Search Documents

By R. E. Head

Under existing economic conditions, the treatment of gold ores occupies an outstanding position in metallurgical activity. The increased price of gold has automatically brought about a reclassification of old dumps and low-grade orebodies, and many that formerly were considered valueless are now being vigorously investigated and worked. This situation has developed problems that have taxed the ingenuity and ability of metallurgists to the utmost. Some gold ores give a high extraction of gold by standardized methods of treatment; other ores of apparently similar character yield but a relatively small percentage of their gold when treated by the same processes. Surface Contamination The experience gained by microscopic study of numerous gold ores and tailings has shown that there are pronounced differences in the physical characteristics of the minerals composing them, more especially of the gold. Repeated studies of tailings from flotation and cyanidation of gold ores has established the fact that surface contaminations on gold particles are often directly responsible for high gold losses; comparison of gold particles isolated from flotation concentrates and the resulting tailings have showed that the clean gold has been recovered and the tarnished or contaminated gold invariably lost in the tailing. Obviously, it is not possible to make such a comparison of gold ores treated by cyanidation, as the clean gold has been taken into solution; but when the gold found in cyanide tailing has a tarnished or coated surface, one may infer, with a reasonable degree of certainty, that the clean gold has been extracted. This premise is supported by experimental evidence obtained by isolating particles of tarnished gold and exposing them to cyanide solution in small parting cups. In one such experiment, tarnished gold particles picked from a cyanide tailing showed but slight evidence 01 dissolving at the end of 27 days. In this test, a cyanide solution of 1.6 11). per ton was used and the leach solution was decanted arid renewed every

Jan 1, 1939

By R. E. Head

Under existing economic conditions, the treatment of gold ores occupies an outstanding position in metallurgical activity. The increased price of gold has automatically brought about a reclassification of old dumps and low-grade orebodies, and many that formerly were considered valueless are now being vigorously investigated and worked. This situation has developed problems that have taxed the ingenuity and ability of metallurgists to the utmost. Some gold ores give a high extraction of gold by standardized methods of treatment; other ores of apparently similar character yield but a relatively small percentage of their gold when treated by the same processes. Surface Contamination The experience gained by microscopic study of numerous gold ores and tailings has shown that there are pronounced differences in the physical characteristics of the minerals composing them, more especially of the gold. Repeated studies of tailings from flotation and cyanidation of gold ores has established the fact that surface contaminations on gold particles are often directly responsible for high gold losses; comparison of gold particles isolated from flotation concentrates and the resulting tailings have showed that the clean gold has been recovered and the tarnished or contaminated gold invariably lost in the tailing. Obviously, it is not possible to make such a comparison of gold ores treated by cyanidation, as the clean gold has been taken into solution; but when the gold found in cyanide tailing has a tarnished or coated surface, one may infer, with a reasonable degree of certainty, that the clean gold has been extracted. This premise is supported by experimental evidence obtained by isolating particles of tarnished gold and exposing them to cyanide solution in small parting cups. In one such experiment, tarnished gold particles picked from a cyanide tailing showed but slight evidence 01 dissolving at the end of 27 days. In this test, a cyanide solution of 1.6 11). per ton was used and the leach solution was decanted arid renewed every

