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By B. S. Gottfried

A generalized mathematical model is presented, which describes the thermal recovery of oil in linear systems with convective external heat loss. Three-phase fluid flow, conduction-convection heat transfer, chemical reaction between oxygen and oil and aqueous phase change are included, making the model applicable to a variety of thermal recovery processes. The complexity of the model requires that numerical solutions be obtained with a digital computer. The numerical approximations of the partial differential equations are presented and the algorithm is discussed in detail. The analysis is applied to the detailed simulation of a forward-combustion laboratory tube experiment. The results of the simulation exhibit with reasonable accuracy all of the principal thermal and bydrodynamic characteristics observed in the laboratory (i.e., the propagation of a combustion zone, a steam plateau, and oil and water banks). Numerical variations in the parameters appearing in the external heat-loss term, the aqueous phase-change term, and the Arrhenius combustion term are examined, and their effects on the predicted temperature profiles, oil and water production histories, and the air-oil ratio are presented. In spite of an oversimplification in the chemical reaction mechanism and the considerable computer time required to obtain solutions, the model represents a major advance in the ability to simulate the phenomena observed in thermal recovery experiments. INTRODUCTION Thermal oil recovery refers to a class of recovery processes where heat is supplied to a reservoir to provide the necessary expulsive energy. This thermal energy can be supplied externally as steam or hot water, or it can be generated in situ by forward or reverse combustion. In either case, however, thermal recovery processes are charac- terized by the simultaneous flow of two or three fluid phases in a variable - temperature field, accompanied by possible chemical reaction or phase-change effects.2-5, 7- 10, 14,16-18,20-22 Although a physical understanding of the thermal recovery processes is far from complete, it is possible to construct mathematical models which describe approximately all of the principal physical and chemical phenomena. However, attempts to solve such models, even with high-speed computers, involve formidable mathematical difficulties. Consequently, theoretical solutions have been obtained only for idealized cases in which important physical phenomena are neglected. For example, consider the process of forward in situ combustion. All such theories which have been developed consider only certain aspects of the process, such as heat transfer, 2-4,8,9,l6,l8 heat transfer with phase change,10 heat transfer with chemical reaction,7 or the hydrodynamics of three-phase flow.21 A general theory including all of the above phenomena has not been developed to date. This paper presents a unified theory of thermal recovery processes in linear systems. A mathematical model is developed which explicitly includes conduction-convection heat transfer with convective external heat loss, chemical reaction between air and oil, aqueous phase change, and the hydrodynamics of three-phase flow. A system of equations is developed which can be solved numerically on a high-speed digital computer, resulting in predicted temperature, pressure, and saturation histories in space and time. The model allows a more detailed simulation of thermal recovery tube experiments than had previously been possible. THEORETICAL DEVELOPMENT Consider the linear flow of gas, water and oil in a homogeneous porous medium. Assume that the oil will react with gaseous oxygen, and that mass is transferred between the water and gas phase by evaporation or condensation. In the absence of hydrocarbon phase change, intraphase diffusion,

