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By R. H. Winn

A method for the selection of the most suitable corrosion inhibitor for a particular system is given. The method involves the evaluation of surface passivity by means of copper ion displacement after the metal surface has been subjected to the corrosive atmosphere. The application of the method to the selection of suitable inhibitors for use in producing wells is described. Correlation with recognized laboratory tests has beet1 found to be good within the limitations of the test. The use of the test to evaluate inhibitor persistencc is described. INTRODUCTION Corrosion as it is associated with the industry shows wide variations in its qualitative as well as its quantitative aspects. This complicates the work of the corrosion engineer. In the past few years the efforts of the corrosion engineer have been further taxed by the large numbers of products being marketed as corrosion inhibitors by various manufacturers. These products are submitted to him together with a limited amount of data to support their use as inhibitors. The data are usually authentic and reliable yet all too often when these products are applied to an actual corrosive system the results are disappointing due to the ineffectiveness of the inhibitor and the corrosive system. The corrosion engineer must select a comparatively limited number of inhibitors for field trial from the large number available. The selection is usually made on the basis of a standardized laboratory test such as that adopted by the National Association of Corrosion Engineers or by field experience in an area; however, testing of this type is discouraging on large numbers of compounds, particularly in view of the specificity of environment. It has been an object of this work to devise a method which will allow the corrosion engineer to select the best inhibitor for a specific environment under field conditions. The test would of necessity be rapid and inexpensive. It would preferably eliminate the need for expensive and delicate instruments. STATEMENT OF THEORY The test as developed makes use of the fact that metal ions will be displaced from solution by metals having a more positive electrode potential. Thus, if an active iron surface is exposed to a solution of a copper salt, free copper will plate spontaneously on the iron surface as it is displaced from the salt solution by iron ions. If the iron surface is passified, as by coating with an insulating-type organic corrosion inhibitor, it is no longer capable of displacing the copper ions due to its own limited ionization. The result will be a change in the amount of copper plated upon exposure to a neutral copper salt solution. In practice it has been found possible to measure the magnitude of the alteration of the cell potential by determining the copper deposited on a standard iron surface under controlled conditions. This means that, as the film builds up, the resulting shift in the electrode potential tends to cause the iron surface to act more like a noble metal, resulting in a reduction in the cell potential to a point that copper will no longer plate spontaneously. Obviously, the salts of other metals such as silver, gold or platinum might be used for this operation; however, copper was selected because of the color difference of the plate, the comparatively low cost of copper salts and the ease of evaluation of the plated copper. Furthermore, its high cell potential provides a substantial driving energy. The determination of the copper is readily done colorimetrically by dissolving it in 5 per cent ammonium hydroxide solution containing 2 per cent potassium per-sulfate. The blue color of the copper ammonic complex ion so developed may be compared with standards prepared by dissolving known quantities of copper powder in the same reagent. In routine screening it is seldom desirable to determine the amount of copper plated. It is usually more important to determine the concentration of inhibitor required to prevent the plating of copper.

