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By John Ward Smith

Dawsonite-bearing oil shale of Colorado's Green River formation offers a unique and vast (more than 5.9 Gt of A120 j) resource of easily extractable alumina. The processing methods required by the thermal reactions of dawsonite and its oil-shale carrier also require production of shale oil, soda ash, and nahcolite as marketable coproducts. These production methods are presented. The alumina production process is contrasted with the Bayer process to describe technical advantages of extraction of alumina from oil shale which may offset the problems associated with processing a relatively lean ore. While alumina production from oil shale requires development of new technology, the technical problems appear solvable. Only the political problems arising from the now onerous and completely unnecessary federal oil-shale withdrawal appear less solvable.

Jan 1, 1982

By B. A. Eaton

The subject of many discussions and technical papers in the last 20 years has been the prediction of the well-bore pressure gradients that are required to induce or extend fractures in subsurface formations. The subject merits this attention because of the frequently recurring problems that arise from an inability to predict fracture pressure gradients. Encountered in several common types of operations in the oil industry are problems associated with the prediction of formation fracture pressure gradients. When wells are being drilled in both new and old fields, lost circulation is often a very troublesome and expensive problem. Complete loss of circulation has been disastrous in some cases. Many times, such disasters could have been avoided if techniques for calculating fracture pressure gradient had been employed in the well plans, and if casing strings had been set, and mud weight plans had been followed accordingly. In areas of abnormally pressured formations, the prediction of fracture gradients during the well-planning stage is extremely important. In fact, it is as important as the prediction of formation pressure gradients, which has received a great deal of attention in recent years. There are several published methods used to determine fracture pressure gradients. However, none of these methods appears to be general enough to be used with much reliability in all areas. In 1957, Hub-bert and Willis published a classical paper that included the development of an equation used to predict the fracture extension pressure gradient in areas of incipient normal fau1ting.l Overburden stress gradient, formation pore pressure gradient and Poisson's ratio of rocks were the independent variables that were shown to control fracture pressure gradient, the dependent variable. In 1967, Matthews and Kelly published another fracture pressure gradient equation that is different from that of Hubbert and Willis in that a variable "matrix stress coefficient" concept was utilized.3 Later the same year, Costley wrote about a similar idea.5 Goldsmith and Wilson used a least-squares curve-fitting technique and field data from the Gulf Coast area to correlate fracture pressure gradient with formation pore pressure gradient and formation depth.' They noted that the fracture pressure gradient increased with increasing depth while the pore pressure gradient remained constant. In each of these cases, the problem for which a solution was sought was to determine the bottom-hole pressure gradient required to initiate or extend a fracture. Results of the previous work show that fracture pressure gradient is a function primarily of overburden stress gradient, pore pressure gradient, and the ratio of horizontal to vertical stress. There is argument for a fourth variable in that in many cases breakdown fracture pressure gradient is greater than the fracture extension pressure gradient. However, if the fracturing fluid is able to penetrate the formation through the pores or existing cracks, there is very little

Jan 1, 1970

By R. W. Bartlett

DISILICIDE coatings, MeSi2, on refractory metals are usually grown by a solid-state diffusion reaction similar to the parabolic oxidation of metals. Two or more silicide compounds occur in each of the binary silicon-refractory metal systems. When an adequate source of silicon is available during the coating process, the lower silicide compounds are usually not formed.1 However, during service application of the coated refractory metal, continued heating causes further diffusion and growth of the lower silicides. A study of the growth kinetics of the lower silicides in the molybdenum and tungsten binary systems with silicon was previously reported.2 The present study is concerned with the growth kinetics of Ta5Si3 and Cb5Si3, formed as conjugate layers between TaSi2/Ta and CbSi2/Cb diffusion couples, respectively. Diffusion couples consisting of disilicide-coated tantalum and columbium sheet coupons were subjected to diffusion heat treatments, cross-sectioned, and scanned by an electron-microprobe analyzer to determine the relative X-ray intensity profiles. These profiles correspond closely to concentration profiles for the constituents, and were used to identify phases and locate phase boundaries. The analysis of a single specimen after a diffusion-anneal provides only one value for the Me5Si3 phase thickness, corresponding to the time and temperature of the diffusion treatment. Consequently, each isothermal curve showing the rate of accumulation or depletion of silicide phases required several samples with identical diffusion temperatures but different diffusion times. The disilicide coatings were prepared by pyrolizing commercially pure silane in a hydrogen carrier gas. The hydrogen was purified by passage through a palladium membrane. Commercially pure tantalum and columbium sheet metal coupons, 0.005 by $ by 2 in., were used. All of the coated specimens for each system were prepared together in a single group in order to minimize coating variations among individual specimens. During pyrolysis, the brightness temperature was maintained at 1200°C. With suitable flow rates at this temperature, only the disilicides of tantalum and columbium were formed in detectable amounts. Coated specimens were subjected to diffusion an-neals in a tube furnace with automatic proportional control within ±10°C. A H2-Ar mixture, deoxidized and dried over anhydrous magnesium perchlorate, was used to prevent oxidation during the diffusion anneal. Diffusion couples were cross-sectioned, polished and examined with an A.R.L. electron-microprobe X-ray analyzer. Both metal constituents in each specimen were simultaneously scanned using a 1-p beam spot size and either 1- or 2-µ steps. Analyses were performed using the Ka radiation of columbium and silicon, and the La, radiation of tantalum. For all specimens, an acceleration voltage of 30 kv was used, and integration was made against the specimen current. LiF and A DP monochrometers were used to isolate characteristic radiations. Three or more traverses were made on each specimen. The intensity scales were adjusted using the constituent metals and standard samples of the silicide compounds which had been verified by X-ray diffraction. The relative intensity profiles were used directly, in conjunction with the standard samples, to identify compounds and phase boundaries. The stoichiometries differ considerably between the silicide compounds in both systems, and the homogeneity range for these silicide compounds is narrow. These characteristics result in marked differences in relative intensities of the fluorescing elements—differences which permit ready identification of phases and phase boundaries. Projections of both electron back-scattered images and characteristic

