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By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,' and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.' Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8'7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8'9 Copper minerals sometimes yield elemental sulfurlo'" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,'5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967

By Frances H. Clark

IN wartime, the fabrication and use of metals assumes increased importance, for a modern war of sizable proportions cannot be undertaken with- out a vast supply of this material. Light alloys of aluminum and magnesium, which were comparatively unknown in the last war, will play an important role in this one. Due to research on a vast scale in the interim of years, industry is today well equipped to fabricate metals on an enormous scale. Research for the past year has been most productive and a comprehensive survey in the space of this article would be impossible. It is hoped that the stressing of a few items here and there out of a great quantity of able work will indicate in a small way the advances made within recent times. Specific references to the literature will be omitted at the Editor's re- quest but some authors of papers that I have found of special interest are mentioned.

Jan 1, 1940

By W. G. Scott

Since devising the incline top-slicing method in use at the Coronado mine,l I have had numerous inquiries as to how the same system could be adapted to larger orebodies. Based upon our experience here, I have outlined below some suggestions for its application to orebodies of larger size. Modifications and extensions, of course, would have to be made to take care of different dimensions and irregularities. In order that one may have a better understanding of the scheme, a brief description of the Coronado method will be given first. CORONADO METHOD The portion of the Coronado vein that is worked by the slicing system ranges from 20 to 40 ft. (6 to 12 m.) in width. Preparatory work in this orebody consists of driving sub-levels every 55 ft. (1 6.77 m.) vertically, or in multiples of 11 ft. (3.36 m.) (which is the height of a slice). These levels are usually driven along the hanging wall until the end of the orebody is reached. Crosscuts, at right angles to the strike, 50 ft. (15.24 m.) apart, are then run from wall to wall, or until the lean ore is reached. They are run in the middle of the block, which is 50 ft. in length and the width of the vein. The crosscut on the hanging-wall side is extended in the wall a short distance for a manway and timberway raise. This raise is carried up in the wall to the sub-level above, leaving a pillar about 5 ft. in thickness between it and the vein. Connections are made every 11

Jan 1, 1918

By J. J. Becker

BEAN1 has discussed the magnetic behavior of mixtures of small ferromagnetic particles on the order of 20 to l000A in diam. As he points out, there are three size categories with characteristic properties: 1) Particles large enough to contain many ferromagnetic domains magnetize initially by the motion of domain walls. The initial susceptibility of such particles, if domain-wall motion is assumed to be perfectly easy, depends only on their shape. It is equal to the reciprocal of the demagnetizing factor (and is thus 3/4 tt for a sphere) and is independent of temperature. 2) Smaller particles find it energetically undesirable to contain domain boundaries. They are always spontaneously saturated, and reverse their magnetization only by rotation of their entire magnetic moment. As assemblage of such particles has a remanence which is a large fraction of the saturation of the assemblage; its coercive force is on the order of 2K/1,, where K indicates magnetic aniso-tropy from any source, and I, is the saturation magnetization of the substance of which the particles are made. 3) Particles which are still smaller continue to be single-domain, but the direction of their magnetization fluctuates thermally, as first pointed out by Neel.' They have no remanence and no coercive force and possess the temperature-dependent magnetization curve of a paramagnetic substance with a very large moment. Bean calls this superpara-magnetism. All of these kinds of behavior are observable in alloys consisting of a precipitate of ferromagnetic phase in a nonferromagnetic matrix. Fig. 1 shows a typical aging curve for the room temperature coercive force of a sample of 98 pct Cu-2 pct Co alloy