By A. R. Calawa, T. C. Harman, M. Finn, P. Youtz

A study has been made of the growing, annealing, and diffusion parameters in PbSe, Pb1-ySnySe, and Pb1-xSnxTe. Single crystals of these materials have been grown using the Bridgman technique. For all of the above materials the as-grown crystals are p type with high carrier densities. To reduce the carrier concentration and increase the carrier mobility, the samples are annealed either isothermally or by a two-zone method. From isothermal anneals, the liquidus-solidus boundary on the metal-rich side of the stoichiometric composition has been obtained for some alloys of Pb1-xSnxTe and on both the metal- and seleniunz-rich sides for PbSe and alloys of Pbl-ySnySe. In Pbo.935 Sno.065 Se carrier concentrations as low as 5 x1016 Cm-3 and mobilities as high as 44,000 sq cm v-1 sec-1 at 77°K have been obtained. Inter diffusion parameters mere also studied. The ddiffusion experiments mere identical to the isothermal or two-zone annealing experiments except that the samples were removed prior to complete equilibration. The resulting p-n junction depths were determined by sectioning and thermal probing. Inter diffusion coefficients for various temperatures were calculated for both PbSe and Pb0.93Sn0.0,Se. RECENTLY, there has been considerable interest in the PbTe-SnTe and PbSe-SnSe alloys with the rock salt crystal structure. The unusual feature of these systems is the variation of energy gap EG with composition. Several investigations1-3 have shown that EG for the lead chalcogenides decreases as the tin content increases, goes through zero, and then increases again with further increase in tin content. The possibility of obtaining an arbitrary energy gap by selecting the composition is an especially attractive feature of these alloys for applications involving long-wavelength infrared detectors and lasers. In addition, some unusual magneto-optical, galvanomagnetic, and thermomag-netic effects should occur for alloys with low band gaps. If uncompensated low carrier density crystals can be obtained, then a small carrier effective mass, a large dielectric constant, and the resultant high carrier mobility should yield enormous effects at low temperature in a magnetic field. The relative variation of the energy gap with pressure should also be very large for these low gap materials. The primary purpose of this paper is to provide some information concerning the preparation of low carrier concentra- tion, high carrier mobility, and homogeneous single crystals with a predetermined alloy composition. I) DETERMINATION OF ALLOY COMPOSITIONS In all of the work described in this paper, the composition of lead and tin chalcogenides in the alloys was determined by electron microprobe analysis. Separate X-ray spectrometers are used to make simultaneous intensity measurements of the Pb La1 and Sn La1 lines emitted by the sample under excitation by a beam of 25 kev electrons focused to a spot about 2 µm in diam. These intensities are compared to the intensities of the same lines emitted by standards under the same conditions. The standards used are the terminal compounds of each pseudobinary system, i.e., PbTe and SnTe for Pbl-xSnxTe alloys, PbSe and SnSe for Pbl-ySnySe alloys. The composition of the sample is then obtained from theoretical calibration curves which relate the weight fractions of lead and tin in the alloy to the measured ratios of X-ray intensities for the sample and the standards. The lead and tin calibration curves for each alloy system were calculated by using corrections for backscattered electrons,4 ionization,5 and absorption,6 and assuming that the atom fraction of tellurium or selenium in the sample and standards is exactly +. Results obtained by using the microprobe are in good agreement with those obtained by wet chemical analysis. II) CRYSTAL GROWTH FROM THE VAPOR Early work on the vapor growth of PbSe was carried out by Prior.7 He used small chips of Bridgman-grown single crystals as the source material and frequently converted the whole charge of a few grams into one crystal. In the present work, vapor growth occurred using a metal-rich or chalcogenide-rich two-phased alloy powder as the source material. Small, nearly stoichiometric crystals are formed on the walls of the quartz tube. The procedure will now be described in detail. Initially, a 100-g charge containing (metal)o.51(chalco-genide)o 49 proportions or (metal)o.49(chalcogenide)o. 51 proportions of the as-received elements in chunk form are placed in a fused silica ampoule. After the ampoule is loaded, it is evacuated with a diffusion pump and sealed. The sealed ampoule is placed in the center of a vertical resistance furnace. The region containing the ampoule is heated to about 50°C above the liquidus temper-ature for the particular composition used. After about one-half hour at temperature, the elements are reacted and the molten material homogenized. The ampoule is quenched in water. The quenched ingot is crushed to a coarse powder for vapor growth experiments and to a fine powder for the isothermal annealing experiments which are discussed in a later section. Vapor growth experiments were carried out using the powdered, metal-rich or chalcogenide-rich alloys

Jan 1, 1969

The income of the Institute is derived from dues, subscriptions to MINING AND METALLURGY and sale of publications. These sources are fortunately supplemented by the interest from invested funds now amounting to over $500,000, a considerable portion constituting endowments for especial purposes. Aside from the medal funds the principal endowments are the James Douglas Fund for support of the Library, the Rocky Mountain Fund and the Seeley W. Mudd Memorial Fund. The income from the two last named is available for the support of research and a variety of other purposes. It is allocated by the Board of Directors upon recommendation of standing committees in each case. An active effort is being made to increase the endowments of the Institute, it being felt that unusual opportunities exist for research and public and professional service through the organization.