Jan 1, 1939

By Frank M. Monroe, James R. Cost

The solubility of nitrogen in vanadium is determined from 275" to 575°C by measuring the height of the nitrogen internal friction peak of equilibrated V-N alloys. The proportionality constant at 275°C between the internal friction peak height (Q- 1) and the atom percent nitrogen in solution is found to be 0.095 per at. pct for nitrogen concentrations up to 0.8 at. pct. The heat of solution of the nitride in vanadium is 5500 cal per mole. The solubility of nitrogen in the Group V metals is discussed. LITTLE work has been performed on the vanadium-nitrogen terminal solid solution. Hahn1 found the solubility for nitrogen to be very small and reported the existence of a hexagonal phase of composition near that of V2N at the solubility limit. Rostoker and Yamarnoto2 reported the solubility to be at least 3.5 at. pct at the melting point and to be less than this value at 900°C. In addition, they reported from X-ray diffraction studies that nitrogen in solution produces tetragonality in the vanadium lattice. An X-ray study by Schonberg3 has confirmed the results of Hahn but indicated that the tetragonality observed by Rostoker and Yamamoto was due to the presence of oxygen in their specimens. Beatty4 has performed lattice parameter and hardness measurements on terminal solid solutions and found the upper limit of the solubility to be at least 0.66 at. pct N. No measurements have been made of the pressure-temperature-composition relationships (P-T-X) for the terminal solid solution. As a part of a research program on gas-metal equilibrium, an attempt was made to study the P-T-X relationships in the V-N system using both the internal friction and the gas equilibration methods which have been successful with the Nb(Cb)-N and Ta-N systems (see Ref. 5 for a review of this work). Extensive investigation, using the gas equilibration methods, showed this method not to be applicable with vanadium This was presumably due to the gettering action of vanadium sublimed on the walls of the Sieverts apparatus. Thus, the nitrogen pressure relationships with temperature and composition were not obtained. The internal friction methods were, however, found to be applicable, and the temperature-composition relationships are reported in this paper and compared with similar results for the Nb-N6 and Ta-N7 systems. The existence of a Snoek internal friction peak due to nitrogen in solution in vanadium has been clearly demonstrated. 8-10 Powers and Doyle found the peak to be at approximately 275°C for frequencies near 1 cps.8 In a subsequent paper10 they reported the proportionality constant at 275°C between the internal friction peak height (Q-1) and the concentration of ni- trogen in solution (in atom percent) as 0.06 per at. pct. The studies of Stanley and wert9 indicated qualitatively that the height of the Snoek peak decreased with aging at the peak temperature and thus suggested that internal friction methods were suitable for study of the solubility. EXPERIMENTAL METHOD The vanadium for this investigation was of particularly high purity. It was obtained from the Ames Laboratory of the U.S. Atomic Energy Commission, Ames, Iowa in the form of a 1/2-in. diam, three pass zone-refined ingot. The electrical resistivity ratio (p300ºk/p4ºk) was 160. The initial composition was determined as follows: Carbon 200 ppm Oxygen 150 ppm Chromium <50 pprn Iron 125 ppm Silicon <50 ppm Other metallic 100 pprn The initial vanadium ingot was fabricated to 30-mil wire by swaging and wire drawing without the need of intermediate annealing. Lengths of this wire were then further purified (particularly for oxygen) by outgassing at 10-6 torr at 1400°C for 4 hr. The outgassing treatment resulted in specimens with a bamboo grain structure and a lustrous appearance. Desired amounts of nitrogen were added to the outgassed wires in a Sieverts apparatus in which known amounts of nitrogen were equilibrated with the wire at 1300°C. Nitrogen concentrations were produced in the desired range from less than 1 to 10 at. pct N. Monitoring of the partial pressure of nitrogen in the Sieverts apparatus indicated that at 1300°C equilibrium between the nitrogen gas and the vanadium was obtained within 10 min. Relatively rapid cooling from the nitrogen addition temperature was obtained simply by turning off the specimen heating current and cooling to room temperature in the partial pressure of nitrogen. Internal friction measurements of wire specimens were made under forepump vacuum in a torsional pendulum at frequencies near 1 cps. The torsional pendulum was of low thermal inertia and was designed so that specimens could be heated both by a conventional tube furnace and by the joule heating of a separate current through the wire specimen." Use of a static atmosphere of helium gas as a quenching medium made it possible to cut the specimen current, rapidly cool the specimen to the measurement temperature, and make a measurement of the internal friction in less than 1 min. Because of the large solubility of vanadium for nitrogen, the internal friction peak heights were in some cases greater than Q-1 = 0.1. This high damping resulted in an estimated relative uncertainty in the damping measurements of approximately 10 pct. X-ray analyses made to identify the precipitated ni-

