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By Mohamed Mortada

A practical analytical method is developed in this paper which provides the practicing reservoir engineer with a handy method for analyzing oilfield interference problems. The procedure employed entails the principle of superposition of individual eflects. A set of charts has been developed and can be used to evaluate the individual effects. The charts represent non-steady state pressure distribution in an extensive aquifer due to a constant rate of production from an oilfield which can be approximated by circular geometry; they are constructed from solutions to the diffusivity equation considering a circular sink as distinguished from a point sink. The solutions are obtained partially from mathenlatical considerations and partially from analog and digital computations. By virtue of the method of images, the charts can be used also to treat the case of production near a fault. In addition, provisions are made for treating oil fields, which are produced by partial water-drive. Treating an actual field case is deferred to a subyequent writing; however, illustrative example is presented to demonstrate the method of application. The pressure distribution in linear and limited radial aquifers is currently under study. INTRODUCTION With the increasing difficulty of discovering new oil reserves, attention is necessarily focused on the efficient development and production of existing reservoirs. Efficient production depends on the availability of reliable means for predicting the pressure-production behavior of oil fields. The prediction is usually performed by analytical methods or computers. Analytical methods are often limited to systems which can be approximated by simple geometry. However, analytical methods have the distinct advantage of being readily performed without special equipment. Analog and digital computers lend themselves to a variety of problems, but are not always locally available and consequently their use is limited. One particular situation in which analytical techniques are needed involves studies of multiple, water-drive oil fields sharing a common aquifer. Such oil fields are in hydrodynamic communication. Therefore, production from any of the oil fields is accompanied by a pressure decline which is transmitted through the aquifer to the other oil fields and manifested as pressure interference. The rate of propagation of the pressure decline is such that the pressure may be significantly reduced many miles away from a producing pool. An example of pressure interference is found in the Woodbine formation in East Texas. There. a dozen or more pools, including several of major size, draw on the Woodbine formation for water drive. The pressure in the water-bearing portion of the formation has been significantly reduced over an area of several thousand square miles. This reduction of pressure has been such that when the Hawkins pool was discovered in 1940, the pressure in it had already been reduced 280 psi below the initial value in the aquifer. This resulted from prior production from other Woodbine sand pools, including, in particular, the East Texas field some 20 miles to the east of Hawkins.' The above example indicates that the interference effect can be significant and should be taken into con-

Jan 1, 1956

By Charles R. Holmes

MORE than 70 igneous pipes and dikes are known to occur in Cambrian sediments throughout an approximately circular area of about 75 sq miles in southwestern Ste. Genevieve County and southeastern St. Francois County, Mo., across the southern portion of the Farmington anticline, which is outlined in fig. 1. From evidence obtained from fossil fragments taken from some of the in-trusive~, and from the similarity in composition of the more basic intrusives to those of known age in surrounding states, these pipes and dikes are believed to be at least post-Devonian and probably Cretaceous in age. As first postulated by Rust,' these intrusives are believed to represent explosion tubes, or diatremes, punched through great thicknesses of solid rock by gaseous pressure. The particular intrusive studied is located about 1 mile north of the small town of Avon at an elevation of 880 ft in the EVz SEy4 NEY4 of see. 2, T. 35N, R. 7E. Outcrop is through the Bonneterre dolomite in two separated exposures. The larger outcrop extends east and west for about 50 ft along a tributary in a small ravine (fig. 2). The smaller exposure occurs as a few scattered patches over an area 20 ft square about 100 ft to the north. The area between the exposures is covered, but scattered patches of the Bonneterre dolomite outcrop throughout the area surrounding the diatreme. Where exposed, contact relations show the surrounding dolomite to be shattered and metamorphosed to a fine-grained rock for a distance of 15 to 20 ft from the intrusive. The igneous rock occurs as a dark greenish-gray porphyry near the center of the diatreme and as a fine-grained, greenish-gray material containing lapilli and metamorphosed fragments of dolomite near the contact with the country rock. The most abundant original mineral of the porphyritic rock is olivine now largely serpentinized as the result of extensive hydrothermal alteration at time of emplacement. The most common constituent of the fine-grained rock, which occurs near the border of the intrusive, is calcite. Mica is a common constituent of both types of rock, occurring as tufts or flakes. Magnetite makes up about 2 pct of the diatreme and occurs as small irregular grains or streaks of tiny grains. Singewald and Milton' have termed the rock of this body an "augite-free alnoite." Susceptibility measurements of pulverized specimens were made from selected samples taken from both the diatreme and the surrounding country rock. The susceptibility of the Bonneterre dolomite was found to be less than 40xlO-6 cgs (centimeter-gram-second) units and that of the metamorphosed contact dolomite less than 200x10-6 cgs. Measurements of individual samples of the igneous rock showed a wide variation in susceptibility between limits of 1000x10-6 cgs to 8000x10-6 cgs, with the maximum difference occuring in samples taken only a few feet apart. The maximum value was exhibited by a highly weathered sample taken from the northern outcrop, while minimum susceptibility was determined from a partially weathered sample taken only a few feet away. These extremes are believed to represent small local concentrations of stringers and grains of magnetite crystals in the igneous rock. A detailed magnetic survey of the horizontal and vertical components of the earth's magnetic field was made over the diatreme area. Stations were occupied at 20-ft intervals as shown by the grid on fig. 2. When greater detail was desired, intervening stations were also occupied. The field instruments were supplied by the Department of Geophysics, St. Louis University. The magnetometers are the Schmidt balance type constructed by the Ruska Instrument Co. These instruments are temperature compensated and have a standard sensitivity of 10 gamma. Calibration of the instruments

