic debris, but the latest known igneous activity within 50 miles antedated the Nonesuch Shale. The rocks are unmetamorphosed and only moderately deformed, mainly by tilting and faults. Pyrite, presumably syngenetic, is the only prominent sulfide throughout most of the Nonesuch Shale. The basal beds of the formation, however, contain disseminated copper minerals instead of pyrite and constitute the cupriferous zone. On a regional scale, the top of the cupriferous zone cuts across bedding, and ranges from an inch or so above the base of the formation in some areas to more than 50 feet in others. However, within the cupriferous zone the distribution of copper shows remarkable stratigraphic control. Certain beds are copper-rich compared to the beds that lie between them and the differences persist throughout the White Pine region. Several darkgray thinly laminated beds in the lower 10 to 25 feet of the Nonesuch Shale are rich enough and sufficiently close enough together to constitute a mineable thickness where they lie within the cupriferous zone. Pyrite is the characteristic sulfide of the Nonesuch Shale as a whole. The principal sulfide mineral of the cupriferous zone at the base of the formation is chalcocite. The succession of minerals outward and upward from the center of the cupriferous zone is native copper-chalcocite-bornite-chalcopyrite- pyrite. The bornite and chalcopyrite are confined to a narrow fringe at the margin of the cupriferous zone. This pattern of mineral zones is believed to represent reaction between syngenetic pyrite and introduced copper. The main copper mineralization is independent of structure and apparently antedates deformation. Details of the geometry of the cupriferous zone indicate the possibility that copper was introduced from the underlying sandstone prior to lithification. The source of the mineralizing solutions and their copper is not known.

Jan 1, 1968

By N. A. Gjostein

The real and apparent dependence of the surface self-diffusion coefficient, Ds, of gold on crystallo-graphic orientation has been investigated by isolated scratch smoothing and grain boundary grooving experiments. No systematic variation of Ds with orientation was found along the [100] zone. In view of the experimental scatter in these results, however, only aniso-tropy ratios, p, greater than -1.3 would be detectable. Anomalously low values of Ds were found on the [0ll] and [110] zones when the diffusion direction lies along (the scratch or grain boundary groove is perpendicular to) these zones. By comparing these results with a previous y plot study of gold, it is hypothesized that this is not an intrinsic diffusivity effect, but rather it results from a decreased driving force for mass transfer at orientations where the y-plot curvature is negative and appreciable in magnitude relative to y. The characteristics of this type of anisotropy do not appear sEVERAL investigations1-7 have dealt with the anisotropy of the surface self-diffusion coefficient, Ds, of metals as measured by the decay of single or multiple to be in agreement with the hypothesis of fast diffusion along ledges in the surface structure. In certain cases the Fourier method of determining Ds, described in Paper I of this series9 was compared with the second moment analysis in order to determine whether or not the method of analysis affects the anisotropy ratio. While the type of analysis does influence the magnitude of the anisotropy ratio, this effect is not associated with the shape of the profile, but rather is connected with the iterative volume diffusion correction used in conjunction with the second moment analysis. It is further demonstrated that the volume diffusion correction can be too large by either method when the y-plot curvature effect is large. Certain orientations exhibit an unusual temperature dependence of Ds ; this is discussed in terms of the y-plot curvature effect and/or the influence of impurities on Ds . scratches in the surface. Depending on the system investigated, both large1"3&apos;6&apos;7 and small4&apos;5 anisotropies in Ds have been found. Although adsorbed impurities undoubtedly play an important role in determining the magnitude of the anisotropy,8 there are other factors that can give rise to an apparent anisotropy in Ds, thus obscuring the true nature of an intrinsic anisotropy in