Jan 1, 1967

By J. F. Wilson

An experimental investigation has been made of gas-driven slug displacements in a system of high gas saturation to evaluate the process for use in a California reservoir. Fluid compositions, temperature, pressure and core permeability duplicated reservoir conditions as closely as possible. The temperature was above the critical of the slug materials. The slug composition required for 100 per cent oil recovery in the linear flow systems was found to agree with that determined from equilibrium phase studies. A qualitative theory for the slug displacement of two-phase systems is proposed and found to be in general agreement with the observed flow behavior. The theory predicts that the length of the reservoir fluid-slug transition Zone will increase with increased initial gas saturation and decrease with increased oil swelling accompanying the composition change from reservoir oil to the critical composition. The precipitation of small amounts of an asphaltic phase during the formation of the transition zone had no adverse effects on the flow behavior of otherwise miscible systems. INTRODUCTION Despite the large number of recent publications relating to oil recovery by miscible displacement, little information is available concerning the behavior of crude oil-natural gas systems at conditions likely to be encountered in field application. The laboratory data reported here were obtained during an investigation of the possibility of using a gas-driven LPG slug in a partially depleted California reservoir. Seven gas-driven slug displacements employing slugs of different compositions and sizes were made in 26- to 27-ft long sandstone cores. The equilibrium phase behavior of the systems was also determined. The features of primary interest in this study are the following. 1. Data were obtained on the displacement of reservoir fluids at reservoir conditions. 2. A high gas saturation existed in the long cores at the start of the displacements. 3. The temperature of the studies was above the critical of the slug materials. 4. A comparison between the flow behavior and equilibrium phase behavior, as illustrated by a pseudo-ternary phase diagram, is afforded for a system of considerable complexity. THEORY Phase Behavior The use of the pseudo-ternary phase diagram to illustrate the phase behavior in miscible displacements has been discussed by Clark, Schultz and Shearin. Sie-vert, Dew and Conley and Arnold, Stone and Luffel' have presented both phase equilibrium and flow data for true ternary systems. For the true ternary, the application of the theory is straight-forward; for a reservoir system represented as a ternary, the theory undoubtedly gives a qualitatively correct picture. One purpose of this investigation was to see if the pseudo-ternary phase diagram could be used to predict with reasonable accuracy the conditions necessary for miscible displacements with actual reservoir systems. MiscIBLE Displacement of Two-Phase System A large number of papers "I3 have treated the miscible displacement of a single-phase fluid from both an experimental and a theoretical viewpoint. However, the normal field application of the process will be in a partially depleted reservoir. Often the state of the system will be such that the mobility of the gas phase is greater

By E. J. Bonet, P. B. Crawford

It is fairly common practice to reinject water into the aquifer near the oil-water interface in water-drive reservoirs. There have been many studies of aquifer behavior without reinjection,l-5 but apparently no analytical studies have been made to indicate performance when injection wells are present in the aquifer. The diffusivity equation may be used to describe the pressure behavior in an aquifer. When sources are present it can be written as A general solution of Eq. 1 may be obtained as the sum of two solutions. One is a general solution of the homogeneous equation, obtained by dropping the source term in Eq. 1 and still satisfying the required boundary conditions. Another is a general solution of Eq. 1 satisfying homogeneous boundary conditions.1° The first solution, which corresponds to the aquifer without reinjection, has been given quantitative and qualitative treatment in the literature.l-5,8,9 The latter solution will be treated here. Solutions with variable injection rates are obtained by superimposing solutions with constant rates, so we have considered only the latter. Five cases have been treated here: 1. A linear aquifer of finite width and extent. Water is injected into the aquifer at point xo, yo at constant rate. The pressure along the line x = 0 is maintained at zero pressure. (See Fig. 1.) Equations showing the pressure distribution, rates, velocity and cumulative influx have been developed. Certain numerical results are shown. 2. A linear aquifer of finite width and extent. Water is injected into the aquifer at point xo, yo at constant rate. The rate of production along the oil-water water contact is maintained constant. Equations showing the pressure distribution inside the aquifer are presented. 3. A linear aquifer of finite width and extent. Constant pressures are maintained at opposite ends of the aquifer. Water is injected at constant rates at point xo, yo. Equations showing the pressure distribution are shown. 4. A linear aquifer of finite width and infinite extent. The pressure is maintained constant at the oil-water contact. Water is injected at a constant rate at point xo, YO. 5. A linear aquifer of finite width and finite extent. The pressure at the oil-water contact is maintained constant. Water is injected at constant rate per unit length along a line x,. The Linear Aquifer The linear closed aquifer, performing at constant terminal pressure was selected as the first case to be analyzed. The development of the equations is based on uniform injection per unit of thickness, and gravity effects are neglected. In practical application this condition is probably most closely achieved when the