Jan 1, 1951

By Charles R. Holmes

MORE than 70 igneous pipes and dikes are known to occur in Cambrian sediments throughout an approximately circular area of about 75 sq miles in southwestern Ste. Genevieve County and southeastern St. Francois County, Mo., across the southern portion of the Farmington anticline, which is outlined in fig. 1. From evidence obtained from fossil fragments taken from some of the in-trusive~, and from the similarity in composition of the more basic intrusives to those of known age in surrounding states, these pipes and dikes are believed to be at least post-Devonian and probably Cretaceous in age. As first postulated by Rust,' these intrusives are believed to represent explosion tubes, or diatremes, punched through great thicknesses of solid rock by gaseous pressure. The particular intrusive studied is located about 1 mile north of the small town of Avon at an elevation of 880 ft in the EVz SEy4 NEY4 of see. 2, T. 35N, R. 7E. Outcrop is through the Bonneterre dolomite in two separated exposures. The larger outcrop extends east and west for about 50 ft along a tributary in a small ravine (fig. 2). The smaller exposure occurs as a few scattered patches over an area 20 ft square about 100 ft to the north. The area between the exposures is covered, but scattered patches of the Bonneterre dolomite outcrop throughout the area surrounding the diatreme. Where exposed, contact relations show the surrounding dolomite to be shattered and metamorphosed to a fine-grained rock for a distance of 15 to 20 ft from the intrusive. The igneous rock occurs as a dark greenish-gray porphyry near the center of the diatreme and as a fine-grained, greenish-gray material containing lapilli and metamorphosed fragments of dolomite near the contact with the country rock. The most abundant original mineral of the porphyritic rock is olivine now largely serpentinized as the result of extensive hydrothermal alteration at time of emplacement. The most common constituent of the fine-grained rock, which occurs near the border of the intrusive, is calcite. Mica is a common constituent of both types of rock, occurring as tufts or flakes. Magnetite makes up about 2 pct of the diatreme and occurs as small irregular grains or streaks of tiny grains. Singewald and Milton' have termed the rock of this body an "augite-free alnoite." Susceptibility measurements of pulverized specimens were made from selected samples taken from both the diatreme and the surrounding country rock. The susceptibility of the Bonneterre dolomite was found to be less than 40xlO-6 cgs (centimeter-gram-second) units and that of the metamorphosed contact dolomite less than 200x10-6 cgs. Measurements of individual samples of the igneous rock showed a wide variation in susceptibility between limits of 1000x10-6 cgs to 8000x10-6 cgs, with the maximum difference occuring in samples taken only a few feet apart. The maximum value was exhibited by a highly weathered sample taken from the northern outcrop, while minimum susceptibility was determined from a partially weathered sample taken only a few feet away. These extremes are believed to represent small local concentrations of stringers and grains of magnetite crystals in the igneous rock. A detailed magnetic survey of the horizontal and vertical components of the earth's magnetic field was made over the diatreme area. Stations were occupied at 20-ft intervals as shown by the grid on fig. 2. When greater detail was desired, intervening stations were also occupied. The field instruments were supplied by the Department of Geophysics, St. Louis University. The magnetometers are the Schmidt balance type constructed by the Ruska Instrument Co. These instruments are temperature compensated and have a standard sensitivity of 10 gamma. Calibration of the instruments

Jan 1, 1951

By H. F. Yancey, M. R. Geer

The importance of the size composition of coal is reflected in the difference in price of the various sizes of the same coal and in the large number of primary sizes and mixtures of sizes produced by the modern preparation plant to meet the demands of a market that in late years has grown increasingly conscious of coal size. The importance of size in the industrial and domestic uses of coal has its counterpart in the role played by size composition in the laboratory examination of coal. Investigation of many of the physical properties of coal in their relation to its uses requires an evaluation of size composition. In fact, the Standards on Coal and Coke issued by the American Socaiety for Testing Materials in 1936 contains 12 standard methods of testing that involve some use of size composition. The screen analysis is, of course, the standard method of determining size composition, whether the material is coarse run-of-mine coal or fine pulverized fuel. Custorriarily, the analysis is reported as the weight percentages retained on or passing each of a series of testing screens, the number of which may range from only two or three to as many as 20. When more than two or three sieves are used, which is usual, the number of weight percentages obtained is so great as to make the analysis difficult to comprehend. Direct comparison of analyses made 011 the same sieves is hard, and comparison of analyses covering the same range of sizes but made on different sieves is next to impossible. Consequently, a frequent purpose of sizing tests-—-correlation of size with properties and charactcristics related to size-—is rendered difficult. Less cumbersome means of expressing size composition have been attempted with various degrees of success. An average particle size, calculated by any of several formulas, is useful for some purposes, also the weight percentage retained on a single sieve finds some application as a