Jan 1, 1968

By D. L. King, C. D. Rubert, R. W. Christy, B. A. Schepman

R. W. Christy (Manager of Sales, Sanitary Engineering Equipment, Link-Belt Co.) and C.D. Rubert (Barrett, Haentjens & Co.) — Messrs. King and Schepman have presented an excellent paper which outlines the general practice in the design of thickener mechanisms. Lifting devices, controls, special applications and underflow pumping arrangements have been reviewed in detail. Pumping arrangements were illustrated which eliminate the need for an expensive tunnel beneath the thickener floor. Most of those illustrated have the common feature of a relatively long underflow suction line extending from the hopper floor to the pump located on the bridge at the periphery of the tank. The authors limit these arrangements to comparatively dilute or thin slurrys. It is implied that dense and coarse concentrates, which are difficult to pump, cannot be handled unless a tunnel is constructed. Fig. 1 shows an underflow pump arrangement which negates the need for a tunnel but which permits the operator to convey a heavy dense slurry. The pump is mounted directly on the fixed hoist platform and the impeller is located at the base of the steel center column. Priming water is not needed. The column

Jan 1, 1963

Jan 1, 1967

By H. B. Pulsifer

ONE of the most common basic open-hearth furnace products is a simple carbon steel with a carbon range from 0.05 to 0.15 per cent. The material is widely used for sheets, tubes, bars, wire and the innumerable special objects of secondary fabrication. The properties of the material vary over wide ranges, depending on the more exact composition and details of manufacture or treatment that affect its structure. The present paper is a review of those properties and structures that have been found by studying this steel as used in the cap screw industry. At first glance this might be thought a narrow application of the steel, but, since the industry uses the material in the cold-worked, annealed and heat-treated conditions, the title of the paper may be excused for its comprehensiveness. Yet, in studying the wide ranges of properties and structures that preclude a more specific title, there can be no suggestion of completeness or finality. Even a summary of a few years&apos; work is no more than a preliminary survey of a field that will be fertile in scientific data and industrial products for many years to come. An outline of the structures will be given first, then a list of the previous contributions that are at hand and finally some details of the work and related problems, especially concerning this low-carbon steel in the surface-hardened condition.

Jan 1, 1931

By Euzebio De Oliveira

ONE of a recent batch of samples from the Serra da Baliza, in the state of Parana, Brazil, contained asphalt and a dark heavy oil; and workmen on the railway from Porto União to Uruguay discovered asphalt, coming from eruptives that outcrop along the Rio de Peixe. The occurrence f asphalt in the triassic eruptives of southern Brazil, however, has been known a long time, according to Dr. Gonzaga de Campos. It is generally believed that the Botacatú sandstone is always a hard vitrified rock, from the metamorphic action f. the overflowing eruptive contacts. In this region, however, the contact metamorphism is almost nil; the sandstone is slightly hardened in a narrow zone about 20 to 30 cm. wide. In many places, the sandstone is so friable as to be easily reduced to sand, which is used-.in, mortar for building in Guara-puava and Palmas. South and west from Porto União,. this bench of sandstone is about. 50 m. thick, and is capped by a heavy bed. f basic eruptives, many of which are amygdaloids. Dr. Geo: P. Merrill, after studying the triassic eruptives collected by the Coal Commission, reached the conclusion that. "All these rocks are of typical basalt-diabases, not in any essential different other than in structure. An interesting mineralogical phase is its paucity in olivine, which in many cases is completely lacking. Professor Hussak, who carefully studied these rocks and their accessory minerals, decided that in the dikes they are granular (diabase) and, that in the lava sheets, porphyritic (augite-porphyrite or melaphyre), and that the latter pass evidently to normal diabases and are always typical of effusive rocks. The examination f many slides from dikes and sheets leads us to adopt the opinion of Professor Hussak; the rocks of the dikes are of ophitic structure, while that of the sheets show a great variety f structure and may vary from almost granular to basaltic. The great paucity in olivine had been noted by Hussak, who classes as melaphyres, the porphyritic triassic rocks in Brazil which contain olivine.

