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By Dudley L. Davis, E. C. Peterson

INTRODUCTION THE Darwin District is 30 miles east of Olancha which is 220 miles north from Los Angeles via U. S. Highway No. 6. The ore deposits occur in the Darwin hills that have been elevated above the Darwin Plateau by typical basin and range-type faults. Some of these faults have been active quite recently as shown by the displacement of Quaternary (?) basalt flows and the rejuvenation of erosion in Darwin wash. The ore bodies occur as fissure fillings and replacement of favorable beddings in a thick series of Paleozoic limestones, dolomites, shales and quartzites. Rich oxidized lead-silver ores were discovered in the early seventies. By 1875, Darwin had a population of about 5000, and by 1880 several small mills and smelters had been built. Early exhaustion of surface ores, the isolated location of the district, and fluctuation of metal prices caused intermittent operations until World War II. The district production is estimated at about $3,000,000 prior to 1900 and perhaps $4,000,000 between 1900 and 1945 when Anaconda purchased the major producing mines. For the past two years, daily production has averaged 75 tons of direct shipping and 150 tons of milling-grade ore. At present, 300 tons of mixed oxide and sulphide ore are treated by flotation, the oxidized lead minerals being activated by addition of sodium sulphide after galena and sphalerite have been recovered from the circuit. Extraction averages 85 pct of the lead, 80 pct of the silver, and about 33 pct of the zinc in a bulk concentrate. The mill is designed so that minor changes permit selective flotation of pyritic lead-zinc ores encountered at depth. GENERAL GEOLOGY The oldest rocks in the Darwin hills are a series of Paleozoic limestones, dolomites, shales and quartzites probably Pennsylvanian in age. These rocks have been intruded on the west by the Coso granite batholith and on the east by a granodiorite stock. Numerous sills and dikes grading from orthoclase granite to gabbro are exposed in the underground workings. The sedimentary rocks have been considerably folded and faulted, the most prominent structure being a northwest pitching anticlinal fold, the crest of which lies just west of the ridge line of the Darwin hills. The east limb of this fold has been intruded by the granodiorite stock and east of the stock the sediments show several closely spaced anticlines and synclines. The minor flexures on the west flank of the major fold are structurally important in localizing the ore in the Defiance and Essex mines of the Darwin group. There are three principal systems of faulting and fissuring, most of which are post-intrusive and premineral in age, with minor amounts of postmineral movement. The Darwin tear fault is the largest, most persistent fault in the district. It strikes N 60 to 95°W, dips steeply south and is traceable for about 1o miles. It is a normal

Jan 1, 1947

By B. E. Eakin, A. L. Lee, M. H. Gonzalez

Expeximental viscosity and density data of lour natural gases are presented for temperatures from WO to 340F and pressures from 100 to 8.000 psia. A correlation is also discussed and results reported. INTRODUCTION This investigation is one of several efforts by the authors to provide viscosity data for pure hydrocarbons and mixtures. Results of some pure hydrocarbons and their mix tures have been presented." Several predictive methods and correlations have also been reported.'," This paper presents the experimental viscosity and density data of four natural gases and confirms a correlation in a previous study. APPARATUS The viscometer was described previously. 2,6 A bank of stainless steel pycnometers was included to determine density in conjunction with the viscosity measurements (Fig. I). DATA AND MATERIALS The natural gases were furnished by the Atlantic Richfield Co. (Samples 1 and 21, the Continental Oil Co. (Sample 3) and the Pan American Petroleum Corp. (Sample 4). Table 1 shows the composition of these gases obtained by mass spectrometer analysis. The pure component viscosity data used in the correlation have been published."".'"', '" Experimental and calculated viscosity data for the natural gases are presented in Tables 2 through 5. CORRELATION Starling and Ellington"' have reported several semi-empirical expressions based to a certain extent on the theory of viscosity advanced by Born and Green.' The final expression presented by Starling and Ellingto'n is: i'. (micropoise) -- /t,, exp rX(7') p ..... (I) Eq. 1 was modified by Lee et 01." to represent mixture and pure component data simultaneously. This equation has the form: F = K exp [XpY] :.........(2) where K=- (7.77 i 0.0063M)Ti 122.4 + 12.9M +T .................(3) ' ' ' X= 2.57 + ---1914.5+ 0.0095M .... (4) Y = 1.11 -r 0.04 X ........(5) Over the pressure and temperature range studied in this investigation, this equation represents the data on methane, ethane, propane, n-butane and four methane-n-butane mixtures with a standard deviation* of ? 1.89 per cent. Density data by Sage and Lacey" were used to fit the equations. Eq. 2 gives reliable values of the viscosity of light hydrocarbons without prior knowledge of experimental viscosity values, but accurate density data must be available. Eq. 2 was used to predict viscosity values for the natural gases studied in this paper. The particular set of parameters contained in Eqs. 3 through 5 gave values that reproduced experimental data within 25 per cent. Needless to say, in using Eq. 2 better density values will give better viscosity results. However, those engineers who do not have accurate density values at hand or the time, or such facilities as a library, computer, etc. readily available, may feel uneasy in using Eq. 2. Therefore, the authors sought the easiest but by no means best density prediction method, which was reported by Kaf 30 years ago. A set of density values, which were calculated based on Kay's method, and a generalized compressibility factor chart were used to fit Eq. 2. The results are:

Jan 1, 1967

By R. A. Davidson, L. Silverman

RESIDENTS of many urban centers are becoming increasingly aware of the obscuring effect of fume and smoke discharge from power, metallurgical, chemical, and other industries; and they, as well as the legislatures of these affected cities, are agitating for cleaner air. Management's most pressing problem is to find an economical way to reduce process effluents in response to the growing pressure from population and legislative demands. The removal must be done, if possible, without handicap to the current operation, since the costs of relocating are often excessive or prohibitive. In fume recovery or disposal, an important item to consider is whether or not the material being discharged has any value. If it has commercial value, the cost of its recovery may offset or aid amortization. For this reason, in making a study of the specific problem in hand, a major factor was the nature of the material emanating from the stack: in particular, its particle size, size range, and its chemical and physical composition, as well as its potential value and utility when recovered (in either a wet or dry state). Should the product have no commercial value, it must be disposed of at minimum cost in a way to prevent recontamination. Initial studies were therefore made to determine stack concentrations and volumes of material evolved from the operations. The next phase of the study concerned the physical and chemical nature of the collected fume. The third portion of this paper describes the wet and dry collector studies undertaken to recover the fume. Cleaning Requirements for Ferroalloy Furnace Operation The basic need for any effluent collection equipment is the highest possible efficiency and the lowest tolerable resistance when the power consumption involved is considered. Since the electric furnace effluent is largely composed of fume of small size (less than 0.5u), it has high light obscuring properties, and even low concentrations will cause some loss of visibility and be evident to nearby residents. The permissible limit for fly ash emission in many cities is based on a weight value (viz, approximately 0.4 grains per cu ft), but the smoke density values are dependent upon a shade of color. In the case of the Los Angeles County code, emission is restricted to pounds per pound of material processed per hour basis (but not exceeding 40 lb per hr for any one given plant operation). If an average particle size of the fume from ferro-silicon alloy electric furnaces is assumed to be 0.4u (as shown later, this is the approximate mean size) and an average loading of 1 grain per cu ft (stp), each cubic foot of stack gas will contain approximately 75x10 10 particles (based on assumed, and confirmed, spherical shape and a standard deviation of unity). When it is realized that the air in metropolitan areas, which are also general industrial areas, contains approximately 5x108 particles, the tremendous light scattering effect of this concentration becomes apparent. Consequently, nearly 100 pct collection would be necessary to equal the average concentration. Fortunately, however, discharge from a high point above ground (50 to 100 ft) will result in at least a thousandfold dilution, or the stack concentration reaching the ground in the foregoing case might result in a ground concentration of ' particles. If the concentration at the source could be reduced by a factor of 100 (99 pct efficiency of collection), then a concentration of 75x10" particles would be diluted to 7.5x10' which would be very satisfactory. An efficiency of 90 pct (factor of 10 decontamination) at the source would result in a discharge of 75x109 articles which upon dilution yields 75x10 which is still 15 times the general air value. Another approach to this consideration is to use the value of concentration of 0.005 grains per cu ft for the value of a visible effluent as cited by Kayse.1 To attain this value with an average loading of 1 grain per cu ft would require an efficiency of 99.5 pct. Since the foregoing value is not based on any reported size of fume particles, it is felt that the numbers' approach given previously is more reliable. These calculations serve to indicate the desirability of thorough cleaning, preferably at the source, and with efficiencies well above 90 pct, preferably above 95 pct (dilution 1:20). One of the most important items in any control program is to reduce the concentrations as close to their sources as possible. The use of better furnace design, deeper coverage over the electrodes, and the prevention of blows or breaks in the surface all help to reduce dissemination; consequently, all of these improvements should be made, if possible, to cut down the effluent load. In addition, in order to minimize the volume of contaminated air that has to be cleaned, the furnace should be enclosed as much as possible. Test Arrangements Before fundamental studies with collectors were made, a furnace stack selected for the test program was sampled to determine the gas temperatures and