Jan 1, 1938

By M. R. Geer, H. F. Yancey

The importance of the size composition of coal is reflected in the difference in price of the various sizes of the same coal and in the large number of primary sizes and mixtures of sizes produced by the modern preparation plant to meet the demands of a market that in late years has grown increasingly conscious of coal size. The importance of size in the industrial and domestic uses of coal has its counterpart in the role played by size composition in the laboratory examination of coal. Investigation of many of the physical properties of coal in their relation to its uses requires an evaluation of size composition. In fact, the Standards on Coal and Coke issued by the American Socaiety for Testing Materials in 1936 contains 12 standard methods of testing that involve some use of size composition. The screen analysis is, of course, the standard method of determining size composition, whether the material is coarse run-of-mine coal or fine pulverized fuel. Custorriarily, the analysis is reported as the weight percentages retained on or passing each of a series of testing screens, the number of which may range from only two or three to as many as 20. When more than two or three sieves are used, which is usual, the number of weight percentages obtained is so great as to make the analysis difficult to comprehend. Direct comparison of analyses made 011 the same sieves is hard, and comparison of analyses covering the same range of sizes but made on different sieves is next to impossible. Consequently, a frequent purpose of sizing tests-—-correlation of size with properties and charactcristics related to size-—is rendered difficult. Less cumbersome means of expressing size composition have been attempted with various degrees of success. An average particle size, calculated by any of several formulas, is useful for some purposes, also the weight percentage retained on a single sieve finds some application as a

Jan 1, 1938

By Michael Epstein, Daniel E. Rosner

Fume nucleation sufficiently close to vaporizing suvfaces can augment net vaporization rates into cooler environments. Environmental conditions favoring large vaporization rate enhancements are briefly discussed and a previous theoretical treatment of this nucleation phenomenon is generalized to account for the self-regulating effect of condensalion-heat release within the boundary layer. Despite kinetic limitations on homogeneous nucleation, and latent heat release, non-diffusive condensate removal processes appear to make possible large enhancements in steady-state vaporization rates, provided surface temperatures are well below the boiling point. When condensed phases vaporize (or dissolve) into cooler media, the diffusion-limited mass loss rate can be strongly influenced by the process of nucleation/con-densation (or precipitation) within the thermal boundary layer. This condensation process (which typically leads to mists or fumes in the case of evaporation into cooler gases) has the effect of steepening the vapor pressure profiles near the evaporating surface, since the condensation zone acts as a vapor sink. However. the resulting enhancement in the diffusion-limited evaporation rate can be estimated (as first done by Turkdogan1 for the case of molten iron/nickel alloys evaporating into helium) only if one has independent knowledge of the critical supersaturation, sCrit(T), required to homogeneously nucleate the vapor.* In a recent reformulation and generalization of the theoretical model of Ref. 1 it has been shown that, when log sCrit is approximately linear in reciprocal temperature, rather simple expressions can be derived4 for the ratio of the actual rate of vaporization j" to either the minimum (no condensation) rate j"min, or the maximum (equilibrium condensation) rate j"max In the present communication we wish to briefly report on further developments and implications of the formulation of Ref. 4, with emphasis on i) environmental conditions favoring large enhancements in vaporization rate, and ii) the self-regulatory influence of condensation heat release (neglected in Refs. 1 to 4) on predicted vaporization rates. Additionally, we take this opportunity to correct several misprints appear- ing in Ref. 4, and comment on Elenbaas's recent criticism5 of Ref. 1. MAXIMUM POSSIBLE VAPORIZATION RATE IN PRESENCE OF CONDENSATION A nonequilibrium theory is of interest because of the very large difference between the minimum (no condensation) and maximum (equilibrium condensation) vaporization rate. The magnitude of this maximum possible enhancement can be shown quite clearly by combining a result of Refs. 3 and 4 with the fact that for most liquids there is a simple relationship between the molar heat of evaporation, A, and its boiling point, i.e., A/(RTBp) = C, where the constant C, often called the Trouton ratio, takes on values not very different from 11.* More generally, for any substance (including The Trouton ratio (which for water is 13, for methane, 10, and so forth) will be recognized as the ratio of the molar entropy change upon vaporization (at TBP or Ttransf) to the unlversal gas constant R. Its near constancy reflects the fact that the change in atomic order upon vaporization depends only weakly on the kinds of molecules involved. those that sublime under ordinary conditions) we can define a characteristic transformation temperature. Ttransf, by a relation of the form Ttransf =A/(CR), and then examine the maximum possible evaporation rates as a function of how far removed from Ttransf are the surface temperature, Tw, and ambient temperature, T. Subject to the assumptions: 1) equilibrium vapor pressure, pv,eq, everywhere small compared to prevailing total pressure, p, and 2) negligible effect of condensation heat on temperature profile, the maximum enhancement ratio was found (Eq. [17], Ref. 4) to be: where, for most vapors, Nu/NuD (the ratio of heat transfer coefficient to mass transfer coefficient for the same configuration) is a number near unity.* Ex- *An alternative derivation of the Nu = NuD special case of this equation. revealing its validity for arbitrary velocity/temperature profiles in a laminar boundary layer, is given in Ref. 3. amining this result for a "Trouton substance", one obtains the results shown in Fig. 1, constructed for C = 11. Since we are concerned with vaporization enhancements (j'max/J"min > 1) at surface temperatures below Ttransf, this area of interest is shown unshaded. One notes that at a fixed ambient temperature (hence, T/TtranSf) there is a unique surface temperature, 2T , at which j"max/j"min attains its peak value; moreover, the peak enhancement ratio, see dashed locus. Fig. 1, is: (NuA/NuD)(C/4)(Ttransf/T,). Hence, if Nu = NuD, when the ambient temperature is less than 1/4 of TtranSf the peak enhancement exceeds the Trouton