Jan 4, 1921

By O. U. Bradley

THE extent of losses, due to evaporation, sediment, and water, in crude oil stored in steel tanks, is a very interesting question, and particularly so at this time, when every reasonable measure should be employed to eliminate all possible losses of this important natural product. Available information on this subject is incomplete; e.g., during the development of the Cushing Field, considerable surplus oil was stored in steel tanks, but from time to time, owing to changes in weather, somelosses by evaporation and short storage room on the leases, these tanks were topped out, thus rendering inaccurate any system designed to determine the average rate of evaporation or other losses of the oil over a given period. , Furthermore, the losses, as shown by the records at the time, as a result of hasty gages, failed to take into account the temperature and gravity of the oil. Losses may be classified roughly as occurring from evaporation, presence of sediment and water, and leakage. The coefficient of expansion and contraction of crude oil, in relation to temperature conditions, is of material importance; also, the rate of evaporation is dependent upon the gravity of the oil, as the escape of the lighter hydrocarbons in fresh Cushing oil, of from 40 to 42 gravity, on a warm day is considerable, and from available records of temporary storage, it is safe to assume that a loss of 1 to 13 per cent. in volume will easily occur in light crude oil of Cushing grade over a period of. 6 months, including the summer season. The presence of sediment, water, and other impurities, in the oil will also cause, more or less deterioration in quality, particularly when the fresh production is run direct from the. gage tanks, or from the wells on the lease to steel storage, as is often the case when an oil field is being rapidly developed. The bad oil will settle to the bottom of the tanks and may be determined by thiefing and running a centrifuge test on the sample. The amount of water in the oil depends entirely on the conditions under which it is produced. Sometimes in large producing wells, with heavy gas pressure, some water may come in with the oil, particularly if the well has been drilled to the top of a water sand. Under these conditions, cut oil is often produced, which, if not settled out, is carried over into the steel tanks.

Jan 7, 1918

By H. E. Elliott, R. S. Busk, A. T. Peters

One of the problems of the fabricator of metals and alloys is the propensity of some composition rarnges toward abnoermal grain growth during certain stages of fabrication. In this respect magnesium alloys are no exception among alloys. Fortunately, convenient foundry control methods have been developed by which the abnormal grain growth possible in certain magnesium-alloy castings can be suppressed. An unusual characteristic of magnesium alloys, however, is that castings of some composition ranges are subject to local grain growth during heat-treatment without the necessity of intentional mechanical stressing of the part prior to heat-treatment. This effect occurs only under certain critical casting conditions, and only in certain alloys of greater than about 8.5 per cent aluminum content, such as C alloy (Mg, 9 per cent A1, 2 Per cent Zn, 0.2 Per cent Mn) and G alloy (Mg, 10 per cent Al, 0.2 per cent Mn). The first observation of this phenomenon in cast magnesium alloys occasioned much surprise, since it is not observed in other meta1s- Jeffries and Archer1 have stated that "the grain size of cast metals, provided they have not been plastically deformed, cannot be changed by heating below the melting point." The study of the conditions leading to abnormal grain growth in cast magnesium alloys, and of the mechanism of this phenomenon, has led to some very interesting observations. Perhaps the most significant of these was the observation that stresses originating from cooling contraction in magnesium-alloy castings are the only stresses necessary, under certain conditions, to cause local recrystallization and subsequent grain growth in the casting during heat-treatment. Before recent developments, this phenomenon of abnormal local grain growth Was a definite problem in the production foundry on C alloy sand castings. Illustrated (Fig. I) is a picture of a casting scrapped because of this defect. A mottled effect is produced in coarse-grained areas by suitable etching solutions. The properties of metal in the affected area are much impaired by such grain coarsening. Ultimate tensile strengths of half the normal value have been measured in metal of this nature. In this paper are described the techniques that have been developed by The DOW Chemical Co. for studying, and in large measure solving, this production problem. Also discussed are studies of the mechanism by which excessive grain coarsening occurs, and the fundamental conditions that produce this effect. The abnormal grain growth discussed in this paper will be referred to as "germinasium since this term has been definedl as any process leading to an abnormally coarse grain size. This paper deals only with abnormal local grain growth that may occur during the solution heat-treatment of certain magnesium-alloy castings, as dis-

Jan 1, 1945

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 Philip N. Adler, Harold Margolin