Jan 1, 1970

By C. A. Queener, W. L. Mitchell

In recent years bismuth telluride has received considerable attention, primarily due to its value as a thermoelectric material. Since there seems to be little dependence of thermoelectric effect upon crystal orientation1 many of those who have previously worked with this material have been unconcerned with knowing its crystallographic angles to any degree of accuracy. However, when one studies deformation modes, lattice stresses, or the aniso-tropy of mechanical properties of a material, knowledge of the interplanar angles and their relationships as depicted in a stereographic projection becomes essential. Lange2 originally published crystallographic data which described the structure of bismuth telluride as rhombohedral with the space group A more recent work by Francombe3 presented data which corroborated and refined the original findings of Lange. In addition, Francombe established that there is no coexistence of rhombohedral and hexagonal lattices in bismuth telluride as was suggested by Vasenin and Konovalov,4 and that the structure can be treated as a pseu do hexagonal structure with an axial ratio, c/a, of 6.95 for convenience of presentation and study. The interplanar angles and standard projections for several unalloyed hexagonal metals have been previously published,5-9 but the present work appears to be unique in that it presents data for a rhombohedral compound in pseudohexagonal form. As a pseudohexagonal structure, this material has an extremely large axial ratio as compared to the usual range of approximately 1.5 to 1.9 for the hexagonal metals. Since the interplanar angles are a function only of c/a, the angular relations between various planes for Bi,Te3 will be grossly different

Jan 1, 1965

By William B. Plank

THE growing dependence of our vast industrial civilization (:n mineral products demands today, as never before, the highest technical skill in those who produce these product-;. That the duty of training the engineers, whose responsibility it is to produce these mineral products efficiently and in sufficient amount, falls directly on the schools of mining is beginning to be more fully recognized. The Institute, realizing this fact and that its future membership depends largely on the annual accretion of young men, is showing a keen interest in the problems of the mining schools and in the work of its Committee on Engineering Education. The Committee has, during the past several years, considered the problems connected with the training of men for the mineral industry, whether these have been problems of college training, or placement of the young engineer in the industry, or personnel training after he enters the industry. The field of interest and discussion has been as broad and varied as the mineral industry itself. Coal mining, metal mining and metallurgy have been discussed and the papers on these subjects have been outstanding contributions to the literature on mineral education.

Jan 1, 1931

By Theodor Knutzen, Charles H. Fulton

The plant of the National Smelting Co., a corporation controlled by the Horseshoe Mining Co., was built during 1901 to smelt the dry siliceous ores of the northern Black Hills, extracting the gold- and silver-values in a matte of low copper-percentage which is shipped to Omaha and Denver for refining. Originally, the plant was designed to collect the values of the siliceous ores in an iron-matte, which mas to be resmelted with lead-ores, in a lead-furnace, the lead-bullion produced to be refined into Doré bullion in English cupelling-furnaces. However, the scarcity of lead-silver ores in the Black Hills, owing to the present non-productiveness of the Galena district, led to

Jan 1, 1905

[Alphabetic Section (Page 729): The letter following the member&apos;s name indicates grade: M-Member, A-Associate, J-Junior. The numerals following member&apos;s grade indicate year of election. The letter following year of election indicates primary Divisional affiliation: A-Mining & Exploration F-Coal B-Minerals Beneficiation G-Petroleum C-Iron and Steel H-Industrial Minerals D-Extractive Metallurgy J-Council o f Education E-Institute o f Metals K-Council o f Economics]

Jan 1, 1961

By J. R. Campbell

A dozen years or so ago, the general superintendent of our company, now the president, Mr. W. H. Clingerman, asked me to study the coal-washing problem. This work brought me into contact with the best washery men of the country. I investigated many kinds of coal-cleaning schemes, made numerous tests, and collected voluminous data, yet I confess frankly that I have had little practical washery experience and that little has been at the Middlefork washery of the United States Fuel Co. at Benton, Franklin Co., Ill., which was put in operation last fall. While this washery installation may not be the "last word," I am quite sure it embodies some long steps in advance of the older designs and constructions. From the washery man&apos;s standpoint, the removal of pyrites or marcasite, a disulfide of iron, is the one vital problem, and the one productive of the most beneficial results, so far as elimination of sulfur is concerned. Sulfates and so-called organic sulfur occupy quite a sec-. ondary position and are generally lost sight of in coal washing. The elimination of sulfur in coal in the past has usually been accomplished by jigging in water, but lately concentrating tables have been successfully employed. The flotation process has been applied to fine coal, but is hardly considered practicable. Coal washing is rapidly coming into its own, due to the depletion of low-sulfur coals for coking purposes, and we predict that soon the same careful attention will be given to the design and construction of coal washeries that is now being given to byproduct plants and other allied industries. Heretofore, coal washing has been considered only an incidental and necessary evil instead of the big problem it is—one worthy of the most careful study by men well trained along technical lines and capable of delving into the fundamental principles. Preparation oF Coal It is usually necessary to crush the mine-run coal before sending it to the jigs, the degree of crushing depending on the occurrence of the sulfur and other impurities in the coal and the type of jig over which it is to be sent. The feldspar jig requires finer and more uniform crushing