Jan 1, 1956

By John J. McKetta. Jr., Louis B. Lesem, George H. Fancher

The proration of oil produced in the field frequently is based partially or entirely upon the gas-oil ratio of wells. The measurement of the gas-oil ratio is one of the more important field tests in regulatory and pro-ration work, and the test always should be conducted according to standardized methods and procedure. Obviously, the gas-oil ratio and the volume of gas produced by a well depend upon many factors but should be independent of the method of measurement and of the devices used to measure gas and oil. Consequently, the volume of gas accompanying a barrel of oil produced by a well may be measured by any reliable and accurate device or instrument. Frequently either a critical flow prover or an orifice well tester is used for this purpose, and for a particular well the same rate of flow of gas should be obtained regardless of whether a critical flow prover or an orifice well tester is employed in the test. In Texas, when using either instrument, either Capacity Table 1 or 5' is employed in making the necessary computations. If the tables are used, a discrepancy always is found whenever the two instruments are compared by extrapolation to the same conditions of flow. Clearly, Tables 1 and 5 must be at fault in some respects. The orifice well tester and the Bureau of Mines type of critical flow prover are essentially the same instrument; both devices utilize a square-edged orifice 1/8 in. in di-ameter as the primary element, and both freely discharge gas to the atmosphere. Tables for the orifice well tester' have been published in the ranges of 0 to 15 in, of water and 0 to 40 in. of mercury (Hg) differential in pressure. Coefficients for the critical flow prover have been published for differentials in pressure greater than 75 psia. An extrapolation of either differs from the other set of data as much as 18 per cent at some points. No immediately obvious reasons for the discrepancy was found, and data available from the literature were insufficient to effect reconciliation. Consequently, a series of experiments was performed to check the available data and to determine discharge coefficients for the two devices in an overlapping range of differential pressure. The correlating equation used in preparation of tables such as Tables 1 and 5' is the so-called hydraulic equation, Q = C1 vh .....(1) The tables cover orifice sizes from 1/8 through 1 1/4 in. A second set of tables, for use with greater differentials in pressure, apply only to the 3/4, 1, and 1 1/4-in. orifice plates over a pressure range of 0 to 40 in. of Hg. The correlating equation used in preparation of the tables is Q = C2 vH(29.32 + 0.3H)/G . (2) Each of these equations is valid only for the range to which it has been applied, and neither equation is valid for extrapolation. Theoretical equations for flow through an orifice are based upon assumptions of fractionless flow and an emergent jet the size of the orifice. A multiplier, C,, called the discharge coefficient, is inserted into the theoretical expression to compensate for both frictional losses and the contraction of the jet experienced in the plane of the orifice. Buckingham3 shows that C, should vary with the ratio of upstream to downstream pressure for flow of a compressible fluid at any average linear velocity through the orifice less than the velocity of sound. Work published by the National Advisory Committee for Aeronautics4 indicates that the variation continues into the so-called critical flow region until the vena contracta coincides with the plane of the orifice. The NACA work, however, does not indicate a leveling off of the coefficient. The work of the Bureau of Mines5 for the critical flow prover was based on differential pressures greater than 75 psi and indicates that the discharge coefficient, Cd, is constant in this region at a value of about 0.86.

Jan 1, 1958

By J. L. Rodda, R. L. Wilcox, E. C. Truesdale

In recent years various problems in connection with research work on the preparation and properties of zinc-base alloys have required reliable information concerning the constitution of the zinc-rich portion of the iron-zinc equilibrium diagram. On numerous occasions rather positive indications were obtained that, for example, the solubility of iron in zinc was incorrectly represented on the current equilibrium diagrams. A careful study of all the available literature relating to the iron-zinc system led to the conclusion that much of the early work was unsatisfactory as measured by present standards of experimental accuracy, and as a result it was decided to redetermine the location of the liquidus curve and of adjacent portions of the diagram. Part I of this paper comprises a description of the experimental methods and a summary of the results by means of which the zinc-rich end of- the iron-zinc diagram has been revised in the following ways: 1. Measurements of the solubility of iron in liquid zinc by several different sampling methods, leading to a relocation of the liquidus curve. 2. Microscopic, conductivity, and X-ray studies of the solid solubility of iron in zinc, which, together with thermal analyses, have resulted in new values for the solid solubility and the eutectic temperature and composition. 3. Heating and cooling curves, obtained by a refined differential method, leading to new locations for the two peritectic horizontals. In Part I1 of the paper the attempt is made to review all of the published work having a bearing on the constitution of the iron-zinc system, and to correlate the present results, and some recently published data involving the use of X-ray technique, with the earlier work, much of which was done from 25 to 30 years ago.

Jan 1, 1936

By H. Foster Bain

THE "miracle of production." which was such an essential element in winning the European war, was nowhere more in evidence than in our Western States. In shipbuilding alone the Pacific Coast States -et a mark never before equaled, and in production of war goods of many kinds, both Rocky Mountain and Coast States accomplished more than their proportionate share if measured by population standards. This was only possible because of the building of immense new plants of many types, largely financed with Government money. Their operation has built up payrolls in the West and brought a measure of prosperity which Westerners are naturally anxious to have made permanent. A widespread doubt obtains, however, throughout the nation and even in the Western States themselves, as to whether, and if so to what extent, this may prove possible. The question has been raised as to whether the national treasury has not been raided to stock the Western ranges with a voracious breed of white elephant .