Jan 1, 1966

By G. G. Hancock, H. H. Johnson

Hydrogen gas at atmospheric pressure is shown to cause substantial embrittlement in a martettsitic high-stretzgth steel. Subcritical crack growth is observed at very lom stresses and with high growth rates. It is suggested that an adsorbed layer of hydrogen atoms at the crack-tip surface provides the damaging hydrogen. Oxygen in small quantity, as little as O.7 pct by volume, is shown to eliminate subcritical crack growth in gas environments caused by hydrogen or water vapor. However, dissolved oxygen in water has little or no influence upon crack-growth rates. Oxygen-stopped cracks may be restarted by water, or by hydvogen or water vapor if oxygen is removed from the environment. These observations are interpreted in terms of preferential adsorption of oxygen at the crack tip and the formation of an oxide barrier. RECENT investigations1-3 have demonstrated that environmental factors are frequently responsible for delayed failure in martensitic high-strength steels. The environment causes crack initiation from preexisting cracklike flaws at unexpectedly low stresses, often far below the uniaxial yield strength. The crack then propagates at a rate controlled by the environment and the crack-tip stress-field intensity; during this period crack propagation will cease if either the stress or the aggressive environment is removed, and this may be considered a definition of subcritical crack growth. Fracture occurs when the crack has grown to a critical length, such that the fracture toughness of the steel is exceeded. Several liquids are known to cause delayed failure, but water and water vapor are the most severely damaging of the environments investigated to date.'-3 It has been suggested that hydrogen produced during corrosion reactions may be the actual embrittling agent2 The severe embrittlement caused by water vapor inevitably raises the question as to whether other gas environments are damaging. Previous work4'5 has demonstrated that high-pressure hydrogen (2250 psi or greater) is an effective embrittling medium, as measured by such criteria as reduction in area, notch tensile strength, and time to failure. Moreover, the embrittlement was eliminated by the addition of small quantities of air or oxygen to the high-pressure hydrogen, but it was not influenced by additions of nitrogen or argon.4 In the present study attention is focused upon gas environments at atmospheric pressure, in particular hydrogen and oxygen. The influence of these constituents upon the initiation and growth of a crack from a pre-existing cracklike flaw in a high-strength steel was determined directly by the electric-potential method of monitoring crack growth. MATERIALS AND PROCEDURE The H-11 steel was supplied by the U.S. Naval Research Laboratory as 3 by 12 by 0.065 in. sheet specimens with 1-in. transverse center slots. The slot tips were finished by Elox machining to a radius of 0.001 in. or less. The yield strength was 230,000 psi; chemical composition and heat-treatment schedule are given in Table I. The experimental apparatus, precracking procedure, and incremental loading sequence have been described previously.3 In the only significant change, precracking was sometimes carried out by a hydrogen embrittlement and baking technique. All experiments were conducted at room temperature; the hydrogen gas environment was purified by a commercial palladium purifier. Crack initiation and propagation were followed by the electric-potential method,'-3 using a calibration that has been recently dicussed. Stress-field intensities at the crack tip were computed by the conventional Irwin frmula; the plasticity correction was negligible and therefore not included. EXPERIMENTAL RESULTS A striking brittleness associated with molecular hydrogen at atmospheric pressure is demonstrated by the data in Table I1 and Fig. 1, which indicate that subcritical cracks in hydrogen initiate at lower stress-field intensities and propagate more rapidly than in fully humid argon. Ki and Kf are the crack-tip stress-field intensities at initiation and termination of subcritical crack growth, respectively. Termination, of course, corresponds to fracture. In both hydrogen and humid argon Ki is less than Kf

Jan 1, 1967

By Reynold Q. Shotts

CHEMICAL methods, based on the relative rates of oxidation of fusain, bright coal, and dull coal by nitric acid, have been devised to determine these coal components.1-4 Results obtained by oxidation methods for fusain have been checked against results obtained from microscopic methods5, 6on duplicate samples of the same coals, but to the author's knowledge this has not been done for bright and dull coal components. For this reason it is not certain that the two methods of analysis identify essentially the same chemical or physical units. It would be highly desirable to see results of the application of both methods to duplicate samples, but in the absence of any such data the author has attacked the problem indirectly. From the U. S. Bureau of Mines samples were obtained of three Alabama coals which the USBM had analyzed optically and reported on over the past 30 years. These samples were subjected to analyses by oxidation rate methods. Results of this work, and comparisons with the USBM analyses, have been published." This was the first indirect approach to the problem. The present report attempts a second indirect approach by way of internal validation. By nitric oxidation samples of two whole coals were carefully analyzed for fusain, bright coal, and dull coal. One coal was analyzed in duplicate. Duplicate portions of each of the coals were divided into three density fractions by means of heavy liquids. A duplicate portion of one of the coals was divided by sieving into three size fractions. Each fraction was analyzed by oxidation and its percentage composition calculated in terms of fusain, bright coal, and dull coal. Because the weight percent of each fraction was known, a material balance calculation for the whole coal was also made. The resulting reconstituted analysis of the whole coal could be compared to that determined by direct analysis. In addition, specific reaction rate constants were determined for each component and for each whole coal or fraction. Arbitrary reactivity indexes were calculated by dividing by 100 the sum of the products of the percent of each component in the coal and its specific reaction rate constant. The resulting figure was an average reactivity index for each coal or fraction. Weighting the reactivity indexes for each fraction by the percent of the fraction in the coal gave a reactivity index for each whole coal which could be compared to that calculated directly from the whole coal analysis. If oxidation analyses really delineate definite physical entities within the coal, or even definite groups of similar entities, reconstituted analyses calculated from fraction analyses should check closely those made of the whole coal. It probably is true that optical methods identify and describe a greater variety of components than do chemical methods and that variations are wide in the appearance and quantity of those components identified optically. Chemical methods based upon differences in oxidation reaction rates would of necessity be less discriminating, as between similar components, than would optical methods. The procedures followed for oxidizing the samples, analyzing the residues, plotting and calculating the percentage of each component, and calculating its specific reaction rate constant have been fully described.'-' In brief the method originally proposed by Fuchs et al.1 for the determination of fusain consists of the oxidation of small samples of coal in boiling 8N nitric acid in a condenser-fitted flask. After boiling for periods of 1/2 to 4 hr, the unoxidized residue is filtered and washed. The washed residue is treated with normal sodium hydroxide, diluted, and allowed to stand for several hours. The resulting brown liquor is removed, and the filtered residue dried, weighed, ignited, and weighed again. The ash-free residue is expressed as a percent of original dry, ash-free coal. The percent residue is plotted against time, and the extrapolation of this line to zero time gives the percentage of dry ash-free fusain present in the original sample. The shape of the resulting time plots has been explained' by the assumption that they are the result of two different types of reaction, the first part representing a first order reaction with rate a func-