Jan 1, 1920

By Fred D. DeVaney and

The coercimeter, as its name implies, is an instrument for measuring the coercive forcet of magnetic substances. It was developed by Davis and Hartenheim in the Special Studies Section, Metallurgical Division. A detailed description of this apparatus may be found elsewhere.2 The coercive force determinations of magnetic materials are interesting because of the relationship established by Gottschalk,4 who showed a linear relationship between the magnetization coercive force and the specific surface of comminuted particles. The value of this relationship in determining grinding efficiency has been shown by Dean.3 The determination of the surface contained in the subsieve sizes has always been a difficult problem for investigators. They made approximate measurements of the surface of coarse materials by sizing on screens, but for the determination of the surface of the sub-sieve sizes it was necessary to make detailed grain counts or elutriation tests, or to study dissolution rates. The technical literature contains many references to other methods for determining these surfaces, either by some special apparatus or by mathematical calculations based on distribution lines. Many of the methods are long and tedious, and the results of some, at least, are questionable. he turbidimeter gives quick results on ground cement. By using magnetite as the material to be ground, a simple determination of its coercive force by the coercimeter, requiring 10 minutes or less, can be transposed directly and accurately into units of relative surface. This subject has been pursued further by the U. S. Bureau of Mines in cooperation with the Missouri School of Mines and Metallurgy, Rolla, Mo., and the following is a description of the results.

Jan 1, 1939

By Fred D. DeVaney and

The coercimeter, as its name implies, is an instrument for measuring the coercive forcet of magnetic substances. It was developed by Davis and Hartenheim in the Special Studies Section, Metallurgical Division. A detailed description of this apparatus may be found elsewhere.2 The coercive force determinations of magnetic materials are interesting because of the relationship established by Gottschalk,4 who showed a linear relationship between the magnetization coercive force and the specific surface of comminuted particles. The value of this relationship in determining grinding efficiency has been shown by Dean.3 The determination of the surface contained in the subsieve sizes has always been a difficult problem for investigators. They made approximate measurements of the surface of coarse materials by sizing on screens, but for the determination of the surface of the sub-sieve sizes it was necessary to make detailed grain counts or elutriation tests, or to study dissolution rates. The technical literature contains many references to other methods for determining these surfaces, either by some special apparatus or by mathematical calculations based on distribution lines. Many of the methods are long and tedious, and the results of some, at least, are questionable. he turbidimeter gives quick results on ground cement. By using magnetite as the material to be ground, a simple determination of its coercive force by the coercimeter, requiring 10 minutes or less, can be transposed directly and accurately into units of relative surface. This subject has been pursued further by the U. S. Bureau of Mines in cooperation with the Missouri School of Mines and Metallurgy, Rolla, Mo., and the following is a description of the results.

Jan 1, 1939

By T. L. Joseph

A DEMAND for specialized knowledge has directed engineering curricula towards competency in some particular field or occupation. Preparation for life in a broad sense of completeness has received little consideration. Ways and means are needed for weaving some of the threads of liberal education into the fabric of engineering education. Any effort to develop a humanistic-social stem of engineering education will depend largely upon the content of the courses and the type of instruction offered. Many of the courses in college curricula are intended to lay a foundation for more advanced courses to be taken later by those. who specialize in some particular field. Students in other fields lack the background necessary to take the advanced courses and have too much detailed information, soon forgotten, forced upon them if they pursue the foundation courses. To develop a humanistic-social stem for engineering education existing catalogue courses selected should follow some general plan aimed towards broad educational objectives. Courses packed with detailed factual information are necessary for the stu-