Jan 1, 1958

By R. A. L. Black

13.8-1. Introduction. Table 13.8-1 shows that production from the African continent is an important part of total world mineral production. In three of the major particular resources listed, diamonds, gold, and cobalt, African production accounts for considerably more than half the world output. Overall, South Africa including South West Africa plays a dominant role in the mineral economy of Africa, other than in petroleum production. Table 13.81 also shows that much of the production is won by surface mining methods. In addition to the minerals listed in Table 13.8-1, Africa is a main world source for the following minerals: [Beryl 33% of total world production Columbium-tantalum 50%" " 1' Platinum group metals 20% l' " 11 Corundum 55%" " " 11 Vermiculite 30% (' " (6 Uranium oxide 15 0/, of free world production] South Africa and Rhodesia together account for nearly all of this production, except for columbium (niobium) of which Nigeria is the main producer. Thus the importance of southern Africa as a major mineral province can readily be appreciated. The consequences of serious political or military conflict between white-dominated southern Africa and the rest of the continent would be grave indeed, particularly for the West whose financial and economic interest in Africa as a whole is very large. The development of mineral resources in Africa involves the same basic elements as are involved anywhere else in the world: exploration, drilling and sampling, metallurgical assessment, and economic evaluation before, if it is justified, a prospect is brought to the productive stage. The same range of factors controls the economic viability of a project in Africa as elsewhere, of which the most important are:

Jan 1, 1968

By David B. Reger

The value of carbon ratios in determining the boundaries of possible oil deposits appears to have passed the hypothetical stage. The theory that the ratio of fixed carbon in pure coals is an invariable index of incipient metamorphism in both surface and underground rocks and that it may be applied in defining the limits of petroleum, advanced by David White,' has been received with keen interest by many petroleum geologists. Detailed isocarb maps have been prepared of the Pennsylvanian area of North Texas and Eastern Oklahoma by M. L. Fuller.² A similar map of the coal-bearing area of West Virginia is given here. An isocarb3 is a line showing an equal fixed-carbon percentage, pure coal basis; the term has been proposed by David White to supersede a less expressive nomenclature. The term carbon ratio is applied to the pereentage of carbon in pure coal after water and ash have been eliminated. As a comparatively small number of analyses have been made on this basis, it is usually necessary to compute the ratio by dividing the fixed carbon of the proximate analysis by the sum of the fixed carbon and volatile matter of the same analysis. Many thousands of proximate analyses have been made by the West Virginia Geological Survey, covering nearly every county in which coal is found. Numerous others have been made by the U. S. Geological Survey and the U. S. Bureau of Mines, but as uniformity of results is best secured by adhering to one set of analyses, the tests of the West Virginia Survey have been cxclusively used.

Jan 1, 1921

By Paul Pietrokowsky

THE formation of intermediate phases in the solid state reaction of titanium with silicon, germanium. and tin (of subgroup 4B in the periodic table) was the subject of a recent paper.' Further investigation of the system Ti-Sn revealed the presence of a new compound on the titanium-rich side of this phase diagram. Metallographic evidence indicated that this new phase was situated very close to 75 atomic pct Ti. The present work is concerned with the crystal structure of the intermediate phase Ti3Sn. Iodide-process titanium metal, furnished by the New Jersey Zinc Co., was used in this investigation. The metallic tin was received in powder form from Charles Hardy Inc., New York; its purity was 99.80 pct. The titanium rod was machined into small cups 1 cm in diam and about 1.5 cm in height. The tin powder was compacted, melted, and then placed in the titanium cups and alloyed by electric arc melting in a helium atmosphere. The alloys, weighing approximately 8 g, were sealed in evacuated quartz tubes and homogenized at 1030°C for 5 days. This isothermal heat treatment was terminated by a water quench from the soaking temperature. Filings of the alloyed pellets were sealed in evacuated quartz bulbs and quenched from 1030°C into liquid argon. A 14.32 cm Debye Scherrer X-ray camera was used for the powder diffraction study. The copper radiation was filtered. X-ray diffraction data for the compound Ti3Sn are given in Table I. The data were indexed on the basis of a hexagonal lattice. Good agreement between observed and calculated values of the square of the reciprocal interplanar spacings was obtained with the following expression: (1/d)2 = 0.03810 (h2 + hk + k2) + 0.04410 (l2) Unit cell parameters were calculated by the method of least squares from the reflections (20.3), (22.2), (40.1), and (42.1); ao = 5.916 & 0.004A, co = 4.764 ± 0.004A, and co/ao = 0.805. The relatively small size of the unit cell allowed the unambiguous indexing of most of the reflections from planes of large spacing. An inspection of the assigned indices (Table I) reveals the absence of (hk.l) reflections when 1 2n. A systematic absence of this type leads to the space group C 6/mmc or one of its subgroups. Assuming, for a first approximation, a linear increase in the density of titanium with the addition of tin, it follows that there are two stoichiometric molecules of Ti3Sn per unit cell. The density calculated from X-ray measurements is 5.194 g cm-'. At this point it became clear that Ti3Sn might be isomorphous with Mg3Cd. The 6 Ti and 2 Sn atoms were placed in the following positions of space group D4 6h, C 6/mmc: 6Tiin (h): X 2X 1/4; 22;; 1/4;Xx 1/4;x2x3/4; 2x x 3/4; x x 4; with x = 516 2 Sn in (c): 1/3 2/3 1/4; 2/3 1/3 3/4.