Univariant equilibria between the Ibcc, IIhcp, and UIfee phases of thallium have been determined and indicate a triple point at 110°C and 37 kbars. Calculated II —I transformation curves are compared with the experimental. Transformation volumes and/or enthalpies are calculated and enthalpies are compared with available data. ThE triple point of solid thallium has been reported by Bridgman as 153°C and 38 kbar.&apos; More recently, Jayaraman et at.2 have reported the triple point as near 115°C and 39 kbars. Meyerhoff and Smith,3 assuming the elevated-pressure modification of thallium is fcc, as Kaufman suggested,4 and that it is continuous with the room-temperature fcc phase in the Tl-In system, have used pressure data up to 5 kbars to predict the triple point at 162°C and 35.8 kbars. Piermarini and weir5 have indeed found the elevated-pressure phase to be fcc. The effect of variations of pressure and temperature in the IIhCp — Ibcc transformation in thallium have also been reported by werner6 and more recently by Ponyatovskii.7 The work reported here is part of an investigation of the effects of temperature and pressure on the Tl-In system. I) EXPERIMENTAL PROCEDURE The onset and progress of transformation were determined by changes in resistance. A commercially available tetrahedral-type pressure apparatus was used. Specimens of 0.060 in. diam, representing 0.63 pct of the cell volume, were encased in AgCl and mounted in pyrophyllite, as shown schematically in Fig. 1. It can be seen that the specimen is in series with the graphite furnace. Resistance changes of 0.1 pct could be detected with a Kelvin bridge. Resistance of the sample was of the order of 1 milliohm. Other pertinent details in regard to calibration and cell-assembly design are given elsewhere.&apos; Temperature calibration of the cell was carried out in two ways as a function of input wattage. Through a hole drilled in the graphite furnace, a chromel-alumel thermocouple was inserted into the AgCl to a point 0.010 in. from the sample, with the

Jan 1, 1964

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&apos;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&apos;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.&apos; 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&apos; 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&apos;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.&apos; 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

By P. J. Closmann

Steam zone growth as a function of time has been calculated for the case of constant rate steam injection into a preheated reservoir. To simplify the calculation a linear temperature profile has been assumed in the cap and base rock at the start of steam injection. The results indicate that at early times augmentation of steam zone growth due to preheating should be greatest. At longer times the steam zone development becomes close to that calculated with no preheating. INTRODUCTION With the increasing application of thermal recovery processes to recover viscous oil, cyclic steam injection has become important in many large-scale projects. In this process, the cycle of steam injection followed by oil production is repeated a number of times. At the beginning of the second and later cycles, steam is injected into a reservoir that has already been heated but that has lost part of its heat both in produced fluids and by conductive heat loss away from the injection zone. In such a case, the temperature level of the injection zone and the temperature distribution of the surrounding rock will affect the growth of the steam zone developed during the subsequent steam injection. Knowledge of the size of steam zone developed is important in determining the amount of oil displaced and the extent of heating in the reservoir. It is also useful to be able to compute the size of the steam zone for cases where thief zones take most of the injected steam. This paper presents a fairly straightforward method of estimating the steam zone developed in a preheated formation, based on certain simplifying assumptions. Some cases of steam injection into a reservoir at its original temperature have already been considered elsewhere.1-3 Because it is difficult or impossible to obtain an accurate representation of the temperature distribution in the reservoir some time after initial heating has taken place, in this work, a linear temperature profile in the cap and base rock is assumed (Figs. 1A and 1B). The linear profile has the advantage of yielding heat flow equations that