Jan 1, 1947

By Etienne A. Ritter

The Evergreen mine, located at Apex, in the northern part of Gilpin county, Colorado, has opened a very peculiar and interesting copper-deposit, in which both bornite and chalcopyrite occur as rock-minerals. The country-rocks are crystalline schists cut by dikes of granu-lite and of pegmatite. At the Evergreen property they have been cut by a dike of a uew kind of eruptive rock, to which I have given the name " Evergreenite." The rock is composed of quartz, alkali feldspars, orthoclase and albite (often interlocked as microperthite), with augite of the ægirine variety and long needles of enstatite and diallage. For reasons stated below, I believe the dike to be of Tertiary age. It is easily traced on the surface of the ground, from a point in the bottom of Pine creek, about a mile below Apex, to the top of Nevada hill, 1,500 ft. beyond and 600 ft. above it. (See Fig. 1.) It varies from 3 to 12 ft. in width, and is bounded on both sides by contact-zones about 60 ft. wide, in which the crystalline schists have been changed into pseudo-quartzites or pseudo-gneisees, according to the injection of an excess of quartz or of feldspars through the special layer of the schists. The most interesting feature is the presence of the pyroxenes, which are always found, though in very variable proportions from place to place, in the layers of these metamorphosed crystalline schists. The dike has torn from its walls a large number of fragments of the wall-rock. It must have been in a viscous state when that happened, because these fragments of the wall-rock do not show any sign of resorption or of assimilation by the magma. In places they are so distinct and so numerous that the rock looks to the naked eye like a pseudo-breccia, of which, never-

Jan 1, 1908

The total estimated production of coal in the United States during the first century and a quarter of mining is shown in Table 20. This is the total of the production of the various states already shown in the various tables, and is believed to be the first statement of this sort made. No such table prepared from limited data can be accurate, but it is the writer&apos;s opinion that the totals shown are less than those actually produced. It was thought that this study would enable a reasonably accurate account of the movement of coal down the Ohio and Mississippi Rivers to be written. The searches made have shown that at this time the data do not exist from which such a study can be made, but some of the facts collected may be useful to future students.

Jan 1, 1942

By George J. Simchuk

Selection of an applicable stripping method and the subsequent determination of appropriate sizes of selected equipment are discussed. The case in point is Utah International, Inc.&apos;s Goonyella mine located in central Queensland, Australia. A detailed study of the various types of stripping methods now practiced throughout the world led to the conclusion that large draglines would be the logical choice for Goonyella. The optimal size of dragline was then determined by first designing a series of cut diagrams using an array of machine and pit geometries followed by a cost comparison of the various sizes of machines, in terms of their effective spoil radius. A dragline with a 51-cu-yd bucket was determined to be of optimum size. Further calculations, incorporating total overburden moved from both the highwall and spoil sides, required that four drag lines, two equipped with 40-cy-yd buckets and two with 54-cu-yd buckets, be used to satisfy the stripping requirements at Goonyella.

Jan 1, 1973

By Robert Archer

IT is now well known that the structure of aluminum-silicon alloys can be refined in a rather remarkable manner, with consequent improvement of physical properties, by certain treatments applied to the molten metal shortly before casting. The differences between the treated and the untreated alloys are so marked that special terms are used to distinguish them, the untreated alloys being referred to as "normal" and the treated alloys as "modified." The first practical method of accomplishing this result was that of A. Pacz,1 which consists in treating the molten metal with a, salt flux of which the, active ingredient is sodium fluoride. The result can also be brought about, and in a more economical manner, by the addition of small quantities of metallic sodium (or potassium) to the molten alloy shortly before casting.2 The action of the Pacz flux evidently consists essentially in the production of free sodium by the reaction of sodium fluoride with aluminum. The changing of a normal alloy to a modified alloy is referred to as "modification&apos; and any process for accomplishing this result is a "modifying" process. Modified aluminum-silicon alloys were introduced several years ago, and it has been demonstrated both in the laboratory and in commercial practice that it is no simple matter to produce castings having the maximum or nearly the maximum properties which under favorable circumstances can be obtained. The alloys are rather sensitive to small changes in chemical composition, and the modifying process must be carried out in a very particular manner to obtain the best results. Extensive experimental work has been carried out in the laboratories of the Aluminum Company of America with the object of determining the conditions that must be observed to make these alloys of the greatest possible

Jan 2, 1926

By Prince Gelasio Caetani

PRESIDENT DWIGHT&apos;S invitation to be a guest of the American Institute of Mining and Metal-lurgical Engineers was the first of the subsequently very numerous invitations to dinner I have received from my American friends. When I received his telegram I had not yet been even formally appointed Ambassador. I cannot tell you how deeply I appreciated it. It was a hearty welcome in returning to your country which has been for me a second home and it came from the American mining brotherhood which has been my second family.There are two distinct periods of learning in life. The first one are the years spent in school where we learn many things we after-wards forget; the second one are the years of prac-tical apprenticeship which engrave indelible signs in a man&apos;s character and shape his life. These latter years I spent in the United States and they have influenced the whole course of my life. I owe very much to my American friends who trained me. The earliest was Prof. Robert Peele, of Columbia University. At the Daly West mine, in Park City, Utah, he curbed my futuristic English spell-ing and had a hard time at it. Prof. James F. Kemp taught me that geology is a guess work just as unre-liable as the prediction of international events; he taught me also that a frank, honest and loyal character will lead a man equally straight through a mining report and through public life.

