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By A. W. Sommer, H. H. Kellogg

It is shown that SO3-O2 mixtures react with sphalerite at an appreciable rate ill the temperature range of 361° to 527°C to fornz ZnSO4. The rate of reaction follows a parabolle lax. Oxygen, or O2-SO2 mixtures, have a negligible effect on sphalcrite in the same temperatuee range. PRACTICAL roasting of sphalerite is usually performed at 800°C or higher. The calcine is composed of zinc oxide unless the roaster atmosphere contains relatively large amounts of SO2 and the temperature is held to 800oC or lower, in which case zinc sul-fate may also form. Ong, Wadsworth, and assell' have made a careful kinetic study of sphalerite oxidation under these "normal conditions" and have concluded that the rate of the reaction is controlled by the decomposition of an activated complex adsorbed on the sphalerite surface. They found the rate of oxidation to be small at 700°C. Extrapolation of their data to 400°C would indicate an almost negligible rate at this temperature. In our work sphalerite was reacted with air, mixtures of SO2, O2, and N2, and mixtures of SO3, O2, and N2 in the temperature range 361o to 527OC. Negligible rates of oxidation were found, except for the gas mixtures containing SOs. With this latter gas, the oxidation of finely divided sphalerite was fairly rapid and zinc sulfate was the product. Based on the limited evidence available, the rate of sphalerite oxidation by SO3 is postulated to be controlled by gaseous diffusion through pores or cracks in the zinc-sulfate coating. This evidence for the direct reaction of sphalerite and SO, at low temperature may prove of importance to the understanding of zinc-sulfate formation in the dust-collecting equipment usually associated with zinc roasters. The roaster gas carries off fine dust, much of which may be unreacted sphalerite. The temperature in dust-collecting equipment drops from the roaster temperature (about 800°C) through the range of temperature we studied, to ambient temperature. Such dusts are known to contain far larger amounts of zinc sulfate than the primary calcine. It has been assumed in the past that this sulfate is formed by reaction of ZnO dust with SO3 (or SO, plus 0,) in the partly cooled gases. Our work shows that an alternative possibility exists—the direct reaction of SO3 with ZnS dust. EXPERIMENTAL Reaction rates for sphalerite at 350° to 600°C are relatively small so that it was necessary to use finely divided material with a relatively large surface area in order to obtain measureable amounts of reaction. In the preliminary experiments, pure mineral sphalerite, ground to pass a 325-mesh sieve, and chemically precipitated ZnS (in the form of an impalpable powder) were used. In the quantitative rate experiments the ground mineral sphalerite was processed in an Infrasizer to obtain a product with particle size between 9 and 18 µ. The analysis of this material was 66.7 pct Zn, 0.09 pct Fe, and 32.7 pct S (theoretical sphalerite is 67.1 pct Zn, 32.9 pct S). The sized powder was carefully mixed and divided into l-g samples. The apparatus used for the quantitative rate measurements is shown in Fig. 1. For the preliminary experiments the following change was made: The external catalyst furnace (B, C)* was not used. *Letters refer to Fig._______1 .___- Rather, when catalysis of the SO2 + O2 reaction was desired, the glass beads in basket M were replaced by vanadium-oxide pellets. Procedure—A l-g sample of ZnS was placed on a shallow stainless-steel tray, I, and spread evenly to a depth of about 1mm. The tray was placed in the reaction assembly and the assembly inserted in the cold furnace. The furnace tube was flushed with dry argon and then heated to the desired reaction temperature. The temperature was controlled to ±0.5oC. Gas mixtures (O2 + N2 or O2 + SO2) were prepared from tank gases by means of a mixing device identical to that employed by Darken and Gurry.2 The total flow rate of gas was 205 ml per min to point A of Fig. 1. The accuracy of the individual and

Jan 1, 1960

By F. W. Warnaars

The Los Bronces copper deposit is located on the west side of the Andes Mountains in central Chile about 54 km (34 miles) northeast of Santiago. The deposit consists of a hydrothermal breccia complex that was emplaced in the western part of an earlier porphyry copper mineral system. This system exhibits propylitic, sericitic, silicic to potassic hydrothermal alteration with disseminated and stockwork copper-molybdenum sulfide mineralization over an area of about 12 km2 (5 sq. miles). The Rio Blanco Mine, about 800 m (0.5 miles) east of Los Bronces, is an underground block caving mine located in the central part of this system. The mineralization at Rio Blanco is characterized by one of the highest primary copper grades known for porphyry copper systems. Present mining at Los Bronces is from an open pit located in the northern part of a hydrothermal complex that is composed of at least seven different copper-bearing tourmaline breccia pipes. Together these pipe form one large contiguous body about 2 km (1.2 miles) long and 0.7 km (0.4 miles) wide at the surface. This body crops out at elevations of between 3.5 and 4.1 km (2 and 2.5 miles) above sea level. Each breccia pipe has a characteristic shape, matrix, type and degree of mineralization and alteration. Quartz, tourmaline, specularite, anhydrite, pyrite, chalcopyrite, sericite, chlorite, and rock flour are present in significant quantities in most breccia matrices. The clasts consist mainly of quartz monzonite, andesite, and minor amounts of quartz latite porphyry. The seven different breccia pipes are identified, from oldest to youngest, as Ghost, Central, Western, Infiernillo, Fine Gray, Anhydrite, and Donoso. The breccias coalesce, interfinger, or display gradational contacts. In places they form sharp contacts with each other and with the surrounding intrusive or volcanic host rocks. Early breccias are disrupted or cut by subsequent breccia events. Explosive emplacement was followed by collapse after the release of hydrothermal pressures. The Los Bronces breccia complex has sharp contacts with the surrounding intrusive stock and andesites. These contacts dip inward on the north, west, and south margins. The eastern contact is nearly vertical and/or dips slightly outward and suggests a westward tilting of the body of about 15° after emplacement. The breccia complex is not fully explored at depth, but is known to extend at least below the 3 km (2 mile) elevation in its central eastern part, about 1 km (0.6 miles) below the highest breccia outcrop. Primary copper sulfide minerals are most abundant in the Donoso and Infiernillo breccias where the matrix consists mostly of tourmaline, quartz, sulfides, specularite, and/or chlorite with minor amounts of rock flour, sericite, and clay. The volume of the matrix material is mostly smaller than in the other breccias. Secondary enrichment enhanced the primary copper grade in the southern two-thirds of the Los Bronces breccia complex and in much of the surrounding porphyry system. Primary grades of 0.3% to 0.5% copper have been enriched to approximately 0.9%. This enrichment may extend from surface outcrops to a depth of more than 500 m (1, 640 ft) in more permeable parts of the breccia complex. A leached and oxidized capping of variable thickness covers a large part of the enriched layer and exceeds 300 m (984 ft) at one location. The shape and depth of the enrichment blanket and the capping suggest that the enrichment process is still active.