Jan 1, 1970

By Ernst A. Hauser

IN a paper published three years ago,' the term "silicic chemistry" was used for the first time to emphasize the increasing importance of the chemistry of silicon in science and technology. The development through which the colloid chemistry of siliceous matter has gone since then is in itself ample proof that the coining of this new term for this branch of colloid science was not presumptuous. Until quite recently, however, silicic chemistry concerned itself only with the composition and colloidal properties of natural and synthetic siliceous matter, but had not paid much attention to the genesis of this matter, particularly to that of the clay minerals. What is even more disturbing, particularly from an educational point of view, is the fact that neither mineralogy, geology, nor metallurgy has fully realized the important role colloidal phenomena must have played in the genesis of our planet and the formation of minerals generally speaking. Considering the importance of colloid chemistry today in the fields just mentioned, it is not surprising that the theories most agreed upon by geologists and mineralogists for the origin of clay minerals are not acceptable from a strictly colloid chemical point of view for the genesis of these most important and most abundant components of the earth. Of all the theories pertaining to the origin of clay minerals, those still most accepted by geologists and mineralogists are the "residual clay" and the "transported clay" theories.15 The former is based primarily on the assumption that the formation of clay minerals is the result of surface weathering of fresh rocks, or is due to the action of solutions. Taking the action of water on orthoclase as an example, the most recent ideas have been summarized by H. Jenny13 as follows:

Jan 1, 1952

By R. J. Watson, A. H. Juch

About half a million sucker-rod pumps are installed in oil wells in the U. S. alone. In Venezuela, too, the system is widely used; some 5,000, or 90 percent, of Cia. Shell de Venezuela's wells produce a total of 400,000 BOPD by this method. Most of the crude pumped is viscous, gassy and contains relatively small amounts of free water. API gravities vary from 90 to 16O; dead oil viscosities vary from 10 to 10,000 cp at the pump; and GOR's range from 100 to 2,000 cu ft/bbl. Pumps are set at depths ranging from a few hundred to 6,000 ft; the average setting depth is about 2,500 ft. From the literature, it appears that although recent years have seen significant progress toward understanding the rod pumping system as a whole, relatively little attention has been paid to those key items, the sucker-rod pump and the subsurface gas separator or gas anchor. Perhaps because of proration in the U. S., pump manufacturers have seemingly concerned themselves more with the durability of their product, achieved mainly through robust design and metallurgical know-how, than with its working efficiency. In 1963, CSV commenced a major rehabilitation and expansion of its heavy oil fields along the Bolivar Coast. The advent of the more efficient gravel-packed completion and of large-scale thermal recovery (mainly steam soak) operations resulted in well potentials *Now with B. I. P. M., The Hague, The Netherlands. greater than pump capacities. Hence, an urgent need arose to improve over-all pump efficiencies and to attack those special problems related to the production of both the extremely viscous and the hot, steam-laden crudes that formed an increasing proportion of the total stream. There followed a detailed investigation and testing program, carried out in close cooperation with a major pump manufacturer. This culminated in the introduction to the oil industry of a new line of sucker-rod pumps. Early Investigations and Experiments Field Tests Extensive field tests were carried out in three primary Bolivar Coast wells with an in-situ dead oil viscosity ranging from 400 to 6,000 cp. In these installations provision was made to (1) monitor bottom-hole pressures below, in and above the pump by means of pressure transducers, and record casing- and tubing-head pressures continuously; (2) measure accurately the annulus gas, as well as measure the tubing gas and liquid production from the well; (3) take special PVT samples of the well fluid; (4) measure power consumption of the prime mover; and (5) measure the rod loads at the polished rod. A typical test installation is illustrated in Fig. 1. It was established from the pressure transducers that with viscous oils, there is considerable flow resistance across the pump and gas anchor assembly. Pressure surges were observed over each pump cycle,