Jan 1, 1953

By Clyde E. Williams

IN planning a postwar program for manufactured products, it is essential that the bases for the plans be wisely chosen. First we must make certain assumptions as to the war's ending. Let us assume: (1) complete victory by the United Nations, (2) peace terms that will ensure the direction of the economy of all nations of the world toward peaceful pursuits, and (3) an early ending of the war, that is, before the nations of the world, excluding the enemy, are near the point of physical and spiritual exhaustion. Thus, our manufacturing plants and transportation facilities will still be in good shape. The plants and transportation facilities, as well as the cities of a large part of Europe, however, will be badly crippled. The rich mineral and other raw material resources of the world, little of which was under control. of the Axis powers before the war or will be after the war, will not be used up. Control of these raw materials, or at least an important part of them, will remain in the hands of the strong peaceful nations.

Jan 1, 1943

By E. W. Davis

THIS nation has been depending upon the Lake Superior iron ranges for most of its iron ore requirements for over half a century. Furthermore, it can continue to draw the major portion of its ore requirements from the same source for another century or more, but to accomplish this, great changes must take place in the present ore mining industry. Preliminary preparations for these changes are now underway and in the next few years decisions of far-reaching importance must be made. But to understand the situation, it is first necessary to know something of the nature and occurrence of the Lake Superior iron formation. So far as is known, the merchantable grades of iron ore remaining in the various Lake Superior ranges are as shown in Table 1, which shows that

Jan 1, 1947

By L. C. Graton

At the Tenth International Geological Congress, Mexico, 1906, Waldemar Lindgren presented "The Relation of Ore Deposition to Physical Conditions." Retrospect ranks it as the outstanding offering at that Session and as the most fundamental contribution up to that date on the philosophy of ore deposition. Elaborating thereon in his text-book "Mineral Deposits," Lindgren analyzed ore-forming processes under conditions prevailing from great depth up to surface; explained the nature of deposition in each environment; and developed a comprehensive genetic ore classification, which brought wide acceptance and enriching contributions by many. Since Lindgren's latest edition (1933), have come wealths of material relevant to ore genesis, particularly through amazing renaissance and proliferation throughout science. Current publication regarding ores now emanates largely from a generation caught in pressures of the breathless modern tempo, which tempts scant reflection upon earlier truths. Consequently, today's thrilling output contains not a few offerings that need challenge because supplanting interrelationship and system by what seems, collectively, an assemblage of strange, ad hoc and often self-contradictory concepts. From these latter some merit may eventuate but at the probable cost of present confusion and delayed progress. The following pages, naming numerous post-Lindgren advances, record the conviction, held by many, that Lindgren's philosophy, progressively improved, remains the soundest approach to understanding ore genesis.

Jan 1, 1968

By Howard N. Eavenson

DURING the past year, as in the preceding ones, prices continued to fall, production to decrease, and more mines were closed. Much attention is being given by the industry to suggested plans for betterment of its position, and if the scheme recently brought out for consolidation of sales agencies into district agencies is loyally carried out, it cannot but help to improve conditions. The progress in the anthracite industry is shown in the report of its chairman, E. H. Suender; changes in coal preparation are outlined in the report of J. B. Morrow, chairman of Committee on Coal Preparation, while increased mechanization of the western mines is described by Eugene McAuliffe, chairman of the Committee on Machine and Strip Mining. In spite of the depression, interest in the Coal Division has been increasing, its meetings have been well attended, and its committees are active and have been doing excellent work.