Jan 1, 1956

By R. F. Mehl, J. K. Stanley

THE recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are employed.1 Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystallization is not a heterogeneous reaction within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress .4,5† The theory of recrystallization is not in advanced state; if recrystallization data were obtained in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed .27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert measurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now

Jan 1, 1942

By John A. S. Dow, Garry G. Lowder

Tapadaa is one of several centers of porphyry copper mineralization in northern Sulawesi. Host rocks are mainly varieties of quartz diorite porphyry. Structural control of mineralization is indicated by elongation of the sulfide system (5 x 1 km) parallel to prominent NW-trending structures, but in detail mineralization is strongly influenced by relative age and lithology. Hydrothermal alteration is characterized by widespread occurrence of advanced argillic assemblages and the presence of sodic rather than potassic alkali feldspar. Propylitic alteration surrounds the mineralized area. Phyllic and advanced argillic alteration occur in structurally controlled zones and in limited pervasive areas. Hypogene copper mineralization develops in rocks with sericite-albite alteration and comprises low total sulfide chalcopyrite-bornite or chalcopyrite-pyrite.

Jan 1, 1978

By F. H. Deily, H. W. Lownie, E. A. Loria, L. W. Ledgerwood, M. W. 207-000-000-012 Mallett, J. E. Eckel

MANY investigations have been made of the residual gas content of iron and steel. Very few, if any, quantitative measurements have been made on the oxygen content of cupola-melted iron.' The fact that cast iron is a complex alloy rather than

Jan 1, 1957

By J. C. Wright

A practical program of education for workers of the mining industries is being formulated by the Federal Board for Vocational Education in cooperation with the states in which this industry is a dominant one. The Federal Government last year passed a law, known as the Federal Vocational Education Act, that provides for the promotion of vocational education and for cooperation with the states in the promotion of such education in agriculture and trades and industries and in the preparation of teachers of vocational subjects. More than 1,000,000 men in the continental United States are employed in mines and quarries. The following table, from the 1910 Census Report, shows the relative importance of mining and manufacturing pursuits: Manfactures Mines and quaRRies Employees.......... 7,405,313 1,109,410 Capital............. $18,428,269,706 53,380,525,841 Value of product..... $20,672,051,870 $1,238,410,322 Of the more than 1,000,000 men employed in mining, almost three-fourths are engaged in the production of bituminous and anthracite coal; one-fifth, in the production of copper, iron, lead, zinc, and other metals; and the remainder in getting out structural and miscellaneous materials from quarries. The meeting of the needs of the coal-mining industry, therefore, is the problem of greatest importance in the point of numbers to be served. Moreover, the dangers in coal mining are greater than in metal mining. Practically all states have set up educational and technical standards for the position of foreman, boss, superintendent, etc., and every applicant for these positions must have a certificate of competency. The qualifications, too, are becoming increasingly difficult in the field of technical information. In some states, every miner must have a certificate, which is issued by the mine examining board only after an oral examination. Did these state laws not call for definite and comprehensive plans for the vocational education of men in the mining regions, the conditions