Jan 1, 1970

By M. Felsenthal

Engineers are frequently faced with the problem of having to predict oil recovery from a solution gas drive reservoir in the early life of a field. This is often the time when actual laboratory or field-derived gas-oil permeability (kg/k0) data are not yet available. Although excellent collections of k0/k0 data for various types of rocks may be found in the literature,1,2,3 a need exists for a more detailed correlation of k0/k0 data with core properties such as porosity, permeability, clay content or pore-size distribution. It is the purpose of this article to present this type of correlation for sandstone material. The correlation is based on laboratory tests performed on over 300 core samples from 19 reservoirs in the United States and Canada. EXPERIMENTAL Cores were analyzed by routine procedures, using samples of conventional size (7/8-in. diameter, 7/8-in long) cut parallel to the bedding planes. Air permeability was measured at 1.67 atm mean pressure in a Hassler-type apparatus. Porosity was determined with the aid of a Ruska bulk volume meter and a Boyle's Law rock volume meter, An evaporation method' was used to evaluate irreducible water saturations. Core samples were saturated with 25,000 ppm NaCl brine. The brine was reduced to the irreducible saturation, and the remainder of the pore space was filled with kerosene. This was followed by multiphase flow tests using the so-called "dispersed feed" technique.5 n this technique, gas and oil (kerosene and kerosene-saturated air) were dispersed with the aid of a porous Alun-durn feed head, the face of which contained a waffle-shaped system of Lucite-lined grooves. Oil entered the back side of the feed head and emerged at the raised areas of the front face. Gas was introduced directly into the system of grooves at the front face. The gas-oil mixture then entered the test core which was kept in capillary contact with the feed head. Permeabilities were determined from rate and pressure measurements and saturations from weights. All determinations were performed at equilibrium or steady-state conditions. Pore-size distributions were determined on selected samples by a mercury injection technique.6 GENERAL CORRELATIVE TRENDS When examining data from a given reservoir, it was noted that k0/k0 vs saturation curves became generally less steep as specific air permeability increased, a development that has a favorable effect on oil displacement efficiency by solution gas drive. This trend has also been reported by others in the literature.' An effect of porosity on k0/k0 data was also noted. This effect was not generally discernible in a study of relative permeability data for a given reservoir but became apparent when data for sandstone reservoirs of similar lithology but differing average porosity were compared. For instance, in a comparison of argillaceous and/or calcareous sandstones from 11 reservoirs ranging in average porosities from 14 to 28 per cent, a definite trend was noted, indicating that for a given permeability k0/k0 curves became less favorable (i.e., steeper) as porosity increased. A similar trend was observed for a group of comparatively clean sandstones from five reservoirs ranging in average porosities from 15 to 21 per cent. For a given permeability and porosity, comparatively clean sandstones gave more favorable k0/k0 curves than argillaceous and/or calcareous sandstone or chert reservoirs. The laboratory studies also showed that least favorable k0/k0 curves were exhibited by shaly sandstone, conglomerate, and sandstone containing carbon inclusions. Table 1 lists the various source reservoirs classified by lithology types. To facilitate a correlation of k0/k0 data with core characteristcis, it was found expedient to work with

By Herbert Clark Hoover, Lou Henry Hoover

As stated in the preface, the nomenclature to be adopted for weights and measures has presented great difficulty. Agricola uses, throughout, the Roman and the Romanized Greek scales, but in many cases he uses these terms merely as lingual equivalents for the .German quantities of his day. Moreover the classic language sometimes failed him, whereupon he coined new Latin terms adapted from the Roman scale, and thus added further confusion. We can, perhaps, make the matter dearer by an illustration of a case in weights. The Roman centumpondium, composed of zoo librae, the old German ceniner of 100 pfundt, and the English hundredweight of 1112 pounds can be called lingual equivalents. The first weighs about 494,600 Troy grains, the second 721,900, and the third 784,000. While the divisions of the centumpondium and the centner are the same, the Libra is divided into 12 unciae and the pfundt into 16 unizen, and in most places a summation of the units given proves that the author had in mind the Roman ratios. However, on p. 509 he makes the direct statement that the centumpondium weighs 146 librae, which would be about the correct weight if the centumpondium referred to was a ceniner. If we take an example such as " each centumpondium of lead contains one uncia of silver", and reduce it according to purely lingual equivalents, we should find that it runs 24.3 Troy ounces per short ton, on the basis of Roman values, and 18.25 ounces per short ton, on the basis of old German. If we were to translate these into English lingual equivalents of one ounce per hundredweight, then the value would be 17.9 ounces per short ton. [ ]

Jan 1, 1950

THE IRON HUNTER. By Chase S. Osborn, pp. 316, Ills. 10. The MacMillan Company, New York. 1919. An autobiography, the story of a Hoosier boy who fought his way to manhood and power through early misfortune and poverty, from street urchin and newsboy, to editor and author; from lumberjack and dock walloper to statesman and Governor of Michigan. The reader has the measure of the man in the first chapter, a dramatic recital of how the fighting boy editor cleaned up a lawless mining camp of 40 years ago. The thread of the narrative is the author's life-long devotion to outdoor living, ex-ploration and travel. Residing in Sault de Sainte Marie, Mich., in the heart of the Lake Superior country, he took his delight and, incidentally, found his fortune in prospecting the north woods for iron ore; eventually, extending his travels to the continents and many of the islands of the world, he discovered what, he believes-to be a great iron range in Madagascar. In this book there is plenty of anecdote, a great deal of wholesome social and po¬litical philosophy and some interesting sidelights on the characters of some of the author's prominent contemporaries in the political life of Michigan. The style is direct and animated, flavored and illuminated with the vernacular of Hoosierdom and the woods country of the North. The author levies on the vocabulary of the sciences and the classics for many a noun and adjective and, with Rooseveltian license, now and then coins a word. The reader's interest will be gripped from cover to cover, albeit he may occasionally need a dictionary. R. C. A.

