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By Charles E. Lundin

Pressure-temperature-composition data were obtainedfor the Er-H system. Measurements werecar-ried out in the temperature range of 473° to 1223°K, the composition range of erbium to ErH,, and the pressure range of 10-5 to 760 Torr. Solubility relationships were established from these data throughout the system. Three solid-solution phases were delineated: metal solid solution, dihydride phase, and trihydride phase. The trihydride Phase decomposes at about 656°K and 1 atm pressure. The dihydride phase is stable to about 1023°K, but becomes more deficient in hydrogen above this temperature. The equilibrium decomposition pressure-temperature relationships in the two-phase regions, erbium solid solution plus dihydride and dihydride plus trihydride, were deter- The differential heats of reaction in these two regions are AH = - 52.6 * 0.3 and - 19.8 i 0.2 kcal per mole of Hz, respectively. The differential entropies of reaction are AS = - 35.2 * 0.3 and - 30.1 * 0.4 cal per mole HZ.deg, respectively. Relative partial molal and integral thermodynamic quuntities were calculated in the system to the dihydride phase. RARE earth metal-hydrogen systems have been the subject of general survey,1"4 and all have been found to form hydride phases. The heavy rare earths, of which erbium is a member, form dihydride and trihydride phases with different crystal structures, whereas the light rare earths form only a single-phase dihydride which expands without structure change, as hydrogen is added, to the trihydride composition. These materials are of interest primarily because of their theoretical properties, such as bonding, defect structure, and thermodynamic and electronic characteristics. Erbium has been studied in several previous investigations.5, 6 It was deemed desirable to more thoroughly and accurately define the system, both for the phase equilibria and the thermodynamic properties. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure hydrogen, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GM 100A and CVC, GM 110). Pure hydrogen was obtained by passing hydrogen through a heated Pd-Ag thimble. The hydrogen was analyzed and found to have only a trace of oxygen and nitrogen. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit hydrogen to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to ±1°K. An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to ±0.5 Torr and in the McLeod range (10-4 to 10 Torr) to ±3 pct. The hydrogen compositions in erbium were calculated in terms of hydrogen-to-erbium atomic ratio. These compositions were estimated to be ±0.01 H/Er. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9 pct +. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<1 vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the pressure-temperature-composition relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 grain for each loading of the reaction chamber. The procedure employed to obtain the pressure-temperature-composition data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen of erbium was wrapped in a tungsten foil capsule to prevent contact with the quartz tube. After loading the specimen, the system was evacuated to less than l0-6 Torr, flushed several times with high-purity hydrogen, and evacuated again ready for the start of the experiment. The furnace was then brought to the desired temperature. A measured amount of hydrogen was admitted into the chamber. Equilibrium was allowed to be attained, the pressure read, and the process then repeated many times until 1 atm of gas pressure was finally reached. Other isotherms were then developed in the same manner. The partial pressure plateaus were determined by another manner. In the solid solution-dihydride region a composition of approximately 1.0 H/Er was selected on the plateau. The temperature was varied throughout the range of interest. At each temperature level, equilibrium was achieved, the pressure read, and the next temperature attained. The temperature was cycled both up and down. In the dihydride-trihy-dride region, the plateaus were determined in the 473" to 651°K range only by heating to the desired temperature and not by both heating and cooling. The data were much more reproducible in this manner. Equilibrium required long periods of time. Specimens were initially hydrided to 2.8 H/Er, so that at the higher

Jan 1, 1969

By H. B. Pulsifer

This paper outlines a method for rapid production of flat,, granular surfaces on many of the medium hard alloys. Grinding wheels and fabrics on wheels are not used; the purpose is accomplished by rubbing on emery papers and on fine abrasives heaped on hand boards. The advantages of chromic acid in the solutions for etching nickel and copper alloys are explained. Steels may require an additional step in the mechanical smoothing owing to the lack of an ideal etchant. Chloric acid is a rapid etchant for steel. Thirty-six photomicrographs illustrate the steps in smoothing and the clearness with which structures can be rapidly exposed. New structures in low-carbon steels are announced. After a little practice, many materials can be finished within two or three minutes. CUPRONICKELS In the previous papers on the metallography of copper and magnesiurn which the author has presented to this Institute there has been an attempt to demonstrate the advantages of minimizing the mechanical work of surfacing and depending more on chemical means; the present paper continues the research into a still wider field. It is obvious that the success of a chemical method for smoothing and etching depends almost entirely on the use of a suitable reagent. The etchant must remove the surface granulations and outline the structures. A very special type of reaction between reagent and metal must be displayed. Promiscuous corrosion or the intensification of the attack about local couples formed by impurities or components must not be in evidence. There are several reagents that etch highly polished nickel and copper alloys very well. Acidified ferric chloride solutions, concentrated and dilute nitric acid solutions, and nitric and acetic acids in acetone have been used to good advantage for the purpose. However, if they are expected to etch rather deeply—that is, smooth as well as characterize— the results may be far from satisfactory. Advantages of Chromic Acid In a protracted series of experiments it has been found that the addit,ion of chromic acid may be of the most surprising benefit. The function

Jan 1, 1929

By H. B. Pulsifer

This paper outlines a method for rapid production of flat,, granular surfaces on many of the medium hard alloys. Grinding wheels and fabrics on wheels are not used; the purpose is accomplished by rubbing on emery papers and on fine abrasives heaped on hand boards. The advantages of chromic acid in the solutions for etching nickel and copper alloys are explained. Steels may require an additional step in the mechanical smoothing owing to the lack of an ideal etchant. Chloric acid is a rapid etchant for steel. Thirty-six photomicrographs illustrate the steps in smoothing and the clearness with which structures can be rapidly exposed. New structures in low-carbon steels are announced. After a little practice, many materials can be finished within two or three minutes. CUPRONICKELS In the previous papers on the metallography of copper and magnesiurn which the author has presented to this Institute there has been an attempt to demonstrate the advantages of minimizing the mechanical work of surfacing and depending more on chemical means; the present paper continues the research into a still wider field. It is obvious that the success of a chemical method for smoothing and etching depends almost entirely on the use of a suitable reagent. The etchant must remove the surface granulations and outline the structures. A very special type of reaction between reagent and metal must be displayed. Promiscuous corrosion or the intensification of the attack about local couples formed by impurities or components must not be in evidence. There are several reagents that etch highly polished nickel and copper alloys very well. Acidified ferric chloride solutions, concentrated and dilute nitric acid solutions, and nitric and acetic acids in acetone have been used to good advantage for the purpose. However, if they are expected to etch rather deeply—that is, smooth as well as characterize— the results may be far from satisfactory. Advantages of Chromic Acid In a protracted series of experiments it has been found that the addit,ion of chromic acid may be of the most surprising benefit. The function

Jan 1, 1929

New York Meets first Wednesday after first Tuesday of each month. DAVID H. BROWNE, Chairman. PERCY E. BARBOUR, Vice-Chairman. A. D. BEERS, Secretary, 55 Wall St., New York, N. Y. C. A. BOHN, Treasurer. Boston Meets first Monday of each winter month. W. E. C. EUSTIS, Chairman. - R. L. AGASSIZ, Vice-Chairman E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Boston, Mass. ALBERT SAUVEUR, H. L. SMYTH. Columbia Holds four sessions during year. Annual meeting in September or October. STANLY A. EASTON, Chairman. FREDERIC KEFFER, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. D. C. LIVINGSTON. FRANK A. ROSS.

Jan 12, 1916

By M. R. Geer, J. D. Davis, H. F. Yancey

ALTHOUGH the mechanical cleaning of coal is carried out at plants on the surface, preparation is actually begun at the face in the mine. Here the character of the coal and the amount, character, and distribution of the impurities within the bed may be seen. Blasting methods, dust-allaying procedures, location of mining cut with respect to bands of impurity, and the practice of discarding segregated impurities underground, all have an