Jan 1, 1945

By John P. Hager, Igor A. Wilkomirsky

The thermodynamic properties of the Pb-Ag system have been determined between 775° and 950°C by the cell: Electrotransport measurements on silica-saturated PbO-SiO2 melts established that the conduction was entirely ionic and that lead is present only in the divalent state. The activities of lead and silver exhibit Positive deviations from ideal behavior. In dilute solutions the activities of lead and silver follow Henry's law. The values obtained for yhb and yig at 1200°K are 1.49 and 1.69, respectively. Determination of a portion of the liquidus curve agrees well with the established phase diagram. provides an accurate means for the thermodynamic study of liquid alloy systems. However, Wagner and wernerl have shown that cells of type I are limited to alloy systems for which the reaction at the alloy-electrolyte interface will be extremely small. The traditional electrolyte for cells of type I has been a low melting point mixture of group IA chlorides, to which a small amount of the compound ACIZa has been added. However, the choice of a chloride electrolyte may not always be practical, in that the Gibbs free energies of formation of the compounds ACIZ, and BCIZb may not be sufficiently different to minimize Reaction [I]. On the other hand, the Gibbs free energies of formation of the oxides of metals A and B may be sufficiently different to minimize Reaction [I]. In this case, the use of molten oxide electrolyte would be clearly advantageous. In the present study, the thermodynamic properties of the Pb-Ag system have been investigated using the cell: Previous galvanic cell studies on the Pb-Ag system2'= are not reliable due to the displacement reaction between the alloys and the chloride electrolyte. Wagner and ~erner,' using Laitinen and Liu's' value at 450°C for the standard electrode potential of Reaction 111, have estimated the percent error in the activity of lead bPb) when using a chloride electrolyte. At 1000°C the error for xpb = 0.10 is 12 pct. Taking the Gibbs free energies of formation for PbClz and Ag cI,' and the equations of Wagner and Werner,' the error in apb at 1000°C and Xpb =0.10 was calculated to be 140 pct. However, using the Gibbs free energies of formation for Pb O' and an estimated value for Ag 20, the error in apb when using a molten oxide electrolyte at 1000°C was estimated to be less than 1 pct for The virtual reaction of cell I1 for the passage of n Faradays of positive electricity from left to right in the cell is: where 5 is the Faraday equivalent (23,063 cal per v equivalent), E is the electromotive force of the cell in volts, and n is the number of Faradays of electricity required for the transfer of 1 g-atom of lead through the cell. The value of n should be equal to 2 since lead is generally divalent in oxide melts. However, the presence of either tetravalent lead ions or electronic conductivity through the molten oxide electrolyte will result in a value of n greater than 2. Bockris, Kitchener, and Davies' have determined the amount of ionic conductance in a liquid PbO-SiO2 mixture (xPbO= 0.50) at 920°C by measurement of the volumes of CO and C& evolved at a carbon anode during electrolysis. From their data a value of 2.13 * 0.16 was calculated for n. Although their measurements indicate the possible presence of multivalent lead ions and/or electronic conductivity, their measurements were not at silica saturation and no definite conclusions can be drawn. However, as a result of the electrotransport measurements described in the next section the ;due of n can be taken as equal to 2.

Jan 1, 1969

By G. R. Belton, R. J. Fruehan

The Knudsen cell-mass spectrometer combimtion has been used to study the Fe-Al and Ag-Al liquid alloys. By application of the recently developed integration technique to the measured ion-current ratios, activities have been derived for the Fe-A1 system at 1600° C and for the Ag-Al system at 1340"C. The results are partially represented by the following equations: Internal consistency between the data on silver-rich and iron-rich alloys is demonstrated by application of the literature measurements on the distribution of aluminum between the nearly immiscible liquids iron and silver. The usual restrictions on the ratio of the mean free path of the escaping atoms to the orifice diameter of the Knudsen cell are shown not to be limiting in this technique. DESPITE the importance of a knowledge of the activity of aluminum in understanding deoxidation equilibria in molten steel, no direct studies have been made of activities in liquid Fe-A1 alloys at steel-making temperatures. Lower-temperature direct studies have, however, been carried out on aluminum-rich liquid alloys by Gross, Levi, Dewing, and Eilson' at 1300°C and by Coskun and Elliott' at 1315°C. Apart from phase diagram calculations by Pehlke, other determinations have been indirect and were made by measurement of the distribution of aluminum between iron and silver475 and combination of these data with extrapolated activities in the Ag-A1 system.~-% ecently, however, Woolley and Elliott have made a significant contribution by directly measuring heats of solution in the Fe-A1 system at 1600°C. The present authorslo have recently employed a Knudsen cell-mass spectrometer technique in a study of activities in iron-based liquid alloys. In this technique activities and heats of solution are determined from a series of measurements of the ratio of ion currents of the components; and since ion-current ratios are used, problems caused by changes in instrument sensitivity or cell geometry are overcome. Results obtained for the Fe-Ni system were found to be in excellent agreement with previous work, thus demonstrating the reliability of the method. The present paper describes a similar study of activities in the liquid Fe-A1 and Ag-A1 systems, this latter system being included in order that a meaningful comparison can be made with the above-mentioned indirect studies. INTEGRATION EQUATIONS A detailed derivation of the equations used to determine the thermodynamic properties from the measured ion current ratios has been given elsewhere;'' however it is useful to summarize them here. By the combination of the Gibbs-Duhem equation with the direct proportionality between ion-current ratios and partial pressure ratios, it was shown that for a binary system at constant temperature and pressure: where al is the activity of component 1 with pure substance as the standard state, N, is the atom fraction of component 2 in the solution, and I; and t'2 are ion currents of given isotopes of the components. The activity coefficient is given by: this latter equation being more suitable for graphical integration. Combination of Eq. [l] with the Gibbs-Helmholtz equation gives an expression for the partial molar heat of mixing: EXPERIMENTAL A Bendix Time-of-Flight mass spectrometer model 12! fitted with a 107 ion source and a M-105-G-6 electron multiplier, was used to analyze the vapor effusing from the Knudsen cell. The arrangement of the Knudsen cell assembly was essentially that of the commercial instrument (Bendix model 1030) but with several modifications. Instead of heating with a single tungsten filament, a cylindrical tantalum-mesh heater was employed. Up to 1400°C simple resistance heating was used but above this temperature electron bombardment between the tantalum mesh and the tantalum cell susceptor was necessary. The temperature was measured by means of a Leeds and Northrup disappear ing-filament type optical pyrometer sighted on an essentially black-body hole in the side of the cell. Details of the temperature control, temperature measurement, and in situ calibration of the optical pyrometer can be found elsewhere.I0 In the investigation of the Fe-A1 system the Knudsen cells were constructed of thoria crucibles with fitted thoria lids (Zircoa). The cells employed in investigating the Ag-A1 alloys were made up of high-purity alumina crucibles (Morganite) with lids of recrystal-lized alumina (Lucalox). The cells were 0.370 in.