Jan 1, 1969

By F. I. Stalkup

Vapor-liquid phase equilibrium experiments have been conducted in a static equilibrium cell on mixtures of a light, 45 API stock- tank gravity reservoir fluid and a rich hydrocarbon gas containing approximately 55 mole per cent of intermediate hydrocarbons. Both apressure-vs-composition study of the gas and a simulated reservoir fluid, and a multiple-batch contact simulation of the condensing-gas-drive oil recovery process were performed. In the latter experiments equilibrium gas and liquid compositions were analyzed. Also, conventional, "condensing-gas-drive", long-tube displacement experiments of the reservoir fluid and gases of various richness were performed. The results of these experiments could not be satisfactorily interpreted by the conventional pseudo-ternary-diagram representation of multicom-ponent phase behavior. The results seem to be explained better by considering a bubble-point surface and a dew - point surface joined in a plait-point locus. Portions of the plait-point locus cannot be "seen" directly by the rich hydrocarbon gas because of curvature of the dew-point surface. In such a system, continuous injection of the rich gas over stationary reservoir fluid might form a zone of contiguously miscible compositions from pure rich gas to pure reservoir fluid by: (1) saturating the reservoir fluid with injected gas to the bubble-point surface; (2) creating by mass transfer with fresh injected gas a path of contiguously miscible compositions along the bubble - point surface to the plait-point locus; and (3) creating by mass transfer with additional injected gas a path of gas compositions along the dew-point surface up to the point where direct miscibility results between dew-point fluid and the injected rich gas. INTRODUCTION The use of the pseudo-ternary-phase diagram to illustrate miscible displacement phase behavior has been discussed by several authors.5,7 Such a representation of phase behavior is not rigorous, but the ternary diagram nevertheless gives a qualitative picture of what actually occurs in a miscible displacement process. Fig. 1 is a typical illustration of miscible displacement phase behavior by a ternary diagram. The multicomponent hydrocarbon system is divided into three pseudo-components: a light fraction containing methane and nitrogen, an intermediate fraction containing ethane through hexanes plus carbon dioxide, and a heavy fraction containing heptane and heavier components. A two-phase region is bounded by a dew-point curve and a bubble-point curve, which are joined at the critical point. The concept deduced from such a representation for miscible displacement by a condensing-gas-drive process is as follows: a rich gas G, which lies to the right of the limiting tie line through the critical point C, is injected into the reservoir and contacts reservoir fluid L, saturating the reservoir fluid to give bubble-point fluid L1 and equilibrium dew-point gas GI. Continued injection of rich gas changes the composition of the saturated liquid L1 through a series of liquid compositions lying along the bubble-point curve, until the critical composition C is reached, at which point direct miscibility with the rich gas is achieved. Some equilibrium gas with compositions lying along the dew-point curve from G1 to C is also formed in this process. Thus, continuous injection of rich gas forms a

Jan 1, 1966

By Walter J. Mead

By American tradition, if not by rational decision, publicly owned natural resources have been transferred to private industry for processing. The process of transfer requires specific determination of the price which the patentee, buyer, or lessee must pay to the government in exchange for the right to develop a resource, and selection of the patentee, buyer, or lessee from among several possible contestants. Pricing of natural resources owned by the government presents a set of problems quite different from ordinary commodity pricing. Natural resources in situ are not homogeneous commodities. Within any class of natural resources, specific leasable parcels will differ in value by reason of location and accessibility, as well as quality and quantity. Thus, there is no "going price;" every lease within a specific resource class will have a different value. To complicate further the pricing and buyer selection problems, competition may not be reliable. Natural-resource markets are characterized by oligopsony conditions. In a significant number of cases, as will be shown later, there has been only one bidder for a given lease, and in most lease sales the number of bidders is equal to or less than three. As a further complication, there is great uncertainty regarding the value of specific resources, even among the best-informed buyers, as well as within the leasing agency. In some instances, particularly with regard to oil and gas resources, there may be uncertainty about the presence of resources, as well as the quantity and quality of any resources contained in the tract offered for lease. In other cases, such as oil shale and some deep ocean minerals where new technologies are involved, the presence of the resource is clearly established. There may be a relatively high degree of knowledge about the quantity and quality of the resource, but there is great uncertainty concerning the cost of production. These problems in total make it difficult for the leasing agency to appraise accurately the resource to be leased, as well as for the potential bidder to calculate a bid price that will yield him a normal profit. The pricing goal of the federal government as the seller or lessee may be to capture the economic rent; that is, the price of a resource might equal its discounted present value. A required price substantially above this amount would either generate no bids, or, in the long run, would bankrupt the buyer. A price below this amount is a disguised subsidy to the lessee. A subsidy to mineral lessees, as to any other economic interest group, as a minimum should be justified by a clear showing of net external benefits from the economic activity. In the case of timber sales by the U.S. Forest Service, the Forest Service Handbook asserts that "the aim in national forest stumpage appraisal is to determine market value,"8 and "market value" is equated to "fair market value." Regarding minerals, there is no reference in legislation or regula-

Jan 1, 1976