Jan 1, 1932

By M. P. Tixier, A. Poupon, M. E. Loy

Simple qualitative methods are explained for identifying those shaly sands in a well that are most likely to contain oil. A need for more precise measurement of the variables that enter shaly sand analysis is indicated. Field examples are given to illustrate the methods. A theoretical discussion of the quantitative interpretation of shaly sands is given as a basis for discussion and as a guide for the future. While not generally capable of practical application at the present time because of the lack of sufficient accuracy of the electric log data, these methods may become more feasible in the future as the result of the improved logging methods now being introduced. INTRODUCTION Experience has shown that for porous formations containing only a negligible amount of clayey material, reliable information on the fluid saturation and porosity of the reservoir rocks can usually be derived from the electrical logs. The interpretation is based on empirical formulae relating the true resistivity of a porous formation to its lithologic character, to the resistivity of the interstitial water, and to the proportions of water and hydrocarbons in the pores.' If the resistivity of the interstitial water is not known, its approximate value can be derived from the SP curve.2,3 The porosity can usually be determined to a good approximation from a MicroLog, or a MicroLaterolog.4,5 When the reservoir rocks contain an appreciable percentage of clayey material, an additional factor is introduced into the analysis. In a clean formation, the matrix is an electrical insulator, so that the ability of the formation to conduct current is due only to the conductivity of the electrolytes in the pores; in a shaly formation, the shale constitutes a part of the rock matrix able to conduct current, and influences the resistivity of the formation. On the other hand, the spontaneous emf's and the circulation of the SP currents are also responsive to the presence of the shaly material. All other factors being the same, the deflection of the SP curve opposite a shaly permeable formation is smaller than the deflection which would be observed if the formation were clean. The effects of the presence of shale on the resistivity and on the SP curves in a shaly formation are functions of the amount, of the specific resistivity, and of the geometrical distribution of the shaly material within the formation. The presence of shale therefore constitutes an important complication in electrical log interpretation. It is easy to realize, for example, that the presence of a large amount of clayey material in a sand may have such a predominant effect that the resistivity of the sand will not change very much, whether the pores are entirely filled with connate water, or contain a high saturation of hydrocarbons. Important research projects have been undertaken to investigate the influence of shales and to find a way to allow for this influence in the interpretation of a log. The problem of the SP in shaly sands was analyzed mathematically by H. G. Doll"' for the case of sands with shale laminations. Formulae expressing the resistivity of shaly formations were proposed by Patnode and Wyllie8 and de Witte.9 Other quite interesting theoretical and experimental results have been published by various authors.l0,ll,12,l3,14 The purpose of the present paper is to discuss an approach to electrical log interpretation in shaly sands. This approach is based partly on some of the theoretical and experimental data available in the literature and partly on observations made on actual field logs. Comparatively simple methods for qualitative and semi-quantitative analysis are described. These methods depend principally upon information provided by the electrical logs.