Jan 1, 1983

By S. Saito, P. A. Beck

The crystal structure of MoNi3 was determined by means of X-ray diffraction. This structure is isotype with that of ovgered TiCu3. The lattice parameters are: a. = 5.064A, bo = 4.224A, co = 4.448A, and zf 0.157. If the orthorhombic distortion (slight relative to the corresponding orthohexagonal unit cell) is disregarded, the structure may be described in terms of a close-packed ordered atomic layer, stacked in the sequence: abab. The structztres of ordered TiCu3 and TiAl3 are homotectic. The three types of ordered hexagonal phases, iso-structural with TiNi3, MgCd3, and VCo3, are known to occur in AB3 alloys of transition elements of the first, second, ad third long periods. It was noted1 that phases with the TiNi3 structure occur selectively in alloys of Ti-group elements with Ni-group elements. In AB3 alloys of Ti-group and V-group elements with Co-group elements the AuCu3-type structure predominates.' The vCO3 structure, which was determined very recently,' has hexagonal symmetry, but the actual atomic arrangement here, too, is rather closely related to the ordered cubic structure of AuCu3-type. However, an ordered hexagonal close-packed structure of the MgCd3-type occurs in MOCO33 and WCO3.4 Consequently, the question arises as to whether or not the crystal structure of MoNi3 is also of the MgCd3-type. Grube and winkler5 found that MoNi3 has a hexagonal close-packed structure with a = 2.54A and c/a = 1.65. They pointed out that some additional weak diffraction lines could be observed in the powder pattern, which may have been due to an ordered atomic arrangement in this phase. However, no detailed information was obtained by them and the structure was apparently not further investigated by others. The present work was, therefore, undertaken in an attempt to determine in detail the structure of MoNi3, and to investigate the possibility of ordering. EXPERIMENTAL METHODS Alloys used in the present work were arc-melted in a water-cooled copper crucible under helium atmosphere. Electrolytic nickel and molybdenum, both 99.9 pct pure, were used. Chemical analyses were not made, but the melting loss was not higher than 2 pct for any alloy. Ingots were first homogenized at 1200°C for 48hr, quenched, heavily cold worked, and then annealed at 820" or 860°C for 1 week, followed by quenching in cold water. Powder specimens for X-ray work were prepared by crushing the heat-treated solid specimens. In order to remove strains, the powders were reannealed in evacuated scaled fused silica capsules for 6 hr at the same temperature at which the corresponding solid specimens were annealed. X-ray photographs were taken with an asymmetric focussing camera, using unfiltered CrK or CuK radiation. EXPERIMENTAL RESULTS The X-ray diffraction patterns of alloys containing 20.8, 25, and 26.4 at. pct Mo, homogenized at 1200°C, showed the face-centered-cubic structure of the Ni-base a-solid solution. It was revealed, however, by micrographic examination that the 26.4 at. pct Mo alloy contained in addition very small amounts of a second phase, in accordance with the phase diagram.6 On the other hand, the 20.8 at. pct Mo alloy after annealing at 820°C gave the X-ray diffraction pattern of the ordered face-centered-tetragonal MONi4.7 In this pattern several additional weak diffraction lines were also observed, corresponding to the strongest diffraction lines of MoNi3. The alloys containing 25 and 26.4 at. pct Mo after annealing at 820" or 860°C gave X-ray diffraction patterns, as shown in Tables I and 11, corresponding to MoNi3. Each one of the reflections which could be tentatively indexed on the hexagonal close-packed cell of Grube and Winkler,5 with the exception of the basal plane reflections, was split into a doublet, as seen in Table I. Since microscopically the alloy consisted of a single phase, it seemed probable that the lattice of MoNi3 is actually slightly deformed, as compared with the tentative hexagonal unit cell. In addition to these diffraction lines, several weak lines were also present, as shown in Table 11, which could not be indexed at all on the hexagonal close-packed cell considered. Satisfactory indexing of all diffraction lines observed was found to be possible by using an orthorhombic unit cell with ao = 5.064A, ft = 4.224A, and c = 4.448A. These values, whose accuracy is estimated to approximately ± 0.008A, correspond to 95.14A3 for the volume of the unit cell, and to an X-ray density of 9.50 g per cm3. If no attention were paid to the weak reflections listed in Table II, a reduced -unit cell of half the volume (a = 2.532A, b = 4.448A, and c = 4.224A), closely related to the orthohexagonal cell, might be used. The dimensions of the orthohexagonal cell of the same volume as the reduced cell are: a = 2.562A, b = 4.437 A, and c = 4.183A. It may be seen that in the reduced cell the a axis is slightly shorter, while the b and c axes are slightly longer than those corresponding to the orthohexagonal cell of the same volume. This slight orthorhombic distortion is re-