Jan 1, 1969

By C. A. Stetefeldt

In a former paper (Runs., xxi., 286) I described the plant of the Marsac Refinery, and the manipulations of the process, but cou1d not, at the time, give reliable statistical results. To supply the latter is the object of the present paper. I shall give actual facts as correctly as possible, without any bias one way or the other. For all statistics I am indebted to Mr. W. G. Lamb, who has charge of the Marsac lixiviation-plant and refinery; to Mr. A. Luebeck, assayer at the Ontario mill; and to the Daly Office, Salt Lake City.* Before starting on the work of the year 1892, a most careful clean-up was made, and any remnants were charged to the refinery. During 1892 the Marsac lixiviation-works produced 48.8 tons of so-called "regular" sulphides, which contained, on an average, 11,449 ounces of silver per ton; 11.77 ounces of gold per ton; and 569.8 pounds of copper per ton. To this must be added, 266 pounds of sulphides and by-products left over from the product of 1891, which contained 1380 ounces of silver, 1.41 ounces of gold, and 63 pounds of copper. Before giving the results of the clean-up, a general discussion of the items of expense, methods of assaying, etc., is desirable.

Jan 1, 1895

By Seymour G. Epstein

Using a modified capillary-reservoir technique, electromigration of dilute solutions of silver in liquid bismuth has been measured with relatively good precision. The effects of experiment duration, temperature. current density, and silver concentration have been investigated. Chemical diffusion coefficients of silver in liquid bismuth were also measured at temperatures ranging from 300°to 600°C. The effective valence of silver in bismuth was calculated as a function of temperature from a comparison of electric mobilities and diffusion coefficients. In an alloy containing 1 wt pct Ag, the electric mobility of silver increased from 1.65 x X sq cm per v-sec at 300°C to 2.38 x 10-4at 600°C; the diffusion coefficient in-creased from 3.0 to 17.5 x 10-5 sq cm per sec over the same temperature range. Calculated values of effective valence decreased from 0.28 at 300°C to 0.10 at 600°c. ALTHOUGH there has been considerable progress in the theoretical treatment of electron-transport properties in liquid metals, the mechanisms of mass-transport phenomena in liquid metals are still not clearly understood. This is especially true for the case of electro migration, alternatively termed elec-trotransport or electrodiffusion, which is mass transport induced by an applied electric field. A thorough knowledge of the mechanisms governing electromigration will considerably aid in understanding the electronic state of an impurity atom in a liquid metal. Electromigration has been long observed and studied in liquid metals and alloys. However, no satisfactory theory to explain the observed effects has been developed. The disparity in the present theoretical treatments, summarized by Verhoeven,1 has been attributed to the difficulty in describing the momentum transfer between electrons and ions and to the lack of precise measurements in liquid metals, especially at elevated temperatures. Prior to the last decade most of the electromigration studies were qualitative, in that only the direction of migration of alloy constituents was determined with any degree of reliability. These results have been summarized by schwarz,2 who was able to measure the electric mobility of several elements in mercury. More recently electromigration in liquid metals has been measured by a variety of techniques, with a varying degree of success. Mangelsdorf3,4 made precise measurements on dilute amalgams at room temperature, using a technique relating changes in composition to changes in alloy resistivity, but was unable to make measurements at elevated temperatures. Using a modification of this technique, Verhoeven and Hucke5 measured electromigration and resistivities in liquid Bi-Sn alloys. However, the resistivity technique is not sensitive to small composition changes and is impractical for very dilute alloys. Verhoeven and Hucke6 also measured electromigration of several solutes in liquid bismuth by adapting the capillary-reservoir method for determining diffusion coefficients in liquids. The reported precision of these measurements was poor, however, primarily due to the large uncertainties in the chemical analyses to determine concentration changes. Belashchenko7 has summarized the recent Russian investigations of electromigration, many of which, however, are of questionable accuracy. The present study was initiated to develop an experimental technique which would be both versatile and sufficiently sensitive to yield precise measurements of electromigration of solutes in dilute metal alloys at elevated temperatures. Using this technique, a comprehensive study of silver in liquid bismuth was made to determine the effects of experimental variables on the apparent electric mobilities. Chemical diffusion coefficients of silver in liquid bismuth were also measured over the same temperature range for comparison with the electromigration data. EXPERIMENTAL TECHNIQUE Electromigration Measurements. Electromigration of silver in liquid bismuth was measured by the capillary-reservoir technique, similar to that used by Verhoeven and Hucke,6 but modified to yield more