Jan 1, 1955

By Howard E. McKinney

A high-pressure wellhead lubricator has been developed to facilitate telemetering electrical measurements from subsurface reservoirs to the surface with the well under normal flowing conditions. The field unit in use at the present time employs a 5/16-in diameter, single-conductor armored cable and is to be used in wells with surface pressures up to 5,000 psi. It has a pressure sealing element that maintains a continuous and absolute seal around the cable as it enters or leaves the tubing at speeds up to 175 ft per minute. A cable injecting device is used which obviates sinker bars or weight sections on the instrument. INTRODUCTION The development of instruments for securing physical measurements in pressure wells has been confined in the past to those instrument which would operate on a wire line and record the necessary measurements in the downhole instrument itself, or those which would operate on an electric cable in a well with the surface pressure killed by the use of weighted fluids or by the use of tubing plugs. In one case the accuracy of the measurements is questionable, and in the other the range of application is very limited. Considerable work has been done by other interests to provide effective means to accomplish the necessary telemetering. The U. S. Bureau of Mines developed a wellhead lubricator prior to 1947 which permitted a 5/16-in diameter single-conductor cable to be lowered into a well with a surface pressure of approximately 500 psi. This unit was used successfully in a number of tests in Oklahoma. A company which tests wells has recently offered on a service basis a wellhead lubricator with a 3/16-in diameter cable that reportedly operates up to 2,500 psi surface pressures. Each of the above operates on a staging principle to effect a seal. In both of these units some leakage of well fluid occurs when the cable is moved. SPECIFICATIONS FOR DESIGN In order to provide the maximum flexibility in its use, the following parameters were established for the design of our high-pressure wellhead lubricator: L An absolute well fluid seal up to 5,000 psi surface pressures. 2. Means for raising and lowering the instrument at speeds of at least 100 ft per minute. 3. Provision for the instrument to enter and leave the well without disturbing the well flow or the reservoir conditions. 4. A cable large enough to provide suitable electrical characteristics and suitable mechanical properties. 5. A method of operation that will not damage the well in any way. The present high-pressure wellhead lubricator field unit fulfills the above requirements. DESCRIPTION OF THE UNIT AND ITS OPERATION The cable selected for this use is the standard Amergraph 1H2 as manufactured by the American Steel and Wire Co. This particular cable is normally used by the Halliburton Oil Well Cementing Co. in their conventional well logging operations. Although the cable presents a noncircular cross-section (Fig. l), its diameter is very consistent; lor example, maximum diameter is 0.325 in., minimum diameter 0.314 in. This [actor permits the use of the sealing element, as later described. Early in the development of the high-pressure wellhead lubricator it was apparent that we could not effect a direct gas seal around a moving 1H2 cable. This becomes evident when an examination of the cable cross-section is made. The voids between the strands of the outer armor provide natural channels lor the flow and escape in large quantities of a low-viscosity fluid such as gas. However, it is relatively simple to

Jan 1, 1952

By A. B. Kinzel

SILICON and its metallurgical uses have been the subject of speculation since the earliest days of modern civilization. The early philosophers, Theophrastus and Pliny, believed that silica was a special form of ice, an opinion that was not seriously challenged until the seventeenth century. The first comprehensive view of the nature of silica was advanced by Lavoisier in 1787. He assumed silica to be an oxide of an unknown metal. In 1808 Berzelius produced ferrosilicon by heating silica, iron and charcoal. Probably the first produc¬tion of crystallized silicon was in 1854 when H. St. C. Deville accidentally produced the material while electrolyzing a double chloride of aluminum and sodium containing siliceous impurities. It is not strange that the early investigators should have given so much attention to silica and silicon, because of the great natural abundance of the former. Although silicon does not exist in the elemental state in nature, it has been estimated that the lithosphere contains approximately 60 per cent silica; quartz and rock crystal are found in practically every part of the world.

Jan 1, 1933

By J. Gurland

THE microstructure of sintered carbides consists of particles of metal carbides, such as WC and TiC, embedded in a metallic binder which is usually a cobalt—or nickel-rich solid solution. One of the important factors influencing the strength of the alloys is the degree of dispersion of the carbide particles in the binder matrix. While it is generally accepted

Jan 1, 1960

By H. D. Wilde

GREAT emphasis is being placed today on petroleum as a source of chemicals. Such prominence is well merited, for rapid strides have been made in developing processes for the conversion of petroleum into synthetic chemical products, which are now being made on a huge scale. These marvelous accomplishments have resulted in some highly optimistic predictions as to what can be expected in the future. Many of these forecasts are well justified, but some writers, especially those contributing to the Sunday supplements and the popular-cience type of publications, have let their imagination run wild and present a rather distorted picture of the possibilities in this field in the postwar period. Commercial manufacture of synthetic organic chemicals had its beginning in England with the establishment of a plant by Sir William Perkin in 1857 for the manufacture of "Aniline Purple" or "Mauve." The preceding year he had discovered in the laboratory how this dyestuff could be made from aniline, one of the many derivatives of coal tar, and he soon made commercial application of his discovery. Influenced largely by his success, organic chemists began research on production of a vast array of synthetic dyestuffs, medicinals, flavors, scents, and explosives. Rapid progress was made and by the turn of the century hundreds of these products were being manufactured. Most of these synthetic chemicals were derived from materials obtained as by-products in the conversion of coal into coke. These by-products are generally referred to as "aromatics" and are obtained by processing coal tar recovered in the coking process, so they are popularly known as "coal-tar chemicals." During the early years of this century, coal-tar chemistry was the wonder of the age, and rightfully so, since the products so made seemed limitless.