Jan 1, 1960

By J. B. Cohen, O. F. Kimball

Aging of specimens of Au-20 at. pct Ni and Au-40 at. pct Ni has been followed with electron microscopy, resistance, magnetic measurements, and X-ray diffraction. The periodic structures observed by electron microscopy in Au-Ni alloys by Fisher and Embury are shown to be due to nickel-rich prepre-cipitates. Assuming this alloy system undergoes spinodal decomposition, our observations and available data on thermodynamic properties and elastic constants indicate that the gradient energy coefficient in this system is of the order of 10-5 ergs cm-1 . Shifts of X-ray peaks in this system have been found to be due primarily to residual stresses, not faulting. A large effect of applied stress during aging was detected by X-rays and electron microscopy for the Au-20 at. pct Ni alloy. The presence of a preprecipitation stage during aging of gold-rich Au-Ni alloys for short times below 300°C has been indicated by several previous investigations. Changes in electrical resistivity,1"3 elastic modulus,4 superparamagnetisrn,5 positions of X-ray diffraction peaks,6 and hardness7 have been studied. Electron diffraction and microscopic studies by Fukano8 and Fisher and Embury9 respectively showed that the precipitation process resulted in the formation of periodic composition fluctuations—perhaps spinodal decomposition. MOSS10 detected a satellite with X-rays in quenched specimens, but the wavelength was much smallerthan that found by Fukano. Recently Woodilla and Averbac11 detected a modulation similar to that found by Moss, but with electron diffraction. They suggested that the microstructures observed by Fisher and Embury may be simply due to a Moir'e effect from a back deposit of gold during electropolishing. Satellites in electron diffraction can be enhanced by small bends or tilts of a foil. Even if this were not the case, asymmetric satellites, as are found in Au-Ni are difficult to analyze. They are principally influenced by the large differences in atomic size in this system, and obtaining information on the associated composition fluctuations depends on assumptions as to whether or not there are isolated clusters or composition "waves", and in the latter case whether or not the entire specimen has decomposed. Assuming that decomposition was complete in alloys aged at low temperatures, Woodilla and Averbach suggested that the satellites indicated a composition which varied about the average value by only± 5 pct, much less than that predicted from the phase limits, Fig. 1; they attributed this small variation to a cessation of the reaction caused by the loss of mobile vacancies. In Ref. 12 it was shown that vacancies are trapped by the preprecipitate in this system. Furthermore, after reversion, aging proceeds at a much slower rate than immediately after a quench from the solution temperature,5'11,13 indicating the importance of vacancies in the kinetics. In some senses Au-Ni is a favorable system for studying preprecipitation and reversion mechanisms because of the simplicity of the equilibrium diagram14 and the availability of good thermodynamic15 and diffusion data.16,l7 The calculations necessary to relate the decomposition process to classical nucleation and growth or to spinodal decomposition, as well as those necessary for understanding reversion mechanisms, can, therefore, be made. As an example, the position of the chemical spinodal, calculated from the thermo-dynamic data of Sellars and Maak15 with the method described by Rundman and Hilliard,18 is included in Fig. 1. It is compared to the chemical spinodal calculated from the equilibrium miscibility gap by Cook and Hilliard's method.l9 Included is the coherent spinodal suggested by Golding and MOSS," using measured elastic constants for their calculations and the same ther-modynamic data. The spinodal estimated by Woodilla and Averbach,11 by determining the temperature limits for the observation of the satellites discussed above, is also given. Actually this last curve is open to question on the following grounds: As a phase boundary is approached the spacing of particles or the wavelength

Jan 1, 1970

By L. K. Nemeth, H. T. Kennedy

The investigation presented in this paper was performd to develop a relationship between the dewpoint pressure of a hydrocarbon reservoir fluid and its composition, temperature and characteristics of the heptanes-plus fraction. This is part of an over-all program to develop correlations for the essential properties of reservoir fluids with the composition, temperature and pressure. In all, 579 dewpoint pressures, determined experimentally on 480 different condensate systems along with their compositions and temperatures, were obtained from the literature and from previously unpublished sources. Compositions were expressed in terms of mol fractions of methane through heptanes-plus, nitrogen, carbon dioxide and hydrogen sulfide, and the molecular weight and specific gravity of the heptanes-plus fraction. Distribution of the samples assured a good representation of most of the major oil-producing areas in the world. A multiple regression analysis program written for the IBhl 7094 digital computer was used to compare numerous equations and to calculate their coefficients. The final equation containing 11 coefficients resulted in an average absolute deviation of 7.4 percent for all the samples. Segregation of data on the basis of one or more variables did not materially improve the results. The correlation developed is useful in predicting the dewpoint pressure of condensate reservoir fluids from variables normally measured in the laboratory. INTRODUCTION In any discussion of the dewpoint of hydrocarbon mixtures, it should be noted that there are two kinds of dewpoints which must be distinguished. The first type, or normal dewpoint, usually occurs at low pressures as dry gas is compressed to the point where liquid first forms. The second type, sometimes called the retrograde dewpoint, occurs when a gas mixture containing heavy hydrocarbons in solution is depressured until a liquid is formed. The first type, as applied to condensate mixtures, would normally be below atmospheric pressure and would be of no interest in reservoir performance. The second type is of great significance in interpreting reservoir behavior and is the property referred to throughout this paper. Laboratory measurement of dewpoints is laborious, expensive and subject to many errors, and it is desirable to find a reasonably accurate method to predict dewpoint pressures from the composition and other readily available properties normally measured on the fluids. A possible method of calculating dewpoint pressures would be to employ a set of equilibrium ratios (K-values). 1 However, the K-values themselves depend on composition as well as temperature and pressure; presently their use adds nothing to the accuracy of predicting dewpoints. If future correlations provide a significantly better method of estimating K-values for heavy hydrocarbons, they may be of greater use. REVIEW OF LITERATURE In 1944, Olds, Sage and Lacey 2 studied the behavior of fluids from the Paloma field. Properties of seven mixtures were studied at temperatures ranging from 100 to 250 F and at pressures up to 5,000 psia. From the information obtained, the influence of composition and temperature upon the dewpoint was determined. It was found that removal of the intermediate molecular weight components from the mixture resulted in considerable increases in the dewpoint pressures. Results indicated that the effect of changes in temperature was relatively minor when compared with the effect of modifying the mixture by removing the intermediate components. Thus, removal of propane and butanes resulted in an increase in dewpoint pressure more than 10 times greater than a change in temperature from 100 to 250 F. The authors stated that althouah