Jan 1, 1936

By R. N. Zitter

PRESENT work was done in connection with a program for obtaining a low energy gap semiconductor suitable for photodetection. The inter-metallic compound InSb, which is now being in-

Jan 1, 1959

By K. Takahashi, I. Iwasaki

it is well known1 that racemic mixtures of optical isomers can be separated by passing their solutions through a column packed with r- or 1-quartz powder so that one of the isomers becomes adsorbed selectively on the asymmetric quartz surfaces. Although the natural occurrence of r- and 1-quartz is more or less equally distributed, some localities show enough deviations toward a higher proportion of l-quartz2 to suggest that optical isomerism might influence quartz flotation. Beta-amines have an asymmetric carbon atom, and therefore optical activity may be expected. Beta-amines are reported to behave quite differently from alpha-amines in the flotation upgrading of certain oxidized iron ores.3 It is of interest, for both practical and theoretical reasons, to determine whether or not optical isomerism plays a role in the amine flotation of quartz. In this article the results of Hallimond tube flotation tests and of adsorption measurements using d-beta-phenylisopropylamine on both r- and 1-quartz are compared. D-beta-phenylisopropylamine was chosen for the tests because it is commercially available in optical isomers. MATERIALS AND METHODS Brazilian quartz crystals were hand-sorted according to the difference in trigonal trapezohedral faces, and each crystal was further checked by the Airy's spiral.4 The respective crystals were then crushed, and the -150 + 200-mesh fractions were screened out for the Hallimond tube tests. The samples were cleaned by brief leaching with warm, dilute hydrochloric acid, and then by repeated rinsing with distilled water. In preparation for the adsorption measurements, they were then dry-ground in a pebble mill for several hours, washed a few times with distilled water, and finally dried in a vacuum desiccator. By means of the Krypton gas adsorption method, the specific surfaces of r- and 1-quartz samples were determined to be 27,700 and 19,800 sq cm per gm respectively, the difference being due mainly to the decantation procedure rather than to the inherent difference in their grindability. D-beta-phenylisopropylamine was the only collector used in the study. It was solubilized by neutralizing with 110% of the stoichiometric requirement of 0.1 N hydrochloric acid. The specific rotation of the d-beta-phenylisopropylamine was determined with a polari-meter using sodium D line to be, Although the d-beta-phenylis~prop~lamine showed absorption maxima in the wave length region of 250 to 270 millimicrons, due presumably to the phenyl group, these peaks were too sensitive to be used for colorimetric determination of the residual concentration in the adsorption measurements. The amine-picrate method, used in the colorimetric analysis of dodecylammonium chloride,' was found to work satisfactorily for the d-beta-phenylisopropylamine. The adsorption densities were thus determined after equilibrating 40 gm of the ground quartz sample with 300 ml of solution by tumbling in separate glass-stoppered Erlenmeyer flasks for one hour. EXPERIMENTAL RESULTS Fig. 1 presents the adsorption densities of d-beta-phenylisopropylamine on the r- and 1-quarts in the pH range of 6 to 7.5. In agreement with data reported in the literature, the adsorption density of d-beta-phenylisopropylamine was slightly higher on the r-quartz than on the 1-quartz, although the difference was not as pronounced as one might expect from the capacity of r-quartz and 1-quartz to separate racemic

Jan 1, 1969

By B. D. Lichter

In a previous paper, Oelsen, Schuermann, and Hey-nertl pointed out the possibility of obtaining complete thermodynamic functions for alloy systems from calorimetric measurements alone. Specifically, if the heat content of a heterogeneous, multicomponent system is known as a function of temperature and composition, then it is possible to derive the heats, entropies, and free energies of formation of liquid phases and of solid intermediate phases of fixed composition. The authors present equations and graphical techniques applicable to eutectic systems and systems with intermediate phases without solid solubility at lower temperatures. eijering has considered possible extension of the treatment to systems with complete solid-state miscibility at lower temperatures; however, experimental difficulties practically restrict the method to systems with very limited miscibility in the solid state. The purpose of this note is to present an alternative derivation of the heats and entropies of formation of liquid phases and of solid intermediate phases from heat-content measurements alone. Fig. 1 shows three types of phase diagram to which the analysis may be applied. If the heat content is determined as a function of composition x, at temperature T, we have quite generally and the heat of mixing of the liquid is obtained directly from heat-content measurements. If the temperature T lies in a two-phase region (solid-liquid) then

Jan 1, 1967

By N. A. D. Parlee, M. M. A. El-Naggar, G. 8. Horsley

The apparatus was of a modified Sieverts type1&apos;2 with a reaction tube designed to function also as the cell component of an oxygen pressure gage. The reaction tube assembly is shown in Fig. 1 and described in Table I. The main body is a 1-in.-OD 15 mol pct calcia-stabilized zirconia tube. The ground-glass joint, g, the male part of which carried a prism for optical pyrometer use, was connected to the remainder of the Sieverts apparatus. The calibration of the cell (at its 1000°K operating temperature) for internal oxygen pressures (PO2in) in the range 0.2 to 10 9 atm was made against internal air pressures measured by mercury manometer and McLeod gage. At very low po2in values down to l<Tn atm the performance was checked by comparing pQ calculated from electromotive force measurement when the apparatus was filled with a) pure CO gas and b) a CO-CO2 mixture of the ratio CO-CO2 = 1:0.398, with Po, values calculated from the equilibrium constants of the following reactions at 1000°K:

Jan 1, 1968

By G. H. Wigton

THE oxidized ores of the Chief Consolidated Mining Co., in the Tintic mining district, have never yielded to metallurgical treatment by any standard method except smelting. These ores occur in comparatively small, irregular, siliceous replacements in limestone, and carry silver, lead, and gold as the principal valuable metals. But smelting methods. are unsatisfactory, as the lead smelters heavily penalize the large amount of silica in the ore, and the copper smelters do not pay for the lead in the ore; therefore, an alternative treatment method was sought. In 1916, a metallurgical research department was organized under; the direction of the writer. Many standard metallurgical methods were investigated but, on oxidized ore, none yielded extraction great enough to make its use feasible. During some chloridizing-roasting experiments in 1916, made in an assay muffle, the writer noted that large proportions of the silver, lead, and gold were volatilized from certain oxidized ores. The possibility of volatilizing the metals and collecting them in the form of a concentrated fume was then studied. But, as it was shown that satisfactory chloride-volatilization would be limited to a furnace feed with a high fusing temperature of the non-volatilizable constituents, and as the results obtained in a rotary kiln with the admixture of common salt with the ground ore were inferior to muffle tests, further volatilization experiments were discontinued until 1920. During this interval, an experimental sulfidizing and flotation plant was operated. After the cessation of attempts to float the oxidized minerals, chloride-volatilization experiments were resumed. The highly infusible flotation. tailing from the operation of the flotation mill was used for furnace feed. The first tests made on flotation tailing mixed with 10 per cent. common salt showed -nearly complete lead and gold volatilization but considerably less volatilization of silver than in muffle tests. In attempts to increase the silver extraction, the percentage salt in the furnace feed was varied, and it soon became apparent that the use of smaller percentages of salt raised the fusion temperature of the furnace charge and thus,

Jan 8, 1925

By David Cole

THE appearance of the Wilfley table in 1897 marked an epoch in the art of concentration of ores. The table has merited and received an almost unprecedented measure of public approval, lasting through its whole patent life. It has been very little improved in itself, or improved upon by competitors. The new machines bidding for popular favor have been of the Wilfley family, but without ability to do markedly better work than the parent m:-chine, or to (to more work except by the use of superimposed decks, the latter having obvious disadvantages. FIG. 1.-The- Butchart RIFFLE System. During the past three years there has been developed at Morenci a new type or arrangement of riffles applicable to the Wilfley type of concentrating table which corrects many of the objectionable features or limitations of the older system and obviates most of the difficulties encountered with it, particularly when handling ores having a low ratio of concentration. The new type is known as the Butchart1 riffle system, and its general arrangement is shown in Figs. 1 and 2.

Jan 2, 1915

By Enrique Touceda

FOR a number of years prior to the world war, the firm of Geo. H. Thacher & Co., of Albany, N. Y., was engaged in the manufacture of marine and other gray-iron castings. At -the outbreak of the war the firm decided to specialize in the manufacture f propeller wheels. It attacked the problem, therefore, from a foundry point of view, seeking to produce a casting that would be so accurate that no subsequent machining would be required on the blades, also from the point of view of the ship builder. There were two general methods f manufacture, the shortcomings of which have been freely acknowledged. In the sweep method, the nowel, or bottom half-mold, for each blade is swept up by a spindle beam and pitch race, while the top half-mold for each blade is built up individually. In the pattern method one individual blade, with the hub or hub portion, is mounted on a spindle and the individual -blade mold formed, the pattern is then rotated on the spindle to the position- for the next blade, etc. In rare cases wheels were made from a solid pattern. Owing to the cost of the pattern, its failure in many instances to be correctly made, and (when made of wood) its early and sure distortion the disadvantage of this practice is obvious, while metal patterns in most instances were prohibitive in cost. In these methods both green-sand and loam molding was practiced. The casting produced by either method can be considered only as a blank from which the propeller must be machined. The back surface f each blade must be chipped too the templet and through this procedure chipped to such accuracy, as will be required for a static balance. Inasmuch as the&apos; work done by the machine tool is confined to the driving face of the blades, not only is perfection most difficult, but corrosion will be greater because of the removal of the dense skin f the casting and the local strains set up by the pneumatic tool in chipping. To produce a finished 9-ft. propeller for a Navy destroyer required from 8 to 21 days f foundry work and about the same length of, time for the machining. Through the use f the Thacher process, only as many hours are required, besides it is possible to produce a finished casting in perfect conformity, with any particular propeller-wheel design,