Jan 11, 1919

By A. Thielen

In experiments for the production of steel the principal problem has always been the introduction into, or removal from, the iron of a definite quantity of carbon. Although the solution of this problem had engaged a more or less blindly and empirically directed effort for a long time, it was only with the development of analytical chemistry that the rôle which carbon plays in the constitution of steel was disclosed in its full significance, and that many of the problems confronting the steel-maker were thereby more clearly defined than before. For a long time, and to a certain extent even to this day, the percentage of carbon in steel has been the controlling means of deter mining its quality and hardness. In many cases the percentage of carbon alone has been relied on for judging large consignments, such as the large deliveries of wire-billets and blooms to America during the past twenty years; and though to-day the influences of the other constituents are recognized and many other considerations are taken into account, and though, moreover, some special steels, such as the Hadfield manganese steel, apparently dispense to a certain extent with the assistance of the carbon, yet fix our Bessemer, Thomas, Siemens and crucible steel the carbon still remains one of the most important constituents, and I venture to say it is indispensable. In order to produce in the Bessemer converter a steel of a certain required percentage of carbon, two methods, as is well known, present themselves. By the one the decarburization process is stopped when the desired carbon limit in the bath has been reached ; by the other the bath is completely decarburizecl, and then a calculated amount of carbon added in the form of spiegel, ferro manganese, etc. In Germany the latter method only was adopted, and it was retained when the Thomas-Gilchrist process for the production of low-Phosphorus steel from high-phosphorus iron eame into use, since from the nature of the new process complete decarburization is neces-

Jan 1, 1891

By A. H. Larson, L. G. Twidwell

DURING the roasting of zinc sulfide concentrates and by-product recovery from flue dusts, the zinc sul-fate phase may occur in various stages of the processes. In addition to zinc sulfide, other sulfide phases are usually present such as CdS, PbS, CuzS, and FeS. Consequently, the effect of these sulfides on the thermal decomposition of ZnS04 was investigated. Merck high-purity, anhydrous zinc sulfate was used as the starting material. The sulfate was heated under an argon atmosphere, at a rate of 10°C per min. With the first slight indication of decomposition as determined by gas analysis, the sample was removed from the furnace and allowed to cool. X-ray patterns showed no other phase present. It is estimated that less than 0.05 pct of the ZnS04 decomposed. The metal sulfides were also heated under an argon atmosphere to drive off any adsorbed water. The materials were then sized (-200 to +270 mesh), mixed in predetermined mole ratios, and pressed into pellets. The experimental measurement of the reaction rate consisted of purifying the argon carrier gas, continuous flushing of the heated reacting mixture with argon, and collection and analysis of the SOn product gas. The reaction system was heated to 600°C and al-

Jan 1, 1967

By D. W. Levinson, L. E. Tanner

DURING the course of an investigation of the zirconium-iron-tin system the zirconium-iron system was reexamined up to 55 pct* Fe. The alloys pre- visible melting3 and X-ray diffraction studies were made of samples of the alloys. The ferromagnetic properties of ZrFe2were determined by Professor P. W. Selwood* using a modified Faraday balance.4 The zirconium-rich portion of the phase diagram is presented in Fig. 1 and compared with the work of Hayes et al.1 The maximum solubility of iron in ß is somewhat decreased while the eutectic temperature is raised. There seemed to be no change in the eutectic composition of 16 pct Fe. Since the base material was so low in iron content, it was possible to establish the maximum solubility in a between 0.017 and 0.025 pct Fe at the eutectoid temperature. The observation of fine ZrFe, particles in the micro structure of a specimen of 0.012 pct Fe alloy quenched from 700°C indicated that the solubility drops below this composition at 700° C and lower. Further study was made of the intermediate phase ZrFe2. wallbaum5 identified the compound initially as ZrFe2 with a C 15 (MgCu2) structure, placing it at 55 pct Fe stoichiometrically. Hayes et al.1 believed they found the phase at about 47.2 pct Fe and called it Zr2Fe3 but reverted to ZrFe, in the discussion of their paper.6 Jordan and Duwez7 confirmed Wallbaum's work as well as finding the same single-phase structure to about 62.3 pct Fe or Zr0-61 Fe2-18. In order to establish the ternary phase relations in the zirconium-iron-tin systema the exact position of this phase had to be known. This was accomplished by X-ray diffraction, visible melting, and metallographic techniques. Elliott8 obtained a single-phase ZrFe2 X-ray diffraction pattern from an alloy of about 55 pct Fe. This was confirmed in the present study with an alloy of 54.81 pct Fe. However, extra lines (attributable to a or ß zirconium) were found in diffraction patterns of the 47.42 and 49.83 pct Fe alloys. The melting characteristics of these same alloys were studied by suspending 47.42, 49.83, and 54.81 pct