Jan 1, 1970

By T. A. Simpson

The search for ore continued at its relentless pace throughout 1967. Canada, South Africa and Australia plus a few scattered localities on the globe reported minerals finds of significant importance. Many of the reported finds were not high grade ore, but they nonetheless will assist in sup- plying a highly industrialized, mineral hungry world. No longer does inaccessibility and remoteness close an area to mineral exploration and development. The communication and transportation systems of today have closed the gap and, moreover, the demand for essential mineral commodities is causing price shifts which encourage exploitation of deposits heretofore considered uneconomical.

Jan 2, 1968

By Samuel Wyer

Over 8,000,000 people in the United States depend on natural gas for their cooking, heating and lighting service. This service has been made possible only by the investment of large amounts of capital in transportation lines connecting the gas wells to the various communities, thus combining a hazardous mining operation with a public utility service. The effect that making these lines " common carriers" will have on the present and future service to these 8,000,000 or more people is of far reaching ethical and economic importance, and deserves careful consideration. As an introduction, it must be conceded that: 1. Natural gas, although a mineral and obtained by a mining operation-with more uncontrollable and uncertain features to cope with than exist in the mining of coal or other minerals-when served to the public becomes a public utility service. 2. The governmental power to regulate all public utilities in the interests of the public cannot be successfully disputed. 3. Mere suggestion of inconvenience to the utility is wholly irrelevant, as it cannot be considered or allowed to influence in making a defense against governmental regulation. Unfortunately it is not generally appreciated that: 1. Legislative enactments are not necessarily laws, and cannot abrogate economic laws or alter engineering facts. 2. There is a clear distinction between "common carrier" and "public utility," although the terms are frequently confused. ' "A common carrier is one who undertakes for hire to transport persons or goods, or both, from place to place for all persons indifferently, the term implying indifference as to whom shall be served, and an equal readiness to serve all who apply, in the order of their application." On the other hand, property becomes a "public utility" only "when for a particular purpose the public have a right to resort to the premises and make use of them."

Jan 5, 1914

By Chester B. White

ARGENTINA is a country that has never been properly prospected. This is my settled conclusion after reporting on mines in this country ever since 1914, crossing all the mining provinces from Chubut, in the South, to the territory of Los Andes, in the North, chiefly on muleback. It is difficult and costly to get from one district to another. Apart from petroleum, some mineral discoveries have been made but they have been the result of casual rather than systematic work. In Neuquen, Mendoza, San Juan, Cordoba, La Rioja, Catamarca, and Los Andes attempts at mine development have resulted in failures, involving in each instance several million pesos.

Jan 1, 1937

By G. Britsianes, T. L. Joseph

THE reduction of a lump of iron ore is a complicated sequence of up to three reactions proceeding simultaneously in a gas-solid system. As the ore moves down the blast furnace into zones of higher temperature and higher reducing power, it is successively reduced through the three oxides of iron into metallic iron. The reduction process involves much more than chemical problems. Physical factors add to the complexity of the overall process. Under optimum conditions, reduction of the ore is completed at a level about one-half way down the blast furnace stock column. At this point, the ore undergoing reduction has attained a temperature of about 1000°C and has been in the furnace for about 6 hr. On the practical side, the behavior of the ore during smelting has been of great interest to operators. Unsatisfactory blast furnace operation on burdens containing magnetite ore or badly slagged sinter has often been attributed to poor re-ducibility. The question of reducibility has also been raised in formulating quality standards for agglomerates such as nodules, briquettes, and pellets. In the present investigation, the solid phases formed during reduction were studied as a step toward a better understanding of the overall process. Equilibrium Studies The iron-oxygen equilibrium diagram shown in Fig. 1 reveal; a number of facts pertinent to the gaseous reduction of iron ores. This diagram is from the work of Darken and Gurryl, 2 and represents a correlation of the best available data. Four solid phases may exist during the complete reduction of hematite to metallic iron. These are hematite (Fe2O3), magnetite (Fe3O4), wustite (FeO), and iron (Fe). The wustite phase is a solid solution which is not stable below 570°C. At this temperature the solid solution undergoes a eutectoid-type of decomposition into the phases, magnetite and iron. Thus above 570°C, the diagram dictates that a hematitic ore should pass through a four-phase sequence on reduction to metallic iron. Below 570°C, only hematite, magnetite, and iron should appear. Information on the iron-oxygen system has been derived largely from CO and H2 reduction equilibria. The Fe-C-0 relationships have been studied extensively by R. Schenck and his coworkers and well summarized by H. Schenck.3 More recent studies have been made by Darken and Gurry.1, 2 Data from these sources have been combined and plotted in Fig. 2. With respect to the Fe-H-O system, the works of Emmett and Schultz4 seem the most reliable, and these data have also been included in Fig. 2. Certain physical properties of the solid phases of the iron-oxygen system are summarized in Table I. The crystallographic information is of special interest as much of the present work has been concerned with the X-ray analysis of the products of reduction. Reduction with Hydrogen The reduction of ore with hydrogen is the net result of two or more gas-solid reactions. Above 570°C, the reaction sequence may be represented by stoichiometric stages as follows: 3Fe203+ H2e2Fe,O, + H20 [1] 2Fe3O, + 2H2 6FeOw + 2H2O [2] 6FeOw + 6H3 ^ 6Fe + 6H=O [3] Fe2O3 + 3H2 ^ 2Fe + 3H,O. [4] These reduction reactions follow the general form: A (solid) + B (gas) e C (solid) + D (gas). This type of gas-solid reaction has been investigated by Langmuirl' who has shown that such reactions can occur only at the boundary between the two solid phases. Furthermore, a nucleus of the second phase must initiate the reaction. Once such an interface exists, the reaction proceeds through a layer of the solid reaction product (C). The specific mechanisms involved will depend a great deal on the properties and condition of this particular layer. A number of heterogeneous reactions such as the dehydration of single crystals of copper penta-hydrate and the calcination of limestone follow this type of process. It should be noted that the inter-facial type of reaction also occurs even in dense polycrystalline material which simulates a mono-crystalline behavior.