Jan 1, 1919

By Henry M. Howe

The striking features of American Bessemer practice aré its large output and its low initial silicon and initial temperature. These are interdependent. Large outputs implies short blows and short intervals between blows. Short blows imply low silicon and fast blowing. Low silicon implies short intervals and fast blowing. Our blows are short because we have little silicon to remove, and because we remove it fast by supplying blast rapidly. We get enough heat even with little silicon, because our blows and the intervals between them are so short that relatively little heat escapes from our vessels. Were we to lengthen our intervals, or to blow more slowly, we would have to meet the increased loss of heat from our vessels, either by using more silicon, or by melting hotter, i.e., by burning more coke, in the blast-furnace or in the cupola. Finally, our short intervals imply powerful machinery, efficient organization, and extreme specialization and subdivision of labor, which can be profitable only when the output is large. Let, us now take these points up in more detail, first glancing at some examples of our large outputs, given in Table I., and of the composition of our iron. Output.—On presenting such results to some foreign metallurgists, I have been told, " Oh yes, we quite understand that. You really turn out no more steel than we do. As a matter of personal pride, your manager gets up a tremendous spurt for a day, or even a week, crowds on men wastefully, rushes through great quantities of metal, and then for months afterwards has to recuperate. The machinery has been strained ; the owner's money has been wasted ; the men have been prostrated—all to gratify the manager's vanity. Your average output is no larger than ours." Personal pride has, doubtless, played its part; without it we would still be savages, or apes, or mollusks, if you prefer. These baser motives are the mudsills of progress, the soiled roots of that growth of which civilization is the flower. Great outputs were made

Jan 1, 1891

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Jan 1, 1938

By F. Peter

I. GENERAL INTRODUCTION. TECHNICAL progress takes place in two directions: the improvement of methods, affecting the quality of the product; and increase in the economy of operations, affecting its cost. In the iron-industry, practice is pretty well settled, and. revolutionary changes of method are, for the present, not to be expected. Hence, in this industry, the principal endeavor is to reduce costs by the use of labor-saving inventions, such as the machines brought into use during the last decade. But it is not alone necessary to reduce the labor-cost; complete economy requires also a saving in raw material. Under this head we may rank the coal employed as metallurgical fuel; and it follows that progress includes the economic use of fuel, so managed as not to injure quality of product. In the present paper it will be shown how, by suitable utilization of the heat from the furnace, a large portion of it may be made available for other purposes. Such utilization of waste-gases is important in all industries which employ furnaces (especially heating- and smelting-furnaces); and in the first rank of these stand the iron-, glass-, and porcelain-manufactures. The following pages are devoted chiefly to the waste-gases of smelting-works, and especially to those reverberatory-furnace gases which are not combustible.'

Jan 12, 1913

By David L. Riley

Organization The Foundling Years - 1901-1921 Two events that occurred in the decade of the 1870's have had far- reaching effects upon the petroleum industry in the U. S. and formed a basis for the birth and growth of the petroleum engineering profession. In 187 1 a group of mining engineers banded together to form the American Institute of Mining Engineers "to promote the arts and sciences connected with the economic production of the useful minerals and metals and the welfare of those employed in these industries by all lawful means". Although it was to be 30 years before an event in Jefferson County, Tex., would cause petroleum to come into prominence as the world's principal source of energy, the founding of AIME provided an organization through which the application of engineering to the recovery of petroleum and natural gas could be developed. In 1875, a Pennsylvania judge who was called upon to make a decision for which there was no precedent reasoned that oil and gas were like wild game - they belong to the man who can reduce them to possession. His decision sired the "rule of capture", which stated that a landowner possesses the oil produced from his well, even though it might have come from beneath his neighbor's land. This interpretation prevailed for more than half a century, during which time gold-rush tactics were employed in the drilling and production of many oil fields in the U. S. The resulting overproduction and tremendous waste led to a virtual economic collapse of the U. S. petroleum industry by the early 1930's. To bring these malpractices under orderly control, proration and conservation policies were developed, and petroleum engineering became the medium through which they were devised and implemented. At the turn of the 20th Century, more than 90 percent of this country's oil production came from the East, but the picture changed with dramatic suddenness on Jan. 10, 1901. Captain Anthony F. Lucas, an Austrian mining engineer, had noticed concentrations of oil and gas near salt domes during mining operations on the Louisiana Gulf Coast. In 1899 he leased a low mound near Beaumont, Tex., began drilling, and after almost 2 years of intermittent operations, brought in the famous "Lucas Gusher"