Jan 1, 1960

By R. M. Kuralt

CONCESSION from the Chilean government granting the company use of the Rio Salado water stipulates that a minimum of 35,000 metric tons of such salty water must be diverted from the Salado daily, and be disposed of in a manner not to contaminate the Rio Loa to the east of its confluence with the Rio San Salvador at Chacance, Fig. 1. Consequently, the selection of a suitable site for the sulphide plant tailing disposal had the additional problem of the disposal of excess brackish waters. Studies of the terrain in the area directly to the south of the plant indicated that construction of tailing ponds would be costly, and generally unsatisfactory due to excessive slope of the ground, lack of flanking hills, danger of raising the groundwater level thus causing springs along the Antofagasta-Bolivia railroad; and the possibility of creating a dust nuisance at the plant site or at Calama due to blowing sands. Further to the southwest the San Salvador river canyon offered some possibilities and surveys were made at sites A to D, inclusive, Fig. 1. Here again costly dams would have been necessary to impound the tremendous quantity of tailing produced by the new plant, and provision would have to be made to handle a considerable flow of water through the disposal area to the west of the Rio Opache. Additional surveys were made in the area to the southeast of the plant which brought to light the existence of a natural basin of about 14 1/2 square miles, flanked by low-lying hills, and requiring only the most rudimentary dams to close the outlets at the western end. It has been estimated that the Salar de Talabre, as this basin is called, has the ultimate storage capacity of 1 billion tons of tailing with dam heights of only 60 ft. Pipe Line Layout After the decision had been reached to use the Salar de Talabre for the main disposal area various methods were considered for transporting the tailing from the 300 ft diam thickeners to the disposal site, 17.7 miles away. The first plan was to construct a. concrete launder on a 11 pct grade but a survey of this grade line indicated it would not lead directly into the Salar but would terminate somewhat to the north, and from that point on the slope would be considerably less than 1 pct along a natural watercourse. A slope of 2 pct or even 2 ¼ pct in such a rough watercourse or ditch is the ideal, judging from the success of operations at Cananea. Since a simple ditch is the most economical vehicle for the transportation of tailing, it was decided to use one with a 2 ¼ pct grade for as much of the distance as was possible with the existing terrain and to construct a concrete headbox, or forebay, at the terminus of the ditch to supply a steel pipe line leading the rest of the way into the Salar. Referring to the maps of the Chuquicamata area outlining the tailing disposal system, Figs. 1 and 2, one can trace the flow of the tailing from the thickeners to the Salar as follows: The 8-in. spigot pipes from the thickeners (1) discharge into a concrete sump feeding a concrete launder with a 2 pct slope. The launder carries the tailing into a concrete junction box (2) located south of the sulphide plant. The purpose of the junction box is to provide emergency facilities for diverting the tailing flow from the main disposal area to the emergency area. It also provides a junction point for the launder from the sulphide plant's future east extension. The box is fitted with a pair of radial gates controlling flow into the main tailing ditch (6) or the emergency ditch (3) which terminates on the pampa. All ditches are of the same cross section, namely 4 ft wide at the bottom with 1 : 1 side slopes and with a minimum depth of 21/2 ft. Where the nature of the ground demands it, the ditches are lined with stone rubble. The overflow from the plant's 10 million gal reservoir (4) is led into the main tailing ditch by way of a spillway ditch (5). The main ditch terminates in a trashscreen fitted, concrete forebay (7) which serves as a headbox for a 24 in. O.D. x 3/8 in. wall, Dresser coupled, steel pipe (10) and a 12 in. x 8-gage spiral welded, wedge-lock coupled, steel pipe (8). The forebay is fitted with two compartments, one for each pipe, and flow into each is controlled by radial gates. Each compartment is fitted with a 6-in. drain pipe controlled by a rubber pinch valve. To protect the forebay from the abrasive effects of the tailing, the sides of the compartments will be lined with old