Jan 1, 1954

By K. Leutwyler, H. L. Bigelow

Jan 1, 1966

By A. M. Sarem, J. M. Campbell

Molecular refraction is introduced as a new and improved third parameter for prediction of the PVT behavior of hydrocarbon systems. This parameter, characterizing the complex as well as the pure hydrocarbon systems (1) is a direct measure of London dispersion forces which affect the PVT behavior; (2) can be measured directly, accurately and easily for complex as well as pure hydrocarbon systems; (3) varies significantly between the reference substances thus allowing accurate interpolation of PVT properties; and (4) has a fundamentally sound basis. Molal average molecular refraction was used with the pseudocritical mixing rule proposed by Leland and Mueller to predict the molal volume of liquid and vapor for 84 published data points on nC4-nCI0, Cl-nC5, Cl-nC4-nC10 systems in the region of coexisting vapor-liquid and at the critical point. The same technique was applied to predict the densities of liquid hydrocarbon mixtures in the two-phase and single-phase regions near the critical point for seven different systems each having different properties of the heptanes-plus fraction, but all simulating the fluids of either gas-condensate or volatile oil reservoirs. A modification of the Leland-Mueller mixing rule for the determination of pseudocritical properties is also presented which yields more accurate liquid density predictions than the original form when used with the proposed third parameter. INTRODUCTION The PVT behavior of multicomponent systems has received widespread attention in the literature in recent years. A large portion of the reported work has stemmed from attempts to overcome the inherent difficulties encountered when using the standard compressibility-factor chart which shows 2 as a function of reduced temperature T, and and reduced pressure p,. This chart assumes that z, is constant for all systems. The error in this assumption is not pronounced for pipeline-type gases high in methane and low in heavy ends, particularly when contained at moderate pressures. For such gases the error in the calculated z is usually less than 2 to 3 per cent. However, the reliability of this approach becomes somewhat nebulous for gas condensate and volatile oil systems at high pressure. One logical approach has been to recognize the variation of 2,. This idea was first suggested by Meissner and Seferianl and used by Lyderson, Greenkorn and Hougen2 to prepare extensive tables of thermodynamic properties. Other third parameters have been proposed by Stockmeyer, Kihara, Riedel, Lightfoot, Bloomer and Pitzer. These were tested by Satter and Campbel13 for many gas mixtures and it was shown that they were inter-related. All of these third parameters have a common fault — they cannot be directly evaluated for the heptanes-plus fraction. Consequently, one necessary requisite of an improved method for predicting the density of multicomponent hydrocarbon systems, was development of a third parameter that could be evaluated for that fraction. PREVIOUS MULTICOMPONENT DENSITY PREDICTION METHODS Sage and Lacey4 suggested a method of using partial molal volumes for computing the density of hydrocarbon gas mixture for pressures to 3,000 psi. In this technique, they approximate the complex multicomponent gaseous mixtures by a quarternary system of methane, ethane, propane and butane. Sage, Hicks and Lacey5 suggest a method of using partial molal volumes for computing the density of hydrocarbon liquids. The results agree within 3 per cent of the experimental values. However, the composition range is limited to about 10 per cent by weight of methane. Consequently, this correlation does not cover the low-molecular-weight liquid similar to natural gasoline and high-pressure gas condensates.

Jan 1, 1966

By B. M. Larsen

NEVER having actually tried to engage in the systematic education of anyone, and having little direct knowledge of the practical problems and limitations in the field of education, I can pose only as a "nonexpert" in this field, one whose ideas are to be regarded as personal opinions. The necessity for compromise between educational ideals and the practical limitations of time, money, and mental capacities of both student and teacher is evident in the preparation of an end product that we may regard with a reasonable degree of conviction as a professional engineer. We need to do so many things. The engineering student must have a clear understanding of the basic sciences; he should develop manual skills and co-ordination; he should speak and write the language with simple clarity and directness; he should gather knowledge of a special field; and, he should be educated for living in a broad ..