Jan 1, 1967

By B. W. Roberts, V. A. Phillips

A copper alloy containing- 25.5 at, pct Zn and 19.0 at. pct Ni, which was previously found to show an anoma1old.s hardening effect on quenching- from 600 "C and aging- at 400oc, has now been examined by neutron diffraction. No evidence of long-range order was found. The aged sample showed diffuse scattering- consistent with clustering. The anomalous hardening effect is now attributed to lattice strains caused by clustering rather than (long-range) order hardening. SOLID-solution Cu-Ni-Zn alloys (the commercial 'nickel silvers") have been reported to show anomalies in: change of resistivity on cold working,1-6 temperature coefficient of resistance,2-12 resistivity at low temperatures,13,14 parameter (vs temperature),2"4 calorimetric data,2,4 specific heat,15,16 dilation,2-4 and elastic modulus.17 The structure responsible for the anomalies is produced by annealing typically near 400°C and is rather loosely referred to as the ('K-Zustands" (K state), a term coined by Thomas1' who apparently meant simply that the arrangement of atoms on the sites deviated from that expected statistically. Thomas proposed that the K state occurred in a variety of (solid-solution) alloys such as Cu-Ni-Zn, Ni-Cr, Ni-A1, Ni-Cu, Fe-A1, and Fe-Si and is recognized because its formation is strongly temperature-dependent and results in an increase in electrical resistance which can then be decreased by cold working. Later workers on ('nickel silver" have interpreted the K state variously as short-range order, long-range order. or a combination. The present work was prompted by the discovery by Phillips and Jones19 of a substantial hardening effect when an 18 pct "nickel silver" alloy which is fairly close to the Cu2NiZn composition, was reheated in the range 150" to 450 C after previously quenching from 600°C or, alternatively. was slow-cooled from 600°C or above. The phenomenon was attributed to (long-range) order hardening. Due to the similarity in the atomic scattering factors of copper. nickel, and zinc atoms, the ''nickel silvers" are unfavorable for X-ray diffraction studies aimed at detecting ordering. Nevertheless Bialas et a1.,20 using a powder sample containing 47.96 wt pct Cu, 24.03 wt pct Ni, and 27.98 wt pct Zn, slow-cooled from 400" to 200°C taking 500 hr, observed weak super lattice lines. Further unpublished work" using an anomalous dispersion X-ray technique indicates that zinc atoms are regularly ordered at the corner points of the lattice cell, while the nickel and copper atoms are statistically distributed on the remaining sites. Köster 17 also observed X-ray superlattice lines, for example, in an alloy containing 43.5 wt pct Cu, 28.6 wt pct Ni, and 27.9 wt pct Zn superimposed on the basic fcc cell with a = 3.62 kX. He proposed a Cu3Au-type superlattice with the Ll2 structure in which the A sites were statistically occupied by copper and nickel atoms and the B sites by zinc. He adds that substitution must be possible so that zinc atoms partly occupy A sites. Below about 35 pct Cu, Koster had some evidence for a CuAu-type superlattice with the Llo tetragonal fcc structure with a = 3.82 kX, c/a = 0.88 which could be preserved by quenching. This is suggested17722 to correspond to CuNiZn. While the present work was in progress Hirabaya-shi et a1.23 made an independent comprehensive neutron-diffraction study of a single crystal containing 50.05 at. pct Cu, 26.57 at. pct Ni, 0.25 at. pct Mn, 0.13 at. pct Fe, balance zinc. The presence of manganese and iron is surprising since the crystal was supposedly grown from high-purity metals. The homogenized crystal showed evidence of long-range ordering after an anneal of 5 months at about 300°C. Three possible crystal models were proposed. A curious feature of their results23 is that they could not find any neutron-diffraction evidence of ordering in a powdered polycrystalline near-stoichiometric Cu2NiZn alloy. There appears to be some essential difference between a near-stoichiometric Cu2NiZn alloy and one somewhat further off stoichiometry as used by the present authors. Thus Sato14 was able to reproduce the low-temperature resistivity anomaly reported by one of the authors13 on the present alloy if he used a similar composition, but found the normal behavior of the residual resistivity in a near-stoichiometric alloy. satol2 found that the resistivity of a cold-drawn slightly off-stoichiometric alloy increased to a maximum on isothermally annealing at 300°C and then decreased ("over-aged"). Since he could not explain this on the basis of ordering phenomenon, he proposed that zinc atoms were segregating to stacking faults (Suzuki effect) and found etching bands on the surface by replication which were attributed to the widening of faults. Sato suggested14 that the hardening effect observed by Phillips and Jones19 is partly due to the Suzuki effect. EXPERIMENTAL The starting material was 1/4-in.-diam hard-drawn rod of a commercial 18 pct "nickel silver" alloy identical with that used in a previous study by Phillips