Jan 3, 1923

By O. U. Bradley

The methods of handling the oil output of the Mid-Continent fields are not unlike those practised in other oil fields of the United States, and it is not expected that this paper will present any entirely novel ideas. Some features of the practice of handling this oil may be of interest, however. Wooden Gaging Tanks Practically all of the oil sold to pipe line? and other purchasing agencies throughout the Mid-Continent field is gaged from wooden tanks. Steel gaging tanks are slowly coming into use, and are preferable in many ways—leakage and evaporation are reduced, and the strapping and recalculation of capacities are unnecessary. The wooden tanks are slightly coned to facilitate tightening the hoops. The sizes in common use are 250, 500, 800 and 1600 bbl. The number and the capacity of the gaging tanks upon any producing oil property depend upon its production, and the facilities for disposing of the output. The 1600-bbl. size was the most common in the Cushing field, particularly during the period of flush production. The tanks are distributed over the leased premises in groups of two, three, and four tanks each, and these are filled from flow tanks, or through direct pipe connections with the heads of the wells. Flow tanks are merely temporary reservoirs to facilitate the transfer of oil from the wells to the gaging tanks. They diminish fire risk, and are considered indispensable on small producing properties where water is pumped with the oil, as they permit the refuse and water to &apos;settle out before the production is run to the gaging tanks. strapping and Calculations After a gaging tank has been strapped (measured) and its contents computed, a deduction of 3 per cent. is made from its computed volume. The strapping of a tank requires four steps: (1) The outer circumferences

Jan 1, 1920

By Terkel Rosenqvist

THE desulphurization of molten iron and steel is a very complicated process. One way to arrive at a better understanding of this process is to break it down into several simpler chemical processes that can be studied individually in the laboratory. For a study of the different factors that influence the equilibrium distribution of sulphur between liquid metals and slags, several simpler equilibria may be investigated. One very important subject is the determination of the escaping tendency of sulphur in the liquid metal and its dependency on temperature and composition of the melt. Several papers in this field have recently been published.&apos;, &apos; Another subject is the study of the sulphur capacity of the slag. A molten slag is indeed complex, and even if sulphur distribution data for a large variety of molten slags may give empirical data about their desulphurizing power, the importance of the individual components is still not quite clear. It is accepted generally that lime is the most important desulphurizing component in the slag. The present investigation has as its purpose to study the desulphurizing power of lime in its standard state, and to provide a basis for thermodynamic calculations of the desulphurizing power of various lime-containing slags. The standard state of lime at steelmaking temperatures is solid calcium oxide, CaO. It can react with sulphur to form solid calcium sulphide, CaS. The relative stability of calcium oxide and calcium sulphide is expressed by the free energy of the reaction: 2Ca0 (s) + S1 (g) = 2CaS (s) + O2 (g) The existing free energy data for this reaction, listed by Kelley5 nd Osborn,&apos; are uncertain to about 10 kcal and are of limited value for a calculation of equilibrium constants. Under the conditions prevailing in a melting furnace, the sulphur pressure may be expressed conveniently by the ratio H,S/H2 and the oxygen pressure by the ratio H,O/H, (or CO,/CO). The desulphurizing power of calcium oxide may, therefore, be studied by the reaction CaO + HIS = CaS + H2O. A study of this reaction may be complicated by certain side reactions: Water vapor and hydrogen sulphide may react. to form sulphur dioxide, and calcium sulphide may be oxidized to calcium sulphate. A thermodynamic calculation shows that these side reactions will be suppressed to insignificance if the equilibrium is studied in the presence of an excess of hydrogen. The apparatus used is shown in Fig. 1. About 10 g calcium oxide and 20 g calcium sulphide (laboratory qualities) were intimately mixed, and some water was added to make a thick paste. The paste was put into a thimble of zirconium silicate, which was placed within the constant temperature zone of a furnace, and capillary refractory tubes were attached in both ends. After the mixture had been heated in dry hydrogen at 1000°C for several hours all Ca(OH), and CaCO, had decomposed and CaSO, was reduced, so only CaO and CaS remained in the thimble forming a porous plug. The mixture was examined by X-ray diffraction after the initial reduction in dry hydrogen as well as after the subsequent experimental runs up to 1425 °C. It was shown that crystalline calcium oxide and calcium sulphide were always present together in about equal amounts. The unit cell edges were found to be 4.80A for CaO and 5.68A for CaS in good agreement with existing literature values." This shows that the mutual solid solubility is very small, and that the compounds are present in their standard states. Purified hydrogen was passed through water sat-urators kept at constant temperature in a thermostat bath. The amount of water vapor saturation was checked by means of a dew point method, not shown on Fig. 1. The gas mixture was passed through the capillary inlet into the furnace, where it was sifted through the porous plug of calcium oxide and calcium sulphide. The hydrogen sulphide present in the outgoing gas was absorbed in a zinc acetate solution and the hydrogen was collected over water. When one liter of hydrogen had been collected, the amount of hydrogen sulphide was determined by iodometric titration. As one molecule of H,O is used for the formation of each molecule of H,S, the equilibrium ratio H,S/H,O would be , where (H,O) is the molar concentration in the ingoing gas, and (H,S) the molar concentration in the outgoing gas. In the present work (H,S) was always very small compared to (H20). In order for the observed H,S/H20 ratio to represent the true equilibrium ratio the gas flow has to be: 1—Sufficiently slow to give a complete establishment of equilibrium, and 2—sufficiently fast to counteract thermal diffusion. Incomplete reaction would give a value decreasing with increasing flow rate, and thermal diffusion would give a value increasing with decreasing flow rate. When inlet and outlet tubes of about 2 sq mm cross-section were used, the observed gas ratio was independent of the flow rate between 15 and 125 cc per min, Fig. 2. In this range, therefore, the observed gas ratio represents true equilibrium.* For the rest of the in-