By AIME AIME

THE complete list of papers for the meeting of the Petroleum Division that is to be held" at Tulsa,' Thursday and Friday, Oct. 3 and 4,, with assignment to individual sessions is given below. THURSDAY MORNING First Session Well Spacing Theory of Well Spacing-By W. P. Haseman. Discussion by S. C. Herold, J. R. Suman and Lester C. Uren. Well Spacing in the Long Beach Field, California-By - Stender Sweeney. Discussion by C. H. McNeese; R. R Brandenthaler and W. V. Vietti. Well Spacing in the Bradford Field, Pennsylvania-By Paul D. Torrey. Discussion by A. F. Melcher, R. M.. Haskell, J. B. Umpleby and J. B. Newby. Results of Different Well Spacing in the Salt Creek Field, Wyoming-By Fred E. Wood. Discussion by Sam Grinsfelder and Kenneth B. Knowles.

Jan 1, 1929

By E. T. Turkdogan, P. Grieveson, J. F. Beisler

Jan 1, 1963

By R. C. Hyslop

The object of this experiment was to obtain a usable set of field curves for determining the susceptibility of rocks with the vertical magnetometer. The need often arises for determining the susceptibility of rocks in the field in order to interpret magnetic anomalies obtained. This is particularly true when diamond drilling has been done and the relation to the surface rocks of the samples taken is desired. Many methods of measuring rock susceptibility have been developed, but in general they require careful shaping of the sample or pulverizing it in addition to delicate laboratory measuring instruments designed for the purpose. The requirements for a practical method for the determination of susceptibilities are as follows: 1. There should be as little alteration as possible of the specimen. 2. A minimum of time should be required in the preparation of the specimen and the calibration of the equipment. 3. Theequipment used should be portable. 4. An accuracy within the limits of the survey at hand should be obtainable. 5. A means of measuring the remnant magnetism should be available. Laboratory Procedure With these ideas in mind, the problem was approached in the manner in which Koenigsbergerl developed his method using the principle of the electrical theory of images of Lord Kelvin and applying it to the magnetic case. This solution of the problem states that the apparent change in the magnetic field intensity AZ due to the proximity of a specimen is given by: mk AZ = 2a2 Where k is the susceptibility of the specimen, m the strength of the pole of the needle, and a its distance from the surface of the specimen, as shown in Fig. r.2 This relation is true only for an infinite body and corrections are necessary for a finite body. Koenigsberger used in his work a variometer of special design. He suggested that a Schmidt vertical balance or horizontal magnetometer, as well as some other instrument, might be used. The Colorado School of Mines horizontal torsion magnetometer operates on this principle. In the

Jan 1, 1946

By R. C. Hyslop

The object of this experiment was to obtain a usable set of field curves for determining the susceptibility of rocks with the vertical magnetometer. The need often arises for determining the susceptibility of rocks in the field in order to interpret magnetic anomalies obtained. This is particularly true when diamond drilling has been done and the relation to the surface rocks of the samples taken is desired. Many methods of measuring rock susceptibility have been developed, but in general they require careful shaping of the sample or pulverizing it in addition to delicate laboratory measuring instruments designed for the purpose. The requirements for a practical method for the determination of susceptibilities are as follows: 1. There should be as little alteration as possible of the specimen. 2. A minimum of time should be required in the preparation of the specimen and the calibration of the equipment. 3. Theequipment used should be portable. 4. An accuracy within the limits of the survey at hand should be obtainable. 5. A means of measuring the remnant magnetism should be available. Laboratory Procedure With these ideas in mind, the problem was approached in the manner in which Koenigsbergerl developed his method using the principle of the electrical theory of images of Lord Kelvin and applying it to the magnetic case. This solution of the problem states that the apparent change in the magnetic field intensity AZ due to the proximity of a specimen is given by: mk AZ = 2a2 Where k is the susceptibility of the specimen, m the strength of the pole of the needle, and a its distance from the surface of the specimen, as shown in Fig. r.2 This relation is true only for an infinite body and corrections are necessary for a finite body. Koenigsberger used in his work a variometer of special design. He suggested that a Schmidt vertical balance or horizontal magnetometer, as well as some other instrument, might be used. The Colorado School of Mines horizontal torsion magnetometer operates on this principle. In the

Jan 1, 1946

By JO. E. SHERID

THE Dawson coal-mines are owned and operated by the Stag Canon Fuel Co., of which Dr. James Douglas is President and E. L. Carpenter general manager. The property is situated in Colfax county, N. M., and the openings now in operation are in townships 28 and 29 N. R. 20 E., and township 28 N. R. 21 E., shown in Fig. 1. The mines are part of the southern end of the Raton coal-field, which extends north into Colorado and embraces many coal-camps of the Trinidad section. II. GEOLOGY. Geologically, the coal-measures, commonly known as the Laranmie series of the Cretaceous system, have a thickness of about 800 ft. in the vicinity of Dawson. The coal makes an excellent coke, and, according to some authorities, its coking properties are clue to the action of intruded sheets and sills of igneous rock, the sheets occasionally thickening into masses resembling laccoliths, at such places making nearer approach to the coal and sometimes producing small areas of natural coke. There are but few dikes through¬out the entire southern portion of the field and little or no faulting along the dikes. In some parts of this great coal-field the intrusive sheets are far removed in the green shales below the coal-measures, and are so much altered as to be difficult of identification. There is but little disturbance of the strata through¬out the Raton coal-field in as far as it extends into New Mexico. There are two workable seams in the coal-measures, and two or three smaller coal-seams, ranging from 1 to 2.5 ft. in thick-