Jan 1, 1967

By J. R. Campbell

In order to discuss the subject intelligently, it will be necessary to touch briefly on the forms in which sulphur is supposed to exist in coking coal to be carbonized in beehive or byproduct ovens. Sulphur is known to exist in coal as sulphides and sulphates, as can be determined experimentally. Then there is the so-called organic sulphur, i.e., sulphur in combination with the carbon, 'hydrogen, and oxygen of the coal, about which much has been written, but nothing definitely proven in an experimental way. In fact, so far. as we know, there never has been developed a satisfactory and conclusive method in the laboratory for the direct determination of organic sulphur. For most coking coals, it can be safely assumed that the preponderance of sulphur is in the form of pyrite (FeSz). When exposed to comparatively low temperatures during the coking process, it loses its sulphur according to the following chemical reaction: 7FeS2 = Fe7Ss + 6S. It will be seen, therefore, that six out of the 14 atoms of sulphur (or 42.8 per cent.) are expelled, or volatilized. FelSa remains in the coke as pyrrhotite, or magnetic sulphide of iron; this accounts for the highly magnetic properties of the powdered coke. A more commonly accepted reaction is FeS2 = FeS f S, in which the straight sulphide of iron is produced with 50 per cent. volatilization of sulphur. In the beehive methods of coke making, air is introduced in sufficient amounts to carry on the distilling and the coking processes, and the sulphur is oxidized along with the other volatile products: First, into sulphur dioxide (SO2), known by the pungent andsuffocating odoremitted from the trunnel head; second, into sulphuric anhydride (SOa); and, finally, into sulphuric acid, as it comes into contact with the air and moisture. In a properly regulated draft on a beehive oven, there is never complete combustion of the gases. In other words, the coking process should be carried on in a reducing atmosphere, and a low-grade producer gas kept issuing from the trunnel head. For coals of about 30 per cent. volatile matter, the ratio of air to gas is 3½ to 1. In complete combustion, the ratio is 6 to 1, producing an extremely high temperature

Jan 1, 1916

By AIME AIME

STRIP coal mining in the United States has-become noted for its massive equipment, especially its power shovels. Notable among the latest examples of this trend is the Bobolink mine of the Binkley Mining Co., at Seeleyville, Ind.,. eight miles from Terre Haute. This is only one of the Binkley company's operating properties; in all, the company owns or controls 26 mines, in fourteen seams. The Bobolink, however, is the largest strip mine in America and probably also in the world. It has an estimated life of fifteen years. The shovel used to strip the over¬burden is electrically operated, of Bucyrus-Erie make, and was. shipped to the property for assembling, a job

Jan 1, 1936

By William A. Johnson

The mathematical analysis of diffusion curves in solid metals is carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. Experimental Procedure If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By William A. Johnson

The mathematical analysis of diffusion curves in solid metals is carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. Experimental Procedure If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By A. L. Ph. B. Holley

(Read at the Philadelphia Meeting, February, 1878.) THIS paper is an abstract and a discussion of results obtained by the United States Test Board in experiments upon 14 brands of wrought iron, most of which are well known and of high repute.* The iron was all intended for chain-cables; it was tested in the form of bars, usually of nine sizes, from 1 inch to 2 inches round, and also in the forms of single links and short chains. Not less-than 2000 tensile tests were made, each showing elastic limit, elongation, and reduction of area. This work was done with conspicuous intelligence and fidelity, at the Washington Navy Yard, by Commander L. A. Beardslee. Some important practical results and principles which he has developed, and others which he has confirmed, will be referred to. The chemical part of this work consists of 42 complete analyses (including slag), by Mr. Blair, chemist to the Board. EFFECTS OF COMPOSITION ON STRENGTH. Variations in the physical qualities of iron may he due to different composition, or to different treatment in manufacture, or to both these complex causes. In order to determine the specific causes of variation, one class of altering conditions should be made to vary largely, while the other classes should be kept uniform. Then another class should be varied, and so on, until the value of each is ascertained. As all the irons under consideration were intended to have that purity and refinement which was deemed indispensable in chain-cables, their chemical analyses are perhaps more important in proving that physical variations result chiefly from treatment, than in pointing out the specific effects of certain ingredients. While the subject of treatment-especially the increase of strength by greater reduction in rolling-may be the more important one, it can be best appreciated after we have familiarized ourselves with the gen¬eral chemical and physical characters of the irons. The typical facts are given in the following tables. * As the present object of the Board is not to compare the products of different makers, but to discover the physical effects of various composition and treatment, the irons are designated by letters rather than by their trade names.

Jan 1, 1878

By S. B. Patterson, A.R. Amos

Log washers have been used for many years in the washing of clay iron ores, phosphate rock and manganese ores, but not until the past 15 years have they been employed to any extent in the preparation of aggregate materials and fluxing stone. For a machine of such importance where tenacious clay or soft rock must be eliminated, there are few data generally available. The purpose of this paper is to set forth the results obtained from several operations, together with a few suggestions for planning a specific installation. Where the material to be washed out consists of loose surface soil, silt, or small amounts of quickly soluble clay, there is little competition with other forms of washers, because greater power and maintenance are required for the operation of log washers, but where the foreign matter is a stiff clay, such as occurs with high-calcium limestones and in marginal gravel deposits, the ability of other kinds of washers to eliminate completely the hard clay balls is at least uncertain. Then the log washer comes into its own field, for with the breaking and churning action of the logs it will clean out the toughest clay. Even with material from the hydraulic dredge, if it contains tough clay, the log washer is desirable unless the gravel is subjected to a costly soaking and rehandling process. Recently there has been a considerable development in other types of machines to accomplish these results but it is not within the scope of this paper to make comparisons between competitive types, but to present the best obtainable data on log washers only. From the primitive design that gave it its name, a long log hewn from a tree, with paddles forged to shape from strap iron and attached by lag screws, the log washer has gradually been developed to the present all-steel type. As now manufactured, the log washer consists essentially of two built-up logs on which are mounted a series of paddles, carried by shafts fitted at the ends of the logs on bearings fastened outside the enclosing steel box, or trough, which is set at an angle of about 5" to 10" and into which the material is fed. Stuffing boxes at the places where the shafts pass through the box at the lower end are equipped with water-