Jan 1, 1944

By Gustav Egloff

AN unexpected and unprecedented demand for its products now challenges the petroleum industry. Between 1939 wand 1946, domestic oil demand increased nearly 45 per cent and in the first half of 1947 it was 10 per cent higher than in 1946. In 1939 the United States produced 1,264,962. 000 bbl of crude oil and indications are that about 1,860,000,000 bbl will be produced in 1947, a 47 per cent increase. Runs to stills are more than keeping pace with production. The crude capacity of 365 operating refineries is rated as 5,400.000 bbl daily and almost 100 per cent of this capacity was running crude oil in August 1947. The oil industry is cognizant of our need for a greater volume of petroleum products and is expending the huge stun of four billion dollars on exploration. production. transportation, refining. and marketing of petroleum. Of this amount about half will be spent on exploration and production. a billion on refining. and another billion on transportation and marketing facilities.

Jan 1, 1947

By H. A. Deans

A three-parameter mathematical model for one-dimensional flow in porous media is developed. The objective of the model is to predict accurately the longitudinal dispersion associated with the flow of either gases or liquids over a wide range of Reynolds number. A qualitative analysis of the model parameters is given. Published experimental pulse-response curves are compared with results predicted by the model. Several general types of problems are given for which the model can be used. INTRODUCTION The problem of multicomponent single-phase flow through porous media is encountered in the study of petroleum reservoirs, gas chromatographic and ion-exchange columns, industrial fixed-bed con-tacters and elsewhere. These particular examples span the wide range of flow conditions possible; Reynolds numbers of less than l0-4 are not unusual in oil-production problems, while values in excess of 103 are common in large fixed-bed operations. The study of flow-dependent transport phenomena is complicated both by the changes in the character of the flow over this range, and by the irregularity of the flow boundaries inherent to porous media. Dispersion is one of the important phenomena known to depend fundamentally on flow conditions as well as on fluid and medium properties. As used in this paper, the term "dispersion" refers to the observed mixing of fluid elements of different composition which occurs in flow systems. The actual mechanism may be one or more of a number listed below. Only dispersion in the direction of the mean flow (referred to as axial or longitudinal dispersion, or mixing) is considered here, although lateral dispersion arises as part of certain coupled mechanisms. MECHANISMS FOR LONGITUDINAL DISPERSION A number of distinct mechanisms are known3,5,7,8 to contribute to the phenomenon of longitudinal dispersion. The more important of these are as follows. 1. Molecular diffusion in the flow direction. 2. Turbulent (cell) mixing. 3. Lateral transport processes coupled with velocity and/or residence time distributions, including: (a) "Taylor" diffusion caused by the interaction of velocity profiles in individual voids with lateral molecular diffusion; (b) separation and remixing or interdiffusion of streams having different velocities around particles; and (c) the couplipg of gross velocity profiles, caused by viscous instability or inhomogeneous porosity, with lateral dispersion. 4. Finite mass-transfer rate between a porous matrix and the flowing phase, and finite diffusion rate inside elements of the porous matrix. It is a well documented fact that these mechanisms, whether acting individually or in combinations, produce essentially similar integral effects. The observed dispersion can be described approximately by solutions of the diffusion equation with a properly chosen dispersion coefficient. Necessary conditions for equivalence between dispersion and diffusion are discussed by Klinkenberg and Sjenitzer.7 Apparently these conditions are not satisfied exactly in many real systems. "Best fit" solutions of the diffusion equation often depart appreciably from measured breakthrough curves for the usual pulse- or step-forced experimental systems. In particular, pulse response curves usually show some degree of asymmetry and "tailing" which cannot be reproduced by the one-parameter diffusion model. The three-parameter model proposed herein attempts to produce these effects in a realistic manner. Asymmetry and tailing are predicted for certain sets of parameter values, while for other sets the new model agrees with the diffusion model. VELOCITY DEPENDENCE OF DISPERSION Molecular diffusion apparently controls at sufficiently low Reynolds number in both gas and liquid systems.*l3 At Re > 20, turbulent cell mixing is dominant for gases flowing at low pressure; the data of McHenry and Wilhelm8 show that the mixing cell is approximately 1 particle diameter long in random sphere packs. on the other hand, the data