Jan 1, 1971

By W. O. Philbrook, H. W. Hosking, N. B. Melcher

Rates and patterns of gas flow in an experimental blast furnace were investigated by measurements, at three levels, of gas compo-sitions and temperatures and by direct determination of gas transit time by a new method employing mercury vapor as a tracer. Infer-ences were drawn about localized reaction zones and the mechanism of the onset of' channeling. LACK of precise knowledge of the nature of gas movement in the blast furnace has always been an impediment to better understanding of the blastfurnace process as a whole. The effects upon operation of various types of charge distribution are very largely brought about by the modifications to gas flow which they occasion. Intelligent evaluation of these effects demands a better understanding of the factors influencing gas flow and the ways in which the flow pattern is altered by conditions existing in the stock column. The same knowledge is required before a fundamental approach can be made to the problem of establishing optimum lines for new furnaces. An experimental furnace is operated at the Bureau of Mines Central Experiment Station, Pittsburgh, Pa. Advantage was taken of experimental operation to conduct an investigation to develop and evaluate methods of study which could be applied later to industrial furnaces. The gas composition and temperature determinations were made as a preliminary study so far as gas flow was concerned but yielded significant information relating to other processes occurring within the furnace. The direct measurement of gas transit times by the mercury-vapor method constituted the major object of the investigation. Development of the mercury-vapor method was carried out while the data on gas composition and temperature were being collected. A complete description of the principle and development of the mercury-vapor method is beyond the scope of this paper but is available elsewhere. The results obtained and some consideration of the method's effectiveness and its potential value in the study of industrial problems will be treated here. DESCRIPTION OF FURNACE The general lines of the experimental blast furnace are shown in Fig. 1. The hearth diameter was 3 ft at the beginning of the investigation, and this was later enlarged to 3 ft 9 in. and finally to 4 ft to increase capacity. Tuyere to stockline height is 21 ft 4 in. The bosh depth is 3 ft 4 in. over which it opens to a width of 5 ft, and this diameter is carried up for 2 ft in a cylindrical section. The inwall batter of 1/2 in. per ft. is considerably less than in larger installations This may have influenced the movement of gaseous and solid materials. The furnace is inside a laboratory building and is charged from outside by a skip and hoist. Feeding into the first of three bell chambers, the stock is distributed by rotating the upper bell, the other two being used to obtain an effective gas seal. Three water-cooled tuyeres, with a nozzle dia-

Jan 1, 1960

By Horace V. Winchell

This paper, embodying information acquired by the writer in his work in connection with the Geological Survey of Minnesota, is presented by permission of the State Geologist. Historical.—On November 16, 1890, the workmen of Captain J. A. Nichols, of Duluth, Minn., encountered in a test-pit on the northwest quarter of section 3, township 58, range 18, west of the fourth principal meridian, the body of soft ore now called the Mountain Iron mine. Hard ore, chiefly magnetic, had been known for many years on the Mesabi range, and explorations made by Mr. E. W. Griffin, of Minneapolis, near the falls of Prairie river in T. 56-24 and T. 56-25, and by John Mallmann, at the Mallmann explorations, T. 59-14, had revealed some hard hematite interbedded with quartzite and low-grade soft ore; but this was the first discovery of merchantable hematite on the range. Captain Nichols had been exploring more or less along the range for some two years. To him and to the Merritt brothers, of Duluth and Oneota, who, unshaken in Faith by the discouraging reports of explorers, miners, experts, and geologists, had persevered in the search for ore, great credit is due for the final success, and large rewards have accrued to them already.