Jun 1, 1909

By Donald L. Katz

THE Oklahoma City Wilcox sand, discovered on March 26, 1930, has produced 394 million barrels of crude oil and 819 billion cubic feet of natural gas as of July 1, 1941. The 100,000-bbl. wells, pressures of 2600 lb. per sq. in., and flows of "Wilcox" sand caused exciting moments in the early life of the field. Today the reservoir is substantially at atmospheric pressure and produces 75,000 bbl. of crude oil daily through 466 pumping wells. Early estimates of the initial crude-oil content of the "Wilcox" sand' indicated that about 600 million barrels of crude oil would remain after the pumping wells ceased to produce economically. The Oklahoma City Wilcox Secondary Recovery Association was organized in March 1939, to study the possibilities of recovering a portion of this oil. Only a very brief summary of the information available can be presented in a paper of this nature. Some simplification and generalizations are necessary to give the over-all picture in so short a space and statements made may not apply to a specific well or small area. Since the area under consideration by the Association is that north of the south line of section 22-11-3, some information will be presented for areas A, B, C, r, 2, 3 and part of 4 of Fig. 2, and some will be for the entire Wilcox zone west of the fault. This paper is essentially an abstract of an engineering report made by A. D. Small, B. T. Murphree, M. C. Sons and the author for the Oklahoma City. Wilcox Secondary Recovery Association on Sept. 5;.1940. Some information is taken from a report to the Association by C. V. Sidwell on March 1, 1940, and some data are from a recent report by A. D. Small. It gives a brief history of the Wilcox zone, estimates of the initial oil contents of the reservoir, present conditions in the reservoir, and probable results from several programs of "secondary recovery." HISTORY OF WILCOX ZONE The Wilcox sand lies on the flank of the general structure, as shown by cross section of Fig. 12.1 .4 and areal map of Fig. 2. The sand is of Ordivician age and is composed of well assorted, rounded' sand grains with no apparent cementing material. The loose texture of the sand is shown by the enormous quantities of sand production from the wells and from the soft cores. The productive sand varies from zero thickness on the east to 220 ft. maximum and to zero thickness on the west because of water. The development of the pool4 was dependent upon drilling restrictions within the city limits, which accounts for the spacing of drilling operations listed in Table I by years. In 1931, areas I through 7 of Fig. 2 were open for drilling with the exception of some west-edge properties, and all wells drilled before Feb. I, 1935, were in this portion of the field. Nearly all wells drilled from 1933 to 1937 were in areas A, B and C. Since 1939, the newly drilled wells have gradually enlarged the producing area toward the west in the northern portion.

Jan 1, 1941

By N. A. Gokcen, J. Chipman

Aluminum and oxygen dissolved in liquid iron were brought into equilibrium with pure alumina crucibles and atmospheres of known H2O and H2 contents to study the reactions: 1—Al2O3(s) = 2 Al + 3 0; 2—Al2o3(s) + 3H2(g) = 2Al+ 3H2o(g); and 3—H2(9) +O = H2O(g). Aluminum strongly reduces the activity coefficient of oxygen and similarly oxygen reduces that of aluminum. Values of the product [% All" • [% O]3 are much smaller than those found in previous experimental studies and are of the order of magnitude of the calculated values. ALUMINUM is the strongest deoxidizer commonly A used in steelmaking, but the extent to which it removes dissolved oxygen has been debatable. The relationship between aluminum and oxygen has not been determined reliably not only on account of the usual experimental difficulties at high temperatures but also because of uncertainties in the analyses of very small concentrations of oxygen and aluminum. The earliest experimental attempt of Herty and coworkers' was followed by a more systematic study of Wentrup and Hieber.' These authors added aluminum to liquid iron of high oxygen content in an induction furnace and considered that 10 min was sufficient to remove the deoxidation products from the melt. Parts of the melts thus obtained were poured into a copper mold and analyzed for total aluminum and oxygen (soluble plus insoluble forms), assuming that the insoluble parts were in solution at the temperatures from which samples were taken. It is conceivable that the furnace atmosphere in their experiments, consisting of mainly air at 20 mm Hg pressure, was a serious source of continuous oxidation and therefore that their oxygen concentrations were correspondingly high. Scattering of their data was explained to be well within the maximum inaccuracy of 10°C in the temperature measurements and errors of ±0.002 pct each in the oxygen and total aluminum analyses. Maximum and minimum deoxidation values, i.e., values of the product [% All' . [% O] differed by factors of 10 to 15; mean values of 9x10-11 and 7.5x10-9 ere reported at 1600" and 1700°C, respectively. Hilty and Craftsv determined the solubility of oxygen in liquid iron containing aluminum, using a rotating induction furnace. Pure alumina crucibles used in their experiments contained the liquid iron which in turn acted as a container for slags of varying compositions consisting mainly of Al2O3, Fe2O3, and FeO. The furnace was continuously flushed with argon, and additions of aluminum and Fe2O3 were made in the course of each experimental heat. The inner surfaces of their alumina crucibles were covered with a substance other than pure Al2O3, containing both iron oxide and alumina. Although frequent slag additions can change the composition of slag in the liquid iron cup formed by rotation, the inner surface of the crucible must depend upon the transfer of oxygen or aluminum through the liquid iron for any adjustment in composition. It is not clear that their metal was in equilibrium with the crucible wall, but it is clear that it was not in equilibrium with Al2O3. Their deoxidation product, [% A].]" • [% O]3, varied by a factor of more than 50; the average values of 2.8x10- and 1.0x10-7 were selected for temperatures of 1600" and 1700°C, respectively. Aside from the experimental determinations, attempts have been made to calculate the deoxidation constant for aluminum indirectly from thermody-namic data. Schenck4 combined the thermodynamic data for Al2O3 and dissolved oxygen in liquid iron by assuming an ideal solution. His calculated values are 2.0x10-15 and 3.2x10-13 at 1600" and 1700°C, respectively. Later, Chipman5 attempted to correct for the deviation from ideality and derived an expression which led to deoxidation values of 2.0x10-14 and 1.1x10-12 at 1600" and 1700°C, respectively. The errors in these treatments originate mainly from inaccuracies of thermal data and uncertainties regarding the activity coefficients of dissolved oxygen and aluminum. The purpose of this investigation was to study the equilibria represented in the following reactions in the presence of pure alumina: Al2O3(s) = 2Al + 3O K = aAl2.ao3 [1] Al2O3(s) + 3H2(g) = 2Al + 3H2O(g) H2O K2 = aAl2(H2O/H2 ) [2] H2(g) +O = H2O(g) K3 = 1/ao (H2) [3] The experimental method consisted of melting pure electrolytic iron, usually with an initial charge of aluminum, in pure dense alumina crucibles under a controlled atmosphere of H,O and H2 and holding