Jan 4, 1921

By J. A. Berger, R. J. Towner

The pjPocesses of polygonization and subgrain growth were followed in slightly stretched 99.99 pct A1 single crystals heated for cumulative times at 400°, 500°, and 600°C. Changes in sub-grain size and boundary angle were determined from measurements on X-ray micrographs. CAHN1, 2 studied polygonization in stretched and heated aluminum single crystals of 99.99 pct A1 using various techniques, including etch pits, Laue patterns, and a slight restretching of heated specimens to reveal small changes in lattice orientation by the direction of new slip lines. He found that kink bands, which had well-defined boundaries lying in a plane perpendicular to the slip direction (at least in the early stages of deformation), formed during stretching. Also, he noted that bending occurred about the <211> axis lying in the (111) slip plane perpendicular to the <110> slip direction. His studies of polygonization were largely confined to the kink bands rather than to the weakly bent matrix regions between bands. The minimum temperature required to bring about polygonization was established at about 450 "C. Guinier and Tenevin used a focusing Laue X-ray diffraction technique to study polygonization in aluminum single-crystal specimens of 99.99 pct purity. Stretching the crystals 5 pct in tension caused a widening of the focused Laue spots. After heating for 4 hr at 450°C, their method revealed no change in the specimen. Above 450°C polygonization was detected and further annealing near 600°C led to subgrain growth. They concluded that the orientation of the crystal relative to the axis of deformation had no marked effect on polygonization. Gay and Honey-combe4 using an X-ray microbeam technique found that polygonization did not occur in a stretched aluminum crystal heated at 250oC, although some decrease in the yield strength occurred. When the temperature was raised to 475oC, the asterism became broken up as a result of polygonization. Honeycombe5 noted that reflections on X-ray mi-

Jan 1, 1961

By NONE N

Jan 1, 1963

By V. J. Sikora, W. J. McGuire

Several years ago, we used an electric analogue computer to study the effect of vertical fractures on the productivity of wells in expanding fluid-drive reservoirs. The results of this work were used both as a guide to research and as a basis for the design of actual fracturing operations. In 1958, Dyes, Kemp and Caudle&apos; published portions of the data from this study. The results were released in 1959 to service companies for use in fracturing guides. The purpose of this note is to discuss the experimental conditions and assumptions which were made to derive the information which is already partially a matter of public record. ASSUMPTIONS This study applies to fractures which extend in a vertical plane symmetrically from the well. For simplicity, we chose to study the case of a well in a square drainage area with its fractures extending toward two of its nearest neighbors. We have assumed no migration of fluid across the boundary of this area. The quadrant shown in Fig. 1 models this system. We made the usual assumptions that the reservoir is homogeneous and isotropic, that the fluid is homogeneous and that production is effected by fluid-expansion drive. We also assumed that the fracture extends from top to bottom of the reservoir. Of more practical interest is our assumption that the fracture does not change the size of the drainage area. This premise is appropriate if all the wells in the reservoir are fractured in the same way. But where a single well is fractured, its drainage area may be enlarged at the expense of its neighbors. This could be of economic importance. The assumption that the fracture will not extend beyond the established drainage area of the well also limits the application of the results. Such long frac- tures will yield benefits in excess of those predicted here. When we assume homogeneity, we disregard the frequently observed zone of damage in the vicinity of the well. Where damage is severe, the benefits resulting from by-passing it will far exceed those predicted by this study. All comparisons were made of systems producing in the semi-steady state. By this we mean that equal volumes contributed equally to flow (pressure was dropping at a uniform rate throughout the system) when the rate of flow was observed. EXPERIMENTAL SET-UP We used the pool unit of an electric analyzer&apos; in this study. The squase drainage system of a well was rep-