Jan 1, 1952

By J. Wright, R. J. Tyler

Changes in the pore structure of hematite pellets during reduction to iron were investigated under a variety of experimental conditions. Pore structures were determined by a mercury penetration technique. The reduction temperature was found to be the major influence on structure, the pore system being bimodal below 7.50°C and unimodal above 900°C. Pore sizes ranging front 0.04 to 20 m were observed in complete metabolized pellets produced over the temperature range 650 - 1050°C. Gas composition and reduction rates also influenced the pore structure of the metabolized pellets, although to a lesser extent than the reduction temperature. An apparent activation energy of 24 kcal/mole was derived for the pore formation process.

Jan 1, 1979

By Allen D. Garrison

THE chemistry of clays and shales has been assuming increasing importance in the petroleum industry, and two factors have greatly influenced this trend. The first has been the growing evidence that the marine shales are source beds, and that the petroleum compounds have migrated to the sand reservoirs overlying or underlying these shales: the second has been the demand for drilling fluids better adapted to penetrate these marine shales without difficulty and expense. ORIGIN AND GENERAL COMPOSITON OF CLAYS AND SHALES Clays, shales and surface soils are all closely related materials. They are mixtures of finely divided compounds formed during the weathering of the solid crust of the earth. Their nature is essentially colloidal; that is, their behavior is determined by the state of division of the materials and the surface reactions of the smallest grains. Many of their chemical changes affect only the exposed areas and do not involve the interior of the grains of matter. The extent of these reactions is more nearly proportional to the area of the substances than to their mass, therefore it is possible for a small amount of a material in an extremely fine state of division to completely dominate the character of the mixture. More than 83 per cent of the crust of the earth is composed of three elements-oxygen, silicon and aluminum. Consequently, the corrosion products of the crust are predominantly aluminosilicates, or compounds of aluminum, silicon and oxygen. If we add the compounds of six elements-iron, calcium, sodium, potassium, magnesium and hydrogen-more than 98 per cent of the crust has been accounted for. These six elements, together with the first three, also appear in soils, clays and shales. But direct chemical analysis is of little value in describing the nature of such materials. Many chemical individuals may be present in variable amounts, and the extreme subdivision of any one of the individuals may contribute qualities that dominate the mixture.

Jan 1, 1939