Jan 1, 1954

The following is an incomplete list of members and guests who' called at Institute headquarters during the period Mar. 10, 1918 to Apr. 10, 1918. W. Sinclair Brown, Lebong Donok, Sumatra. F. Laroque, Roodepoort, Transvaal. H. B. Catlin, Syracuse, N. Y. A. H. Means, Camp Upton. A. R. Chambers, New Glasgow, Nova Scotia. J. H. Miles, Nome, Alaska. W. M. Corse, Buffalo, N. 1 . Harvey S. Mudd, Washington, D. C. George C. Crossley, Toms River, N. J. Henry Noyes, Melbourne, Aust. F. A. Dalburg, Montoursville, Pa. C. L. Petzel, Camp Upton. Kuno Doerr, El Paso, Tex. J. L. Schueler, Peoria, I11. V. E. Edwards, Worcester, Mass. J. G. Scrugham, Reno, Nev. H. F. E. Gamm, Rutherford, N. J. Frank M. Smith, East Helena, Mont. J. W. Gerhard, St. Louis, Mo. W. G. Swart, Duluth, Minn. Julius H. Gillis, Sudbury, Ont., Canada. A. L. Sweetser, Boston, Mass. S. J. Gormly, Guayacan, Chile. W. N. Thayer, Cincinnati, Ohio. Fletcher Hamilton, San Francisco, Cal. Felix E. Wormser, Cornucopia, Ore. Dorsey A. Lyon, Washington,. D. C. John B. Arnold has opened offices at 606 Lyceum Bldg., Duluth, Minn. E. E. Barker, formerly mine superintendent with the Chile Exploration Company at Chuquicamata, Chile, has resigned his position to become superintendent of mines for the Cerro de Pasco Copper Corporation at Cerro de Pasco, Peru.

Jan 5, 1918

By C. M. Wayman, J. F. Breedis

The crystallography of the martensitic transformation in the Fe-30 Ni alloy was reinvestigated. The scatter in the habit Plane as determined from measurements on the mid-rib plane was smaller than reported previously, and the orientation relationship was determined from a martensite plate having known direction cosines. From agreement with crystallographic theory and from observations of the morphnlogy of the martensite plates, it is suggested that the mid-rib plane represents the starting region of the transformation. THE crystallography of the martensitic transformation in the iron-nickel system has been the subject of many investigations.&apos;-7 However, for iron alloys containing approximately 30 wt pct Ni, a wide scatter in the reported habit planes exists. In only one instance has a Laue determination of the orientation relationship been made, but the habit plane of the martensite plate studied was not determined experimentally. Because the most successful thermodynamic and kinetic analyses8 of the martensite transformation have been based on Fe-30 Ni alloys, it was considered desirable to reinvestigate the crystallographic features of the transformation in this alloy. Lieberman9 suggested that the most significant information for use in a theoretical treatment involves the determination of all the crystallographic observables from a single plate of the product phase. This was first done in essence by Greninger and Troiano10 for Fe-22 wt pct Ni-0.8 wt pct C, and is the method followed in this investigation. Some theoretical approaches11-13 in describing the martensitic transformation consider the overall transformation distortion to be comprised of a Bain distortion, or lattice deformation (PI, which produces the structure change, and a lattice invariant deformation (G), such as twinning, which together leave the interface or habit plane un-distorted. The incorporation of a rigid body rotation (R) results in a transformation distortion (E) such that the interface plane is left both undistorted and unrotated. In matrix notation, E = RPG where the lattice invariant deformation has "taken place" in the austenite. Bowles and Mackenzie14-16 in formulating a theoretical approach proposed an adjustable scaler quantity, denoted as 6, which represents a uniform dilation in the interface plane. This dilation acts to adjust the lattice spacings of the parent and product structures at the plane of contact. Using the dilation parameter as a variable, these authors were able to account for a continuous variation of habit planes in steels along a curve in the stereogram between {225}A and {259}A. she invariant line strain14 of the transformation is 6 RP, and the corresponding transformation distortion is E/6.) With the dilation parameter known, the invariant line is computed as the triple coincidence of the habit plane, the shear plane of the lattice invariant deformation, and the initial Bain cone.14 The contraction axis for the Bain distortion can be taken9&apos;17 as [010]A, and the correct permutation of the habit plane indices used. Kelly and Nutting 18 have established the shear plane (of twinning) in the tetragonal martensite of Fe-22 Ni-0.8C to be {112)M by means of transmission electron microscopy. The reasonable shear system is then {112}M which is equivalent to {011}A <01l>A. The as-