Jan 1, 1948

By J. F. Smith, J. E. Davison

A value for the enthalpy of formation of z2 of -3.14 i 0.21 kcal per g-atom has been measured by the technique of acid solution calorimetry. This result is in quite good agreement with two earlier determinations by tin solution calorimetry and by direct reaction caloriinetry, and averaging of values determined from the three independent calorimetric techniques gives enhanced precision and accuracy with AHh8 (CaMgZ) = - 3.15 i 0.05 kcal per g-atom. For comparison with experimental data, values for the enthalpies of formation of CaMgz, SrMgz, and BaMgz of -9.8, -7.9, and -2.8 kcal per g-atom were estimated from a calculation based on the LVigizer-Seitz approximation as modified by Raimes for polyvalent elements. While complete quantitative accord between these calculated talues and available experimental data is lacking, nonetheless numerical accord is better than might be expected and, more importantly, parallel numerical trends are observed between experimental and calculated vnlues. WITHIN the past decade the enthalpy of formation of CaMg, has been determined a) from measurement of magnesium vapor pressures over binary Ca-Mg alloys,' b) by solution calorimetry with liquid tin as the solvent,' c) from measurement of hydrogen vapor pressures over ternary alloys of calcium, magnesium, and hydrogen,3 and d) by direct reaction alorimetr. The value from tin solution calorimetry is the most precise and is probably the most reliable, and this value is within the quoted uncertainties of the other three experimental results. The overall agreement among the four independent investigations is quite good, particularly so when the diversity of techniques is noted. On the basis of this agreement, CaMgz was chosen as a test material to evaluate the operation of a newly constructed apparatus for the determination of enthalpies of formation of intermetallic phases by acid solution calorimetry. This was believed to be a severe test because of the high chemical reactivity of both calcium and magnesium which reactivity presumably accounts for the fact that an early determination5 of the enthalpies of formation of Ca-Mg alloys by acid solution calorimetry yielded values significantly more negative than the four recent determinations. EXPERIMENTAL APPARATUS AND MATERIALS Experimental Apparatus. The enthalpy of formation of CaMg, was determined by measuring the difference between the heat evolved when dissolving the metallic compound and the heat evolved when dissolving equivalent amounts of unreacted metallic elements in hydro- chloric acid. This was done differentially with an apparatus consisting of twin calorimeters which were constructed to be as nearly identical as possible. The advantage of differential calorimetry is that systematic errors arising from the individual calorimeter design tend to cancel. A schematic representation of the apparatus is shown in Fig. 1. A dead air space around both calorimeters was provided by a large, thermally insulated jacket. Each calorimeter consisted of a 2-liter Dewar flask which was completely enclosed in a copper container. Each Dewar contained 1600 g of 2.5hr HCl to act as the solvent, and thermal effects resulting from solvent evaporation were minimized by covering the acid with 50 g of mineral oil. There was no detectable reaction between the acid and the mineral oil. Equivalent amounts of mechanical energy were added to the calorimeters through twin stirring rods which were driven at the same rpm by a single motor with the intent of the stirring being to maintain thermal equilibrium throughout the solvent. To calibrate the heat capacities of the calorimeters, known amounts of electrical energy could be added by passing measured voltages and currents for known times through submerged heaters, approximately 20 ohms, which were wound noninductively from Manganin wire. A 6-v storage battery was used as a power source, and a dummy heater was used as an exercise circuit to allow the battery to stabilize at a constant electromotive force before energizing one or the other of the calorimetric heaters. A type K-2 potentiometer was used to measure the potential drop across an energized heater while the current was determined from the potential drop across an external standard resistor. Times of energization were measured with an electric timer, and the electrical energy supplied to a heater

Jan 1, 1969

By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton' reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler' stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952

By W. A. Young

Polynomial functions of temperature were obtained for the specific heats, thermal diffusivities, and thermal conductivities of zirconium hydrides containing 4 at. pct U. Three hydrides (H/Zr atom ratios of 1.58, 1.65, and 1.70) were studied over the range a" to 900°C and a fourth (H/Zr = 1.81) was studied over the range 0° to 760°C. The specific heats were determined from enthalpy measurements which were obtained using a unique drop calorimeter specifically designed for use with materials in which high temperature phase transitions and/or high dissociation pressures occur. Thermal diffusivities were measured by the flash method using a pulsed laser. The thermal conductiuities were obtained as the product of specific heat, thermal diffusivity, and density. The specific heats agree, within 10 pct, with values derived using a theoretical model in which the hydrogen and zirconium atoms are treated as Einstein and Debye oscillators, respectively. RELIABLE values of the thermophysical properties of the fuel are required to predict the operating temperatures and temperature response of SNAP nuclear reactors. Among the most important of these properties are the thermal conductivity, specific heat, and thermal diffusivity. A considerable number of investigations1-4 have been made of these properties for the Zr-H and Zr-H-U systems.* However, little of the drides, however, this direct method cannot yield meaningful results, since the hydrogen will redistribute under the influence of the thermal gradient, thus forming a concentration gradient; hence, one has a spectrum of compositions, rather than a homogenous alloy. Although the "average" composition of the material may be identical to the initial uniform concentration, the directly measured value of conductivity will be dependent on the thickness of the specimen, due to the highly sensitive dependence of transport properties on hydrogen content. This dependence is strikingly illustrated by the work of Bickel,5 who found that the electrical conduction of zirconium hydrides ranges from primarily hole conduction to primarily electronic conduction, depending upon the hydrogen content. Fortunately, the direct measurement of thermal conductivity is unnecessary, since it can be expressed as the product of the specific heat, thermal diffusivity, and density, all of which can be directly measured with considerable accuracy. EXPERIMENTAL Specimen Preparation. The combined fuel-moderator material used in SNAP reactors is a hydrided zirconium-uranium alloy containing -10 wt pct U. The alloy used in this work was representative of that used in nuclear reactors except that normal uranium was substituted for the enriched uranium required for reactor usage. It was produced by a triple-arc-melt and double-extrusion process. All specimens were prepared from a single cylindrical extrusion which contained 10.30 pet U, 89,35 pct Zr, and 0.35 pct impurities, The specimens for each composition were hydrided simultaneously with ultrapure hydrogen (10 ppm total impurities) using standard fuel production techniques which routinely yield homogeneous, crack-free fuel with negligible increases in the impurity levels. The hydrogen content of each specimen was determined from its weight gain and the density was measured by liquid displacement, Chemical analyses yielded hydrogen concentrations which agreed with the weight gain data within ±0.02 in H/Zr atom ratio) the concentrations of all other elements agreed almost exactly with the initial values after adjustment for the added hydrogen. The specimens used for the determination of specific heat were centerless ground to 2.00 cm diam after hydriding. A thin slice was carefully removed From each end for metallographic examination. In every case, this examination revealed a uniform structure as evidenced by the appearance and distribution of the two phases present in the fuel at the hydrogen concentrations used. TWO specimens (H/Zr = 1.600 and 1.632) appeared to be entirely 6 phase with equi-axed grains; the specimen with H/Zr = 1.756 showed