Jan 1, 1952

By Frederic P. Dewey

This old and well-known method of determining silver is, in bullion work, so far superior to the furnace-assay that it is looked upon with reverential awe by many, if not by most, users, and its ease of execution, with proper equipment, commends it highly where much commercial bullion work on silver is required. The method is so thoroughly well known that a description of it here may seem to be unnecessary, but many thousands of determinations are annually made by it in the U. S. Mint Service and its practice is there reduced to an art. This is necessary both for the sake of economy of time, and because high-grade work with it requires constant practice. It is useless for a person who uses it only occasionally to expect to attain high accuracy with it, without spending more time upon a detemination than is warranted in a busy commercial laboratory. It is always employed in the Mint service whenever possible, but its chief field is in the determination of silver in standard silver (ingots and coin), which is 900 fine in silver and 100 fine in copper, and I shall first briefly outline its use on this metal and then take up various points in detail, especially as related to the accuracy of the results obtained. For this determination 1,115 mg. of standard metal are weighed and transferred to a glass-stoppered bottle, the metal is dissolved in nitric acid, and 100 cc. of a standard solution of NaCl run in. The bottle is then vigorously shaken and a measured portion of a decimal salt solution added, and again shaken, if necessary. These operations are repeated until the silver is precipitated. Standard metal being 900 fine, 1,115 mg. should carry 1,003.5 mg. of silver, which is a convenient figure to work with.

Jan 1, 1914

By P. K. Guerrero, N. Arbiter

The correlation of power consumed by a tumbling mill with the dimensions, speed, and load has been attempted by three principal methods. One of these, the torque formula, has been reviewed critically elsewhere.' This approach, while analytical, disregards the individual motion and speed of the tumbling bodies and assumes that the gross geometry of the entire load is sufficient to establish the power requirement. A more general approach, using dimensional analysis, has been applied in this laboratory by the present authors1'1, and more recently by Rose.3 This disregards the internal conditions within the mill entirely and in effect is an empirical procedure for correlating data. Finally, the complete analysis of tumbling mill dynamics as first made by Davis' attempts to develop the power requirement from individual ball and rod paths and velocities. Although Davis' result is applicable only at a single speed for a given size and load it could be useful, since his optimum speed is at the upper limits of conventional tumbling mill practice. Where power values predicted by the Davis equation were compared with actual mill requirements, they were found too low for small mills and much too high for the largest mills. This suggested that the agreement with actual intermediate range requirements might be fortuitous, and the development of the equation was examined critically. The probable source of error was found to lie in an erroneous assumption made by Davis in converting the energy of ball or rod motion to power. With the same approach, but with different assumptions, a modified equation has been obtained which predicts results that are usually consistently high. This is to be expected, since it is assumed that there is no slip between load and shell and no interference among tumbling bodies. Both these effects should account for the difference. Development of Equation: When a cylindrical shell charged with a substantial weight of rods or balls is slowly rotated about a horizontal axis, the load surface first assumes an inclination that gradually increases to a maximum. Continued rotation results in failure within the load, characterized by a sliding of the top layers down the slope and a reduction in the angle of inclination. Further rotation again increases the angle, and the cycle repeats. If the speed is increased, there is continuous load failure and build-up and a continuous stream of rods or balls descends over the upcoming mass, which moves in circular arcs. At higher speeds the up-

Jan 1, 1961

By D. H. Gurinsky, D. G. Schweitzer

The empirical equilibrium constantsd the heat of reaction for the reduction have been determined from 300° to 500°C. The mechanisms of the oxidation of uranium and magnesium from dilute bismuth solutions have been investigated. The kinetics of some of the reactions were affected by air adsorbed on the uranium oxides. THE Liquid Metal Fuel Reactor studied at Brook-haven National Laboratory uses a solution of uranium in bismuth as the fuel. Corrosion and stability problems require that the fuel solution contain corrosion inhibitors and deoxidants. Of the additives tested, magnesium has been found to be the best deoxidant and zirconium the best corrosion inhibitor in bismuth. Some experiments1 indicate that magnesium may play a secondary role in increasing the effectiveness of zirconium in inhibiting corrosion. The work reported here was intended to determine the relative concentrations of Mg and U required to prevent oxidation of the uranium fuel in the event of an air leak. In addition, an attempt was made to identify some of the mechanisms of the oxidation and reduction reactions occurring in the liquid bismuth solutions. EXPERIMENTAL Apparatus and Procedure—The equipment shown in Fig. 1 was designed so that the reaction kinetics could be studied as functions of temperature, melt composition, pressure, and flow rate. At the start of a run, the 10-liter bell jar (F) is removed by opening the bottom Dresser fitting (L), and the bismuth and additives are placed in a pyrex crystallizing dish (I). The bell jar is replaced, the system is evacuated to 10-5 to 10-6 mm Hg and then the heater (J) is turned on. When the selected temperature is reached, the oxidizing gas is admitted to the system to the desired pressure as read on the manometer (D). Gas is introduced through the slide tube (Q) which has a pyrex frit (R) sealed to its bottom. Stirring is accomplished by immersing the end of the tube in the melt. To maintain a constant pressure under flow the input and evacuation rates must be equalized. To obtain this condition stopcock (C) is closed and flowmeters (B) are matched. The reaction is "stopped" by closing the inlet flowmeter and quickly evacuating the system. To obtain a liquid metal sample, the system is evacuated with the sampler positioned near the surface of the liquid. The sampler, Fig. 2, is then immersed until its thermocouple reading matches thermocouple (G) Fig. 1. The system is then pressurized with helium which forces the solution through the frit. Twenty to 30 min elapsed between the time the system was evacuated and sampled. During evacuation and pressurization of the system, the temperature variations did not exceed ± 5°C. While bubbling occurred the temperature remained constant to within 1/2 oC. The volume of the equipment was determined by adding a known volume of air at atmospheric pressure to the evacuated system and noting the resulting pressure.