Jan 1, 1938

By A. R. Amos, S. B. Patterson

Log washers have been used for many years in the washing of clay iron ores, phosphate rock and manganese ores, but not until the past 15 years have they been employed to any extent in the preparation of aggregate materials and fluxing stone. For a machine of such importance where tenacious clay or soft rock must be eliminated, there are few data generally available. The purpose of this paper is to set forth the results obtained from several operations, together with a few suggestions for planning a specific installation. Where the material to be washed out consists of loose surface soil, silt, or small amounts of quickly soluble clay, there is little competition with other forms of washers, because greater power and maintenance are required for the operation of log washers, but where the foreign matter is a stiff clay, such as occurs with high-calcium limestones and in marginal gravel deposits, the ability of other kinds of washers to eliminate completely the hard clay balls is at least uncertain. Then the log washer comes into its own field, for with the breaking and churning action of the logs it will clean out the toughest clay. Even with material from the hydraulic dredge, if it contains tough clay, the log washer is desirable unless the gravel is subjected to a costly soaking and rehandling process. Recently there has been a considerable development in other types of machines to accomplish these results but it is not within the scope of this paper to make comparisons between competitive types, but to present the best obtainable data on log washers only. From the primitive design that gave it its name, a long log hewn from a tree, with paddles forged to shape from strap iron and attached by lag screws, the log washer has gradually been developed to the present all-steel type. As now manufactured, the log washer consists essentially of two built-up logs on which are mounted a series of paddles, carried by shafts fitted at the ends of the logs on bearings fastened outside the enclosing steel box, or trough, which is set at an angle of about 5" to 10" and into which the material is fed. Stuffing boxes at the places where the shafts pass through the box at the lower end are equipped with water-

Jan 1, 1938

E. G. WOODRUFF, Houston, Tex. (communication to the Secretary*). -Mr. Matteson has presented to us an idea worthy of our careful consideration. We have real troubles in the petroleum industry and as the supply of crude is exhausted our problems become more complicated and more numerous. Therefore, we who are engaged in field work are forced to consider all possible means which promise assistance in the location of prospective pools and the economic development of pools already located. In our country we are accustomed to turn to the. Government for relief in all our troubles. Do we want an Oil and Gas Bureau doctoring us? Will such a bureau do us practical good? The principal point Mr. Matteson suggests is that such a bureau should he authorized to receive and file all well logs. In analyzing such function, I am led to the following conclusions: If well logs are simply to be filed they would be useless. If they are to be filed and the files opened to the public, what benefit will be derived and can such action be taken justly? There is no doubt that if the record of all wells drilled in the United States were available the petroleum industry would be saved an immense amount of needless expense. Accumulating conditions would be better understood and prospecting more intelligently directed. Our other consideration is: can the oil companies be required to open well records to the public justly? I think all will agree that if any one should have the advantage of a well record it should be the company that drilled the well. If the oil companies are forced to file such record and open the files to the public, the company drilling the well cannot derive the exclusive benefit from the money expended. Would it be just for a small company to be compelled to reveal its records of a well it had recently completed, to its strong competitor who holds near or even adjacent leases? Would it have been just to the successful companies, in the Gulf Coast country to have been forced to display their hard-earned knowledge of 15 years to the host of younger competitors who have recently flocked to the Gulf Coast attracted by the success of those who have labored so long and learned of the conditions controlling the fields through the hazards of the industry.

Jan 10, 1917

By John Riegle

To date. utility company underground storage of gas has generally been restricted to depleted dry gas fields. The Playa del Rey project is probably the first to successfully store gas in a partially depleted oil reservoir with the recovery of large volumes of pas at high rates as the main objective. Oil recovery has been a secondary consideration. Problems encountered unusual to those of storage in a dry gas zone were: (1) the removal and retardation of formation of emulsion. (2) the upstructure movement of fluid during withdrawal periods which formed fluid blocks, and (3) reservoir shrinkage resulting from encroachment of edgewater. The solution of these problems as outlined in the paper has resulted in increasing the withdrawal rate from the original design capacity of 4,000 Mcf per hour to the current 10.000 Mcf per hour. Additional increase is anticipated as the operations continue. Migration. reservoir performance. operational procedure and a historical record are included to make this a resume of the project from its war-time inception in 1942 to the first of 1952. INTRODUCTION The Playa del Rey underground gas storage project is probably the first project in which gas has been stored in a partially depleted oil reservoir, with the recovery of large volumes of gas at high rates as the main objective and the recovery of oil a secondary consideration. Problems unusual to those of storage in dry gas zones have made this a pioneer endeavor. The total storage capacity of approximately 1,500,000 Mcf of this reservoir is small in comparison with other underground gas storage projects. However. by study and experiment the deliverability into transmission lines. operating at pressures in excess of 150 lbs., has been nearly tripled in the past three years. to the current 10.000 Mcf per hour late, without the use of compression. It is anticipated this rate will gradually increase as additional fluid is removed from the formation. LOCATION AND HISTORY Playa del Key is located on Santa Monica Bay about two miles south of the beach commuity of Venice and 15 miles southwest of the renter of the City city Los Angeles. Fig. 1. The discovery well was completed at 6,194 ft in 1929. An upper zone at 3,905 ft was found on June 18. 1930. Townlot development was very rapid and by the end of 1930 there were 141 producing wells in the field. The Union Oil Co. completed a lower zone well south of the Townlot Field in May, 1931, which was believed to be an extension, until additional drilling of about 50 wells during 1934 and 1935 indicated this area to be a separate accumulation as shown on Fig. 2. The lower oil horizon, which is now the storage zone, had no original gas cap and is believed to be a continental detrital deposit of conglomerate that accumulated in valleys and depressions of a weathered schist high. which later subsided and was overlain by an impervious nodular shale. This type of formation has rapid variation of porosity. permeability and thickness due to lack of sorting action common to marine deposition. and the uneven surface of the original schist high. Production was limited on the upstructure sides by the pinching out of the conglomerate, and downstructure by edgewater. Unrestricted production, together with high permeabilities, led to large wastage of gas from this new area as facilities were not available for transport of gas to market. The decline was very rapid and by 1942 the portion of the new area south of Ballona Creek was nearly depleted. ACQUISITION OF PROPERTY The rapid increase in industrialization of Southern California during World war 11 forced upon the local gas com-