By C. L. Magee, H. W. Paxton

PREVIOUS workersl'% ave found that as-quenched ferrous martensites can be plastically deformed at low stresses. They have also found that the stress to obtain small strains can be significantly increased by aging at temperatures up to 150°C. This behavior has been interpreted in two ways: 1) that the deformation at low applied stress is due to internal stresses and thus the aging phenomenon is due to relaxation of the internal stresses;' 2) that the microdeformation arises through the motion of unpinned dislocations and the aging process is the diffusion of carbon to the dislocations to pin them.293 In a recent paper,4 we have shown that under certain conditions the dominant microdeformation mechanism of as-quenched Fe-31Ni marten-site-austenite aggregates is the transformation of retained austenite. Our results on resistance changes during deformation and temperature dependence of the deformation also established that, at temperatures above 300° K, the microdeformation was not due to this transformation. The purpose of this note is to report results of experiments which indicate that explanation 1 is appropriate for this deformation. All results presented here are from conditions where transformation does not make a measurable contribution to the microplastic deformation, in Fe-31Ni-0.002C, or in Fe-29Ni-0.02C-0.25Ti. The experimental techniques that were used for measurement of the plastic deformation are described4 and analyzed5 elsewhere. Fig. 1 shows the microplastic response of 100 pct austenite at 300" and 350° K. The microplastic response of an austenite-martensite aggregate is also given in Fig. 1 and it is seen that, after formation of martensite, the initial plastic deformation occurs at lower stresses. Thus, the softness is not entirely due to retained austenite—the quenched structure can be deformed at lower stresses despite the fact that the macroscopic strength is significantly higher. A result which allows a distinction to be drawn between the alternative explanations for this behavior is derived from aging experiments on the low-carbon alloy containing titanium. We have previously shown4 that the presence of titanium in this alloy reduced the free carbon to a sufficiently low level that thermal stabilization of the austenite-martensite transformation was not detected. Despite this, Fig. 2 shows that the microplastic response is decreased by aging treatments. A similar aging effect in Fe-ZONi, with some titanium, has previously been reported by . Thus, carbon is not necessary for the aging process and explanation 2 is at best incomplete. Since internal stress relief can occur independently of carbon (any temperature dependence of the flow stress can result in decreased internal

Jan 1, 1969

By William P. Blake

The salt-beds at Salton, on the line of the Southern Pacific railway, in San Diego county, California, have been successfully worked for many years by the corporation known as the East Liverpool Salt Co., and the salt has been largely used upon the Pacific coast generally and in the interior. But the industry has lately been destroyed by the overflow from the Colorado river. The salt is dissolved, and the waves of the Salton sea now roll 50 ft. above the site of this once thriving and growing business. The salt-bed was evidently the residual accumulation from the waters of an ancient lake, which I have named Cahuilla, from the name by which a large part of the valley—the home of the Cahuilla tribe of Indians—is known. The deposit covered a comparatively small area in the lowest part of the valley, 280 R. or more below the sea-level. This depressed area is now generally known as the Colorado desert, but has a soil of wonderful fertility wherever water can be had on its surface. The deserted beaches, and the water-lines, only a few feet above tide-level, upon the rocks of the bordering mountains, as well as a great abundance of shells in the soil, all bear decisive testimony to the former occupation of the valley by water. The depression is topographically the northern end of the Gulf of California, from which it is now separated by the delta of the Colorado river, extending practically from the mouth of the Gila river across the valley to the coast mountains on the

Jan 1, 1908