Jan 1, 1962

By L. F. Elkins

In 1946 Littlefield, Gray and Godbold published a thorough geologic description of the West Edmond Hunton Lime reservoir, located in Central Oklahoma, and discussion of its early performance.l They stressed implications of the nature of the reservoir rock on performance to be expected with production both by natural means and by pressure maintenance with gas injection. The essence of their analysis was that presence of an extensive interconnected system of fractures and solution channels constituting about 10 percent of the total reservoir void space in otherwise very low permeability reservoir rock would result in severe channeling of naturally encroaching water or injected gas through the fractures with little or no benefit to ultimate recovery of oil. Considerations were in progress to unitize the reservoir for pressure maintenance by gas injection. Some other engineers involved in the project had considerably different opinions at the time regarding continuity of fractures and regarding effects of such fractures on performance. The field was unitized Oct. 1, 1947. Subsequently, pilot gas injection tests were conducted in four areas of the field; large scale waterflooding was conducted in two parts of the field in the Bois d&apos;Arc or Upper Hunton; and pilot waterflooding was conducted in the Chimney Hill or Lower Hunton. Full scale water-flooding is now in progress in the Chimney Hill section where it is oil productive. The primary purpose of this paper is to divine some of the secrets of this reservoir through analysis of all aspects of its performance, with the hope that it will be of help to engineers and operators in developing and operating other low permeability fractured reservoirs. In part, this considers variance of actual performance from some widely used conventional reservoir engineering assumptions. For brevity, other aspects of unit operation and its benefits to the owners are not discussed. Oil and Gas in Place For unit participation, net pay in the Bois #Arc defined by the gross SP anomaly on electric logs totalled 2,100,000 acre-ft in the 30,000-acre reservoir. Development of West Edmond predated modem logging techniques that now would be used to determine "net" or "productive" pay. In Fig. 1 this log pick is compared with detailed core analysis and core descripfion by Littlefield et a1.l for one well identified as A on the index map in Fig. 2. Not all of the gross Bois #Arc section had oil staining, but all cores with measureable intergranular permeability were stained. (The committee selection of the Bois d&apos;Arc SP interval also includes the Frisco section as identified from cores by Littlefield.) The Bois d&apos;Arc is oil productive throughout the entire 600-ft monoclinal accumulation from the eastern upstructure erosional pinchout to the west-side oil-water contact. (See Littlefield et al.l and McGee and Jenkins for geologic detail.)

Jan 1, 1970

By AIME AIME

THE Coal Division holds its fall meeting in the Pocahontas coal field, at the West Virginian Hotel, Bluefield, W. Va., Oct. 9 and 10. The first day will be a busy one-two sessions for the presentation of papers and a dinner in the evening. Hon. E. Fudge, Assistant Undersecretary, Mines Department, and R. V. Wheeler, head of the Mines Research Board of Great Britain, will be the guests of the Division. Mr. Wheeler will discuss the British Mining Act as relates to the coal industry. George S. Rice, Chief Mining Engineer, U. S. Bureau of Mines, will present an account of the recent meeting at Buxton in England, of representatives of England, Germany, France, Belgium and the United States to formulate a plan and to correlate research work now in progress in the various countries. The second day the members will be the guests of the operators on a trip through the Pocahontas field. The work of preparation for the meeting is being actively pushed by committees headed by T. H. Clagett, R. M. Lambie and H. D. Smith, and a good attendance, both local and from the general membership of the Division, is anticipated. Because many will make the trip by car the principal automobile as well as rail-road connections to Bluefield are given here. The program for Friday, Oct. 9, follows:

Jan 1, 1931

By H. B. Pulsifer

.ABOut 1.5 varieties, or tnodifications, of the best rnagnesiurn available were prepared and subjected to etching tests, then examined for micro-structure. Of the 30-udd etching reagents that were tried, nearly half, mostly ammonium salts, etched the metal satisfactorily. The surfacing and etching of magnesium is shown to be a very simple and quick operation. The density and hardness of magnesium were determined. The most interesting new observations relate to the finding of the hexagonal etch figures, the crystal laminations, and the fact that the metal is plastic, cold, when restrained or quickly deformed. Under slowly applied pressule cold metal deforms slightly, then shears to fracture without plastic flow. The chief structural features of magnesium arc presented in two reduced photographs and 30 photomicrographs. Materials Tested There are only two sources in the United States from which new metal can be procured: the American Magnesium Corpn. and the Dow Chemical Co. No pronounced structural or property differences in the metals from these two companies were disclosed by the work of this investigation. The following materials were obtained from the manufacturers: 1. Massive crystals of distilled metal (American Magnesium Corpn.). 2. Rods of hot-extruded metal, ½-in. squares and 5/8-in. rounds (American Magnesium Corpn.). 3. Sheet magnesium, 0.005-in. thick (American Magnesium Corpn.). 4. Cast stick metal, 13/8-in. dia. (Dow Chemical Co.). 5. Magnesium-aluminum alloy, hot-rolled plate, ½-in. thick (American Magnesium Corpn.). From these materials, were prepared: 6. Sections from a furnace-cooled ingot made from clistilled crystal. 7. Cold-strained pieces from (6), (4) and (2). 8. Pieces cold-squeezed to fracture from (6), (4) and (2). 9. Hammer-struck pieces from (6), (4) and (2). 10. Steam-hammer struck pieces from (6), (4) and (2). 11. Sections from furnace-cooled ingot of the magnesium-aluminum alloy.