By H. H. Bein

Most western industrial sands are feldspathic and contain feldspars in variahle amounts. A few deposits will show alumina contents of less than one per cent while others will contain over twelve per cent alumina. Some industries are not especially concerned with the amount of contained feldspar but are interested only in color and in size gradations. Other industries, however, are very much interested in alumina content and set up quite rigid specifications as to this content. Several western plants are beneficiating crude sands both to reduce the iron content and to control the feldspar content. At present, most of these plants are using flotation processes for both controls although a few plants do use magnetic separators for the reduction of iron content. Some work has also been done with electrostatic separators for the feldspar-quartz splits. The Sand Division of Del Monte Properties Company, Pebble Beach, California, has been operating a flotation plant for iron removal and the separation of quartz and feldspar since 1950. As mentioned before, control of alumina, especially in the quartz product, is very important. Some users require an alumina content of less than two per cent and others will demand a product of less than one per cent Al2,O3,. The standard Quinolate method for determining alumina is lengthy and time consuming. The HF —H2SO4 evaporation step is especially critical and, if forced, spattering is apt to occur with a resulting loss of sample. Standard procedure is to evaporate to dry ness overnight at a low temperature. Even with forcing under optimum conditions the procerlnre will take two or three hours to complete. A new method has been developed which allows an alumina determination to be made, in 10 or 15 minutes, on a sample of the quartz product as it is being produced. This pocedure, although simply an approximation, has been most helpful in showing whether or not the product being formed is meeting specifications. This procedure has also allowed a great reduction in samples formerly taken and analysed by the orthodox method. Whether a sample assays 1.75% A12O3, or 1.95% .41,0, is not so important as the fact that it is below the allowable maximum of 2.00%. Similar thinking would apply to products required to contain less than 1.00% A1,0,. The step by step procedures for the method are as follows: 1. Collect sample, drain or filter, and dry. 2. Split sample through standard Jones sample cutter to quarter or eighth sample, depending on size of original sample taken, then split down to about 5 grams through Sepor micro-splitter. 3. Screen through 50 mesh sieve (U.S. Series) and reject undersize. 4. Weigh out 2 grams and place in platinum crucible. 5. Etch with 3-5 mls 38.40% HF for 1 minute at room temp. 6. Decant and wash. 7. Stain for two minutes in same crucible with a 1% water solution of Nigrosene dye. 8. Decant and wash well. 9. Dry.

Jan 1, 1961

By Charles S. Barrett

NUMEROUS determinations1-7 of the tex-ture of cold-rolled polycrystalline iron, steel, and ferritic alloys have been made with good agreement among the various observers as to the principal features of the texture common to all, but there has been no adequate explanation of the texture in terms of the behavior of individual grains. This study presents an explanation of the texture based on the observed rotation of single crystals when deformed in a manner similar to a grain in the aggregate, a method we have found useful in leading to a better understanding of compression and tension textures;8,9,10 in particular, the aim has been to determine experimentally the end orientations of rolled single crystals of iron. These are discussed in connection with the point of view of Wever1 and of Boas and Schmid2 that the rolling texture is a simple compression texture (compression normal to the rolling plane) superimposed on a simple tension texture (tension in the roll-ing direction), and the point of view of Kurdjumow and Sachs3 that three ideal end orientations exist.

Jan 1, 1940

By D. G. Westlake

Levine has concluded that prismatic slip in titanium is controlled by two distinct thermally activated processes in the temperature ranges O° to 220°K and 220" to 300°K. We feel that his evidence is not convincing. He has drawn a curve through the plot of activation volume u* vs temperature T with a break at 22WK, Fig. 2. We believe that considering the possible experimental error apd the fact that there are only four points between 4° and 196°K, one could be justified to represent these points by the smooth curve we show as a solid line in Fig. 12. Levine believes that (8rf/aT)+ is discontinuous at 220°K, but he hints that he recognizes the possible doubt. We doubt seriously that the results shown in Fig. 1 indicate a discontinuity at 220°K. Certainly if he were justified in drawing a straight line through only four points on Fig. 2, we are even more justified in drawing straight lines through the seven points between 77" and 297°K on Figs. 1 and 3, because a straight line touches all seven of his circles. If his measurements of t were so precise that his decision to draw two curves in Fig. 3 is valid, then the experimental technique is deserving of further mention. We have drawn a smooth curve through the results in Fig. 3 and used this and the curve in Fig. 12 to obtain the values of shown in Fig. 13. Finding continuous is a contradiction of Fig. 4, which deserves comment itself. Levine obtained the solid circles in Fig. 4 using Fig. 2 and a smooth curve through the points shown in Fig. 3. We have replotted these solid circles in Fig. 14. We submit that there is no basis for his two straight lines (dashed in Fig. 14), and therefore have superimposed the curve that we believe is indicated. Certainly, there is reasonable doubt that a discontinuity in dH/dT exists at 220°K, even when one accepts Fig, 2. Furthermore, if one draws the straight lines indicated by least-squares treatments of the results presented as open circles in Fig. 4, their intersection is at about 196°K, not at 220°K as shown. Thus the alleged agreement between Figs. 3 and 4 with respect to "break" temperatures is not apparent. In Fig. 9, Levine has drawn a straight line very much different from the one indicated by a least-squares treatment. Obviously, he has done this because he recognized that H = 0 when T = 0. He is consistent in drawing the low-temperature curves in