Jan 1, 1953

By D. S. Bloom

RECENTLY a report has been published on an investigation of the MO-RU system by E. Raub.' In this report it is stated that below approximately 1200°C the system consists of two terminal solid-solution phases and the intervening two-phase field; at 1200°C and above, an intermetallic compound labeled Mo,Ru, makes an appearance. Along with some other little known systems in which it was considered possible for a u phase to form, the Mo-Ru system had been under investigation in this laboratory. Since molybdenum and ruthenium have very high melting points and also since ruthenium is expensive, the investigation was confined to X-ray diffraction by sintered powder compacts. The compositions which were studied were (in atomic percentages): 75 Mo-25 Ru, 67 Mo-33 Ru, 50 Mo-50 Ru, and 25 Mo-75 Ru. All compacts were made from the pure powders, and no chemical analyses were attempted. Each compact weighed about 5 g. All annealing was done in evacuated Vycor capsules, and even though the capsules completely collapsed at 1250°C, they still admitted no air. The results of this investigation in general corroborate the work of Raub. Up to 1150°C the two terminal solutions and the intervening two-phase field were found, and at 1200°C and above an intermetallic compound was found. However, the composition limits of the compound were estimated to lie close to 70 atomic pct Mo rather than 62.5 atomic pct Mo as Raub had reported. At least the X-ray diffraction results indicated that the 75 atomic pct Mo specimen consisted of the molybdenum solid solution plus the compound, while the 67 atomic pct Mo specimen consisted of the ruthenium solid solution plus the compound and the equiatomic composition contained only very little of the compound. The most interesting observation, however, was that the diffraction pattern of the compound was similar to that of the well known u phases, except that unusually large lattice constants were indicated. The d-values, or interplanar spacings, of the diffraction lines (as produced by filtered copper KCX radiation) of the compound are given in Table I, as determined from specimens annealed at 1250°C for 9 hr and then quenched in water. Also shown are the lines of the Mn-Mo u phase as given by Decker, Waterstrat, and Kasper,' the lines of the Fe-Mo a as given by Goldschmidt," and the lines of the Mo-Ru phase multiplied by constants in order to make comparison with the Mn-Mo and Fe-Mo patterns easier. These results indicate that the compound in the Mo-Ru system is apparently isomorphous with the other o- compounds. The rather large lattice constants of the Mo-Ru a phase are acceptable in view of the comparatively large size of the constituent atoms. The data in Table I for the Mo-Ru compound check quite well with those given by Raub, not shown here, though there are some discrepancies between the two sets of data in the estimated intensities of a few lines. Although very little is known at present about this u phase, there are some things which may be pointed out, mainly in comparison with other better known u phases. Even though molybdenum and ruthenium are in the same columns in the Table of Elements as chromium and iron, respectively, the Mo-Ru u phase contains much more molybdenum than ruthenium, while the Cr-Fe u phase centers around or very nearly around the equiatomic composition; furthermore, the Mo-Ru u is stable only above approximately 1200°C, but the Cr-Fe u is stable only below about 825 °C. With respect to its being unstable below 1200°C, the Mo-Ru u is similar to the other binary molybdenum u phases in the Co-Mo and Fe-Mo systems. Similar to the latter two systems, the Mo-Ru u apparently exists over a rather narrow composition range, whereas the Cr-Fe u at lower temperatures is stable over a much wider composition range. The Mo-Ru u thus is closer to the other molybdenum u phases than to the Cr-Fe cr phase. The most striking feature of the Mo-Ru u phase, however, is the absence of any of the transition elements of the First Long Period.

Jan 1, 1956

By F. E. Bachman

There is such a great variety of opinion concerning the best method of determining phosphorus in pig iron and steel, that a list of determinations, on a uniform sample of pig iron, together with a short description of the methods used by different chemists, and a few experiments on the accuracy of some of the methods used, [nay be of interest to members of the Institute. All the results given in List A are from the same lot of drillings, thoroughly mixed, except Nos. 8 and 9, and 28 to 32 inclusive, which are from the same pig, but were taken at a later period.

Jan 1, 1882