By W. C. Knopf, G. Samsel

For several years International Minerals & Chem-ical Corp. has used a radiation method to assay potassium content of products from potash and feldspar beneficiation. The procedure is rapid, accurate, and inexpensive and is easily handled, if necessary, by nontechnical personnel. Data are presented to show the accuracies that may be expected if the technique is used for control of pilot plants or large-scale plants. Natural potassium is composed of three isotopes —K, K and K. Five other isotopes, artificially produced, have been detected. In natural potassium only the K isotope, with a half life of 1.4x10 years, is radioactive. Its modes of decay are beta and gamma rays, positrons, and x-rays. Only the more abundant beta rays, however, are important in radiation measurements using geiger tubes. Barnes and Salley&apos; measured radiation of potassium salts in solution in 1943. Gaudin and Parnell2 first reported the use of solid salts arranged in a vessel surrounding the ß counter in 1948. Later, Scheel used the method to assay potassium content of various crude and finished potash salts. Experimental: Dip-type Geiger-Muller tubes (TGC-5) supplied by Tracerlab Co. were used in all radiation counting measurements. The tube was encompassed by a glass container about M in. larger in diameter than the tube. This container, which served as a sample holder, was closed at the bottom with a rubber stopper to facilitate removing the samples. Samples were not weighed, but about 40 g of sample were needed for each test. Electrical impulses from the tube were counted on either a Tracerlab scaler or a rate meter. To obviate the need for constant attendance, preset features were incorporated into the scalers, so that at a predetermined time or count the units were automatically deactivated. When rate meters were used, counting rates were read directly from instrument or from a recorder used in conjunction with the rate meter. Each tube was calibrated, according to the manufacturer&apos;s instructions, to determine the correct operating voltage to insure reproducible results. A linear calibration plot of percent K2O vs counting rate was also obtained for each tube by recording the counting rate plus background count of several standards of different K2O content chemically analyzed by the chloroplatinate method.&apos; These standards were of approximately the same particle size distribution as samples to be assayed. Specific background count caused by cosmic rays and other surrounding radiation was checked periodically by counting a sample of pure NaCl. Fig. 1 is a representative calibration plot. Assays were determined directly from the standard plot or calculated by subtracting the background count from the counting rate, then multiplying by the slope of the line. Chemical assays of the test samples were made by the Sherril method," a flame photometric technique, or the chloroplatinate method. Data: The radiation assay method has been used for three years by International Minerals & Chemical Corp. in the laboratory and in pilot plants processing ores containing potassium. These dry concentration plants process sylvinite and langbeinite ores at Carlsbad, N. M., and feldspar ores at Top-sham, Maine. Sylvinite ore is predominantly a mixture of syl-vite (impure KCl) and halite (impure NaCl). Contaminants include sulfates, such as langbeinite (2MgSO - K2SO4), kieserite (MgSO H2O), poly-halite (MgSO4.K2SO, 2CaSO, . 2H2O), and slimes. Langbeinite ore is predominantly langbeinite and halite with small amounts of sylvite, sulfates other than langbeinite, and slimes. Several variables, in addition to correct calibration and standardization of tubes, were found to be important in obtaining reproducible results. Particle size distribution of standard samples should be

Jan 1, 1959

By Mary Barrett, Walter Rose

INTRODUCTION The conventional way to program reservoir problems* for solution on the electric analyzer1 is one which concentrates the block units towards the inner radius of the prototype system being represented by the analog model. This is achieved by the device of considering block units of equal value radial resistance, leading to the consequences: (1) the ratio of the external to the internal radius of each block unit is a constant (i.e. r1/ri-l = constant a); (2) the external radius of the nth block unit is equal to the innermost radius of the system times the constant a raised to the nth power: (3) the capacitance of the block units increase by a factor of a2 going out radially from the innermost to the outermost boundaries of the system; (4) given n block units in the radial direction, the capacitance ratio of the outermost to the innermost block unit is a (2n-2); and (5) the vertical resistance of the block units decrease by a factor of a going out radially from the innermost to the outermost boundaries of the system, such that the ratio of the maximum to minimum vertical resistance is also given by the factor a(2n-2) PRESENT PROGRAMMING METHOD While this conventional way of programming problems is quite adequate for routine uses of the electric analyzer, it leads to difficulties in those cases where the inner radius of the prototype system (e.g., the well-bore) is small compared to the external radius (e.g.. the external reservoir boundary). To handle such a case by the conventional method would require either that a large value be selected for the constant a or that a large number n, of radial block units be chosen. In consequence, the capacitance and vertical resistance ratios become impossibly large, as will be evident from the relations given above. In any event, the size of the smallest and largest capacitors will always be limited by the size of commercially available components, and the analyzer itself will determine how many mesh points are available for radial block units. For example, it can be shown that if the maximum capacitance ratio which can be electrically handled is a factor of l04, the maximum external radius of the system which can be considered (assuming an internal wellbore radius of 0.25 ft is: It is thus seen that in direct consequence of having the inner wellbore radius small compared to the external radius, models extending beyond 30 to 40 ft are not possible when the capacitance ratio is limited to l04. (NB. A value of 10-9 farads can perhaps be taken as the minimum electrical capacitance possible if corrections for the capacitance of the lead wires are to be avoided. Values greater than 10-5 farads would require the use of unstable and inaccurate electrolytic capacitors). On the other hand, models extending out to 500 to 5,000 ft may be desired in single-well problems, and hence the need for a revised method of problem programming. * REVISED PROGRAMMING METHOD The revised method of programming is one which attempts to retain the desirable features of the conventional method (viz. concentration of block units towards the inner boundary, simplicity in computation, etc.) without having as a consequence that impossible capacitance and vertical resistance ratios will be required. Other advantages will also be achieved by the revised

Jan 1, 1957

Jan 1, 1969