Jan 1, 1968

By Eugene Stephenson

CRITICAL analyses of the work expended in producing oil by the utilization of gas energy have appeared in the publications of Shaw,1 Pierce and Lewis,2 and Herold,3 authors who have ably discussed the factors which must be taken into consideration in comparing energy consumed per barrel in various wells which are flowed by means of gas-lift. However, two distinct phases of oil production are concerned with the ratio of gas energy consumed to oil produced. One of these phases is the gas-lift, which utilizes the differential gas pressures for the purpose of flowing oil, whether these pressures be natural reservoir pressures or be induced by artificial compression of gas or air. The other phase has to do with prorating oil production in pools which are operated either as units, or are subject to such restrictions as those imposed at Oklahoma City by the Corporation Commission, or, by similar controlling groups in other fields. An abundance of literature is available relative to the problems of flowing wells by gas-lift, but the first suggestion that the energy of the gas within the oil and gas pool might serve as a basis for proration, appeared in the timely article by McWilliams.4 Much of the. dissatisfaction with proration in certain fields is because some operators feel that besides the hazard to the wells which accompanies the test, the method of allocating production on the basis of the "potential" gage is inequitable and gives some operators a distinct advantage over others.5 The most severe penalty may be exacted from the most progressive operators or those who attempt to produce their oil with a minimum quantity of reservoir gas. If :no difficulties ever

Jan 1, 1931

By T. C. M. Pillay, John Chipman

The Si-0 equilibrium in liquid iron was investigated in some detail by Gokcen and Chipman1 who reported equilibrium constants of the following reactions: In each case the thermodynamic equilibrium constant K was obtained by extrapolating K&apos; to infinite dilution. Their results on reaction [I] were consistent with those of earlier observers, and there seems to be little doubt as to the approximate validity of the equilibrium product determined. On the other hand, the results on reactions [2] and [3] indicated unusual curvilinear relationships between the activity coefficients of silicon and of oxygen and the silicon concentration. Since a linear relation is observed in all other similar instances, it was concluded that some source of error had affected the gas-metal equilibrium relationships. Recently the authors undertook a restudy of these equilibria with the view especially to establishing the equilibrium constant of reaction [2]. Their experiments, however, were discontinued before a tbroughly satisfactory answer had been obtained and consequently have remained unpublished until the present time. Quite recently Matoba, Gunji, and Kuwana2 published the results of a very thorough study of these equilibria. It is the purpose of the present note to Compare these three sets of experimental data, a comparison which leads to Confirmation of the results of Matoba and coworkers. The experimental arrangements described by Dutilloy and Chipman were employed. A controlled mixture of Hz, H,0, and argon was led into the induction furnace over the surface of the Fe-Si melt contained in a silica crucible. On account of the slow approach to equilibrium, runs were continued for at least 8 hr and, in some cases, as much as 12 hr. Samples were taken by means of silica tubes at the start and during the final 4-hr period of each run. Out of twelve runs only seven appeared to have approached equilibrium with sufficient certainty to be reported here. The results of these experiments, all at 1600°c, are shown by the triangles in Fig. 1. Equilibrium was approached from both oxidizing and reducing conditions and the direction of approach is indicated by the shape of the triangle. Attempts to extend the study to higher silicon concentrations were unsuccessful on account of the transfer of silica from the metal bath to the upper portions of the crucible by means of a silicon-monoxide mechanism. Matoba, Gunji, and Kuwana used similar methods and approached equilibrium from both sides. Their results at three temperatures are shown by the solid lines of Fig. 1. A line corresponding to 1600 deg is interpolated from their equations and is shown by the dotted line. The results of Gokcen and Chipman at 1600 deg in the range 0.02 to 2.0 pct Si are also shown. At concentrations up to about 0.6 pct Si, these investigators approached equilibrium from both directions, and their results in this range appear to be trustworthy. Above 1 pct Si, however, all of their experiments involved oxidation only, as shown by a decrease in the silicon content of the bath. It now seems certain that they failed to reach equilibrium at these higher silicon concentrations and that the curvilinear relation shown by their results is incorrect. It is evident that their results in the lower silicon range are in good agreement with those of Matoba and coworkers. In fact, a straight line drawn through their results would parallel the dotted line and would differ from it by only 0.05 in log K. The new data also lie close to that line. It may thus be concluded that the three sets of data are in good agreement and that the equations proposed by Matoba and coworkers for reaction [2] are satisfactory . They take the limiting value of log K&apos;, at 0 pct Si as log K ,. The slope of each line gives the value