Jan 1, 1893

By V. Carlson, J. A. Rowe, E. O. Bennett

This report concerns the microbial flora found throughout the surface facilities of six water-injection systems in Texas and Oklahoma. Each system is described in detail and water quality data are presented when available. Pseudomonads and sulfate-reducers (Desulfovibrio) were the predominate organisms found in the systems. The genera Sphaerotilus, Bacillus, Achromobacter, Minococcus, Clostridium, Flavobacteriurn, and Sarcina were also isolated in significant numbers. Molds, iron bacteria, sulfur bacteria and soil bacteria were found less frequently in the systems. It is concluded that a complex microbiological flora exists in oilfield water-injection systems. A tendency for waters to deteriorate in passage through solid bed filters is also noted. INTRODUCTION The injection of water into a subsurface formation is often accompanied by numerous problems, the origin and nature of which are only partially understood. During the past few years, investigators have indicated that bacteria are involved in some of these problems even though very little specific information is available concerning this matter. It is surprising that investigators working on microbiological problems in water injection have never made a complete study of the flora of these systems. The logical course to pursue is that of identifying the microbial flora and then examining each organism individually and in combination with others to determine if they produce a particular problem. The objective of the present investigation is to identify the microbial flora in water-injection systems. In addition. the quality of the water in most of the systems was determined and some observations made on the extent to which passage through surface-handling facilities affects water quality. The information derived from this study can serve as a foundation for additional basic investigations. EXPERIMENTAL PROCEDURE The microbial flora of six water-injection systems were studied at 50 sampling points. These systems are experiencing problems which may be attributable to micro-organisms, and two were being treated with antimicrobial agents at the time of this study. The samples were obtained by inoculating 1.0 ml of the water onto the different media at the sampling point. The media used for primary isolation included nutrient agar, Strokes agar, M-10-E medium and semi-solid thioglycollate medium. The cultures were returned to the laboratory, incubated at 30°C until growth occured; then, pure cultures were obtained from individual colonies. The pure cultures were identified according to standardbacteriologica1 procedures. Those organisms not fitting identification criteria exactly, even though exhibiting close similarities to known species, are listed as unidentified organisms. Membrane filters were used to make water-quality tests at intervals before and after collection of the microbiological samples. The filter discs were 47 mm in diameter with a 0.45-micron particle-size retention, and the tests were done under closed conditions at 20) psi. Membrane flow rates are plotted as increasing filtrate volumes, and the total solids contents arcs given when available. An effort was made to sample at each place in a system where a change in environment occurred. In this manner, the effect of passage through filters, tanks, hay sections, etc., on the microbial flora and water quality could be observed. RESULTS SYSTEM A This waterflood system (Fig. 1) is about four years old and daily pumps approx&ately 110,000 bbl of oil-free sour water from a 3,700-ft deep reef. The

By T. Sterry Hunt

At the meeting of the Institute in Easton, October, 1873,I made a communication on the Ore Knob copper mine, in Ashe County, North Carolina (Transactions, vol. ii, p. 123), in which I called attention to the chemical decomposition alike of the pyritous lode and the inclosing gneiss rock to a depth of 60 feet, by which the feldspar of the latter had been converted into clay, and the whole rock very much softened. Such a decomposition is well known to be almost universal in the crystalline rocks of the Appalachians south of the Potomac; and if it is only seen in rare and exceptional cases farther to the northward, this, as I have elsewhere pointed out, is due to the fact that the decomposition began and ended in the ages anterior to the drift period, and that the decayed portions which still remained were at that time removed from the surface, except in some localities which were protected from the emding agency. I have lately had an opportunity of studying a remarkable instance of this kind in an examination made last month for the corporators of the Hoosac Tunnel.* The locality is at the western base of Hoosac Mountain, the western slope of which rises rapidly 1300 feet above the town of North Adams, in Berkshire County, Massachusetts, itself 700 feet above the sea level. Through this mountain, as is well known, a tunnel for the Troy and Boston Railroad has lately been opened, a distance of 25,081 feet from east to west. The rock of the mountain consists of mica schist and micaceous gneiss, including in its western half a great mass of harder feldspathic and quartzose strata in part a granitoid gneiss, the strata for the most part dipping to the eastward with variable angles, but with occasional western dips, apparently due to inversion. The crystalline strata of the mountain crest and sides are in many places exposed, and present rounded surfaces, often deeply grooved and striated, but with no appearance of decay. At the western base of the mountain, however, the gneissic rock is in a state of complete decomposition, which was well displayed in opening the tunnel, which, for a distance of several hundred feet, was driven through highly inclined strata so much decomposed that they were excavated with pick and shovel, and without the aid of blast-