Jan 1, 1962

By Grafton Thrasher

For the proper discussion of this subject it is necessary to incorporate in this paper the substance of part of an article published by rite in Metallurgical and Chemical Engineering for January, 1915. CAST-IRON TEST PLUG, SHOWING LOW MOTTLED AND MOTTLED FRACTURES. Several years ago, while I was thief chemist for a malleable-iron company, it occurred to me that the mere regulation of silicon was not sufficient to produce the desired degree of chill. But only after repeatedly encountering this fact in befit open-hearth and air-furnace, as well as cupola metal, was I led to regard variation in the total carbon as the principal cause of disturbance; and I resolved to determine the total carbon as well as the sill on ill every heat, and by a carefully prepared test piece to gauge the approximate degree of chill. The test piece selected was a round plug, 2 in. in diameter and 12 in. long, cast on end

Jan 10, 1915

By Malcolm T. Hepworth

RECENT interest in thermoelectric devices has been directed toward studies of the properties of thermoelectric materials of semiconducting solid compounds with little attention given to ionic and semiconducting liquids such as aqueous solutions, fused salts, and mattes. One type of thermoelectric system is the thermocell: a nonisothermal galvanic cell with two identical electrodes at different temperatures connected by an electrolyte bridge. An electromotive force, v, is generated which is a function of the electrode reactions and the properties of the electrolyte according to the Eastman' equation: where S* is the entropy change of the system arising from the electrode reactions and by heat transferred by ion migration and by thermal conduction. The quantity nF is the product of equivalents passed and Faraday's constant. A value of S* of 23.06 cal per "C is equivalent to 1 mv-Faraday per "C. The symbol, a, is used for dV/dT in analog to the See-beck coefficient of solid-state thermoelements. de Bethune2 has calculated the temperature coefficients of the electromotive force of a large number of nonisothermal aqueous cells from measurements on the nonisothermal temperature coefficients of the standard hydrogen electrode, combined with data on the isothermal temperature coefficients of half-cells tabulated in the literature. Values of these coefficients (a) in de Bethune's compilation ranged up to 3 mv per C. In particular he reported a value of +2.059 mv per "C at 25'C for the cell: Fe (aqueous, unit activity) (aqueous, unit activity) written for the hot-electrode reaction. The positive sign indicates that the hot electrode is positive (an "n-type thermocell"). In analog to a solid-state p-n system, it would be possible to couple two thermocells together to form a system in which the figure of merit could be calculated by adding the temperature coefficients according to the relationship described by offee:' where a is the Seebeck coefficient in volts per "C, p is the specific resistivity in ohm-cm, and K is the thermal conductivity in watts per cm "C. Even though ionic systems have rather high electrical resistivities compared with semiconducting and metallic systems, it was felt that a preliminary study of one ionic system should be made to establish some basis for evaluating the possibility of a p-n thermocell for energy conversion. Accordingly the Fe", Fe"' system was studied as a possible component for a p-n system. A glass system was constructed consisting of two vertical water-jacketed tubes connected by a horizontal tube, Fig. 1. Platinum-black electrodes 1 cm by 1 cm in dimension were inserted in each vertical tube with thermometers to register the electrode-compartment temperatures. The temperature of the electrode compartments was controlled by circulating water from thermostatted baths around the electrode compartments. The electromotive force of the cell was then read by a potentiometer for zero current as a function of the temperature of the hotter electrode. Current output of the cell for varying external loads was also measured. The cell resistance was measured by means of a bridge circuit with 10,000 cps signal and oscilloscope. Resistance measurements were converted to specific resistivity by calibrating the cell with a solution of known conductivity.

Jan 1, 1965

By D. F. Malott

The Michigan Dept. of State Highways makes extensive use of geophysics for subsurface surveying which would be applicable for uses in other fields. Examples of resistivity surveys are given which include a proposed large-volume excavation with suggestions for land use after excavation, subsurface evaluation for engineering design, and a subsurface survey for land appraisal. An example of a combined refraction seismic and resistivity survey is shown where the resistivity is used for outlining the unconsolidated soils, while the seismic method is used to outline bedrock and to evaluate it for rippability. A refraction seismic survey at the bottom of bridge caissons for evaluation of bedrock uniformity and a rehtive aid in assessing rock strength is reported. These past several years have been a period of unprecendented construction and commercial expansion. Vast private manufacturing complexes and government road, power, and office projects are being built or are in planning stages. Nearly everywhere, municipalities are expanding outward and upward. Many towns are developing into cities and many cities are displaying new skylines, and the building boom shows little sign of slowing down.

Jan 1, 1970