Jan 1, 1962

By T. G. Sieber, T. D. Tiemann

The extraction of quartz from siliceous iron ores by dissolution in sodium hydroxide solution has been described in detail in AIME Transactions. l923 data reported covered the temperature range from 230-416°F, where a continuous increase in the amount of silica extracted with increase in temperature was found. It is the purpose of this paper to describe some unexpected results of more recent work exploring principally the range of 500600°F where higher rates and greater amounts of silica extraction were antici-p ted. In brief, the experimental procedure consists in digesting the ore under pressure in solutions of sodium hydroxide, filtering the suspension and weighing and analyzing the dried residue for iron content. The amount of extraction is calculated from the weight loss or from the iron analysis of the residue and that of the original ore.

Jan 1, 1969

By J. C. Martin

Stmplified equations are developed for the flow of fluids in gas drive reservoirs in which the effects of gravity can be neglected. The results show that the pressure distribution is governed by a nonlinear heat flow type of equation, and the saturation distributions are related to the pressure by the same equations QS those developed by Muskat for the average pressure and saturations in gas drive reservoirs. Unrler certain conditions the equation for the pressure can be approximated by the linear form of the heat flow equatlon. This equation tk analogous to the equation for the pressure in single-phase compressible flow The analysis reveals that the equation for the pressure in n~ultiphase flows can be obtained directly from the equation for the pressure in slngle-phase flows by simply replacing the single-phase compressibility by the total compressibility and the single-phase mobility by the sum of the mobilities of all the fluids present. Perrine&apos;s method of pressure buildup analysis for multiphme flows is based on these same substitutions. Thus, the development presented in this paper constitutes a theoretical justification for Perrine&apos;s method of pressure buildup analysis. One of the most difficult problems associated with the production of oil is the determination of the flow of the fluids within the reservoirs. One purpose of this paper is to present the development of simplified equations for the flow in gas drive reservoirs. The other purpose is to present some of the needed theoretical foundation for the methods currently being used in the analysis of multiphase pressure buildup data. The analysis presented in this paper makes use of a partial linearization of the equations governing multiphase flows. It is felt that the process of linearizing or partially linearizing the nonlinear equations of multiphase flows can lead to useful results since this process has proved extremely valuable in the study of other fields of science and engineering where nonlinear equations are encountered. Pressure buildup data of shut-in wells have been used for many years to estimate the static reservoir pressure. These data have also been used in studying the aver- age permeability both away from and close to the well-bores. The majority of the buildup data are obtained from wells producing two or three fluids. As yet the theoretical foundations for the methods of buildup analysis used in connection with rnultiphase buildup data have not been established. A number of methods of analysis of pressure buildup data have been developed." Most of these methods apply only to single-phase flows, and almost all of the theoretical analysis is confined to single-phase flows. Perrine&apos; developed a method of analysis for rnultiphase flows from the method for single-phase flows of Miller, Dyes, and Hutchinson.&apos; He did this by simply replacing the single-phase compressibility by the multiphase compressibility and replacing the single-phase mobility by the sum of the mobilities of the fluids in the rnultiphase flows. Obviously, such a procedure lacks a certain amount of theoretical justification, and such practices can lead to erroneous results. Fortunately, Perrine&apos;s results have a theoretical justification, and this justification is presented in the following discussion. It is assumed that gravitational effects and the cornpressibility of the rock can be neglected. Under these assumptions the equations governing the simultaneous flow of gas, oil and water in porous media areo* The preceding equations can be expanded into the following expressions.