Jan 1, 1970

By H. B. Kinnear

THE first copper stool used under an ingot mold to receive molten steel has recently been taken out of service after it had received ingots amounting to 6012 gross tons. This stool, weighing 8330 lb. had been in continuous service for 1822 heats since its installation. From this modest beginning the use of copper for ingot-mold stools grew to 425,000 lb. in 1934, with an additional 50,000 lb. of copper used in the form of inserts in cast-iron stools. During 1935 the quantity of copper used for stools increased by about 350,000 lb., making a total of 775,000 lb. now in use for that purpose. Copper used for inserts has increased during this time 180,000 lb., or over 350 per cent, to a total of 230,000 lb. The total of copper, therefore, in use at present under ingot molds is slightly over 1.000,000 lb.

Jan 1, 1936

By H. N. Hall

Various factors must be considered in an engineering evaluation of gravity-drainage reservoirs. Among these are: (1) the effect of producing rate on total oil recovery; (2) the effect upon well productivity and ultimate recovery of the pressure level maintained during the producing life of the reservoir; (3) the economic advantage of full or partial pressure maintenance; and (4) estimate of the rate of gas production and injection and the possible purchase of gas under conditions of full pressure maintenance to ascertain compressor facilities needed. All of these factors can be evaluated only when a reliable method is employed for determining reservoir performance in gravity-drainage reservoirs. The purpose of this paper is to present a general method for calculating the performance of a gravity-drainage reservoir. This method is applicable for conditions of complete pressure maintenance, partial pressure maintenance and normal pressure depletion. Provisions are made to take into account variations throughout the reservoir of reservoir configuration, changes in permeability and fluid composition. Based on the method presented in this paper, an IBM 650 computer program has been developed. The past performance of an actual gravity-drainage reservoir producing under conditions of declining pressure and no gas injection was duplicated using this program. INTRODUCTION In tilted reservoirs the production of oil is influenced by drainage of oil from upstructure to downstructure locations. When this downstructure drainage of oil is sufficient to cause effective segregation of the gas and oil in a reservoir, the reservoir is usually classified as a segregation drive or gravity-drainage reservoir. (Discussion will be restricted to gravity-drainage reservoirs which have no encroachment of edge water.) The important feature in gravity-drainage reservoirs is the density difference between reservoir oil and gas. These phases tend to segregate in the reservoir with the result that in the gas cap the oil saturation is maintained at a higher level by drainage of oil from the gas-cap area. Oil can be produced from the oil zone at a low gas-oil ratio and reservoir energy is thereby conserved. The standard material balance in not adequate for predicting gravity-dramage reservoir performance because it does not take into account the difference in saturation above and below the gas-oil contact. Several authors'.' have presented methods for calculating the performance of gravity-drainage reservoirs in which reservoir pressure is maintained constant by gas injection into the gas cap. Using some simplifying assumptions, these methods can be employed with a desk calculator to give acceptable results. The problem of predicting the performance of gravity-drainage reservoirs under the conditions of declining reservoir pressure is many time more complex than that of constant pressure. fierefore, attempis to develop a method suitable for desk calculation have required excessively simplified assumptions. In the past several years, highspeed digital computers have become more widely available for reservoir engineering problems. These corn puters are well suited to problems such as the prediction of the performance of gravity-drainage reservoirs with pressure decline. Many of the simplifying assumptions necessary for hand computation can be eliminated so that a realistic approach to the gravity-drainage process can be made. CONCEPTUAL PICTURE OF OIL MOVEMENT IN GRAVITY-DRAINAGE RESERVOIRS Before attempting to develop an analytical treatment for conditions occuring in a gravity-drainage reservoir, a concept should be formed concerning the movement of fluids in the reservoir as oil is produced. A review of the literature'.' shows that it is customary to classify gravity-drainage operations into two categories—(1) with complete pressure maintenance, and (2) with declining pressure. The same line of reasoning will be followed in presenting the concept of the movement of fluids in the reservoir because it is easier to visualize the movement of fluids under conditions of complete pressure maintenance. After discussing complete pressure maintenance, an analogy will be made between that and the case of declining pressure. It should be kept in mind throughout that the final aim for the problem of solving gravity-drainage performance with digital computers will be to develop a general program for any kind of gravity-drainage reservoir. COMPLETE PRESSURE MAINTENANCE One feature which is generally common in gravity-drainage reservoirs is a gas cap located at the top of the structure. This is shown in Fig. 1(a). Fig. l(b) shows oil saturations that might occur through the reservoir. In the gas cap, oil saturation is lower than