By J. Kent Smith

Vanadium is generally spoken of as a rare element; but, even in the light of our resources as known a couple of years ago, this description could be accepted in a qualified sense only. In fact, vanadium is very widely distributed, being a constituent of most clays, while even caustic soda has been shown to contain almost regularly a minute proportion of it, although the quantity in each case is so small as to render impracticable the extraction of the metal therefrom with profit. The opening-up of a large deposit of vanadium sulphide ore in South America has put a new phase on the commercial outlook of vanadium, the technical value of which for the improrement of steel has been proved by rigorous scientific investigation. This sulphide ore has the following analysis: Per Cent. Vanadium sulphide,.39.84 Molybdenum sulphide,.1.57 Nickel sulphide,.........1.49 Iron sulphide,.........4.07 Arsenic sulphide,.. nil. Copper sulphide,.. nil. Manganese sulphide,..nil. Free sulphur,..30.57 Phosphorus,...nil. Silica,....13.60 Alumina,..........2.46 Combined water, 5.00 Carbonic acid, Lime, magnesia, potash, soda and unaccounted for, 100.00 Being a free-burning ore it is calcined with ease, losing 45 per cent. of its weight in the process. The calcined ore has the following analysis:

Jan 1, 1908

By Shiro Ban-ya, John Chipman

Using the same experimental method previously described, the activity of sulfur in a number of quaternary and more complex liquid iron alloys at 1550oC is determined. A "cross-product term zj.zk is determined for each of the quaternary alloys to take account of the mutual effects of the combinalion on the indi-vidual contributions to In 5 The interactiotl coefjicienls delermined for ternary solutions and cross-pvoducl coefficierlts from the quaternary systems are used to estimate the activity coefficient of sulfur in more complex alloys. OUR recent papers 1,2 have described new determinations of the activity of sulfur in Fe-S binary and Fe-S-j ternary solutions, but the practical applications of these data require the estimation of activity of sulfur in more complex systems. Previously, Sherman and chipman3 devised an approximate method for calculating the activity of sulfur in complex systems by summing the contributions to the logarithm of the activity coefficient of each element in the alloy. This procedure is more successful, as one of us has pointed out,4 when the concentration variable is taken as zs = ns/(nFe — nS t CLJ~ nj) rather than the conventional atom fraction x~ = nS/(nF, + nS + Enj). In the former definition, which is based on analogy to interstitial solutions, the value assigned to uj is normally +1 for metallic and -1 for nonmetallic elements." In addition, however, the effects of mutual interaction between alloying elements must be considered for the accurate estimation of the activity of sulfur in more complex systems. The purpose of this investigation has been to devise a more reliable method for estimating the activity coefficient of sulfur in nmIticomponent iron alloys. The measurements were carried out on some quaternary systems Fe-S-j-k for combinations of silicon, chromium, nickel, cobalt, molybdenum, and tungsten. Manganese was not included since the experimental method has been found unsatisfactory for volatile, sulfide-forming elements. The experimental method was the same in every detail as described previously. 1,2 The concentrations of sulfur, silicon, chromium, and copper in the quenched metals were determined by chemical analysis but those of nickel, cobalt, molybdenum, and tungsten were calculated from charged amounts. Iron sulfide was included in the charges in amounts estimated to furnish approximately the final sulfur content. CALCULATION W2 have shown2 that when zs and zj are the concentration variables in a ternary Fe-S-j solution the logarithm of the activity coefficient S = a~/zg is a linear function of the variables as and aj defined as follows:

Jan 1, 1970

By William Newnam

WHEN Hugh Lee Pattinson discovered, in 1829, that the crystals formed during the slow cooling of molten lead were poorer, and the remaining liquid richer in silver, than the original lead, an important step was made in the metallurgy of this metal. Being the first process applicable to the desilverization of low-grade lead bullion, it soon found its way into all European countries having such a product to treat, thereby effecting the saving of many ounces of silver annually which previously had been thrown away. The old hand process was expensive, as viewed from the standpoint of more modern methods; the labor was great anti the tonnage was small, but on the other hand the results were fairly, satisfactory. This process flourished for some time after the introduction of the cheaper Parkes process in 1852 and it is still in use in a few European smelteries. Only one notable improvement was made on the original process, that of Luce and Roan at Marseilles, France. It consisted in the application of steam for stirring and the tapping of one-third of the liquid lead, through perforated plates covering the tap holes flush with the bottom of the kettle, thus leaving two-thirds in the form of crystals in the original kettle. This modification considerably lowered the operating costs as it permitted of much larger kettles, an increased tonnage and eliminated much of the slow, hard labor of the hand process.. The Luce and Rozan process has persisted in its original form to the present clay. Stephen Tredinnick, English born, spent most of his years around the Luce and Rozan plants at Marseilles and elsewhere in Europe, coming later to Eureka, Nev., in 1878, to operate the Luce and Rozan plant at that point. Mr. Tredinnick was a competent Luce and Rozan operator and being devoted to the process he firmly believed that with modifications the costs could be so lowered as eventually to supplant the Parkes process.

Jan 5, 1917

Discussion of Papers. Meetings of the Institute offer opportunity for social acquaintance and exchange of ideas, for the presentation of papers, and for discussions thereon ; also incidentally for viewing under especially favorable conditions mining operations and industrial establishments, and for hospitals-ties which demonstrate the brotherhood due to kindred interests. Placing sociability prominent is not to be assumed as relegating other features of meetings to subordinate positions; but during about 40 years of membership in the Institute, the value of acquaintances formed (often ripening into close friendship), and the interchange of data, have frequently demonstrated that the social feature of meetings is of great and lasting value to the membership. Of' a roll embracing 4,011 members, resident in all parts of our country, and scattered in various portions of the world, only a small fraction are able to attend meetings, even if the localities selected are alternately widely separated. Hence, the return which most -members receive for their annual assessment of dues is limited to the publications issued, and the credit of being recognized as a member of a great and worthy organization. Tile greater the value of tile contents of our publication, the fuller the return which goes to members. While the Institute disavows responsibility for views or statements made in papers which appear in its Transactions, the fact that these contributions, after passing proper censorship, are accepted by the Institute and spread before the world may properly be received by the writers as endorsements of their (the writers') ability to present a specific technical or industrial proposition worthy of being carefully read. But the mere presentation and publication of contributed papers falls short of fulfilling one important feature of our meetings. If the purpose is confined to having the writers' views, discoveries, theories, or methods published, this can be obtained through the technical or trade journals and magazines.

Jan 7, 1913

By N. A. Gokcen

EQUILIBRIA in the reactions between gases and liquid metals have been the subject of many interesting investigations. The experimental realization of true equilibrium, however, is questionable in certain cases due to the lack of conclusive studies in reaction rates. It -will be shown here that a systematic interpretation of rate studies with the analysis of prevailing experimental conditions leads to valuable practical information. The reactions of particular interest are: H2(g) +S(inFe) - H2S(g) [1] H2(g) +O (inFe) =H2O(g) [21 2H2(g) + SiO2(s) = 2H2O(g) + - (inFe) [3] The usual and perhaps the most convenient method of investigation may be illustrated with reaction 1. A stream of gas mixture consisting of H2 + H2S is passed over or bubbled through the liquid metal at constant temperature. The ratio of H2S/H2 in the entrant mixture is fixed in each experimental run, and, therefore, the composition of melt varies until the establishment of equilibrium. The purpose of this paper is to derive a formula expressing the minimum time required for the establishment of equilibrium and to compare the calculated values from such a formula with the available data. Equations Reaction 1 is used for the purpose of illustrating the derivation. Let E represent the equilibrium and X the nonequilibrium sulphur in weight percent at any time t in minutes. For the sake of simplicity, it is first assumed that E > X although the results are of general applicability without restriction. It has been shown by Morris and Williams' that within a difference of 1 pct S or less, i.e., E-X5 1.00, the value of K'1 = Ph2s/Ph2.S% is very nearly constant. The maximum ratio of available Ph2s/Ph2 = H,S/H,, from which sulphur can be absorbed by metal, is equal to H2S/H2 in equilibrium with E (which equals H2S/H2 in the entrant gas), minus H,S/H, in equilibrium with X. Thus: Available H2S/H2 = EK'1 - XK'1 [4] Eq. 4 expresses that sulphur can be absorbed by metal from the H2S/H2 in the entrant gas until the gas leaving the metal assumes a value of H2S/H2 which is in equilibrium with the dissolved sulphur X at that time. H,S constitutes up to approximately 1 pct of the gas mixture. Its disassociation into H2 and SL is about 1 pct at 1600°C, hence, the H2S/H2 impinging on the surface of metal is very close to that in the entrant gas. The rate of flow of hydrogen entering the reaction chamber is kept constant experi-

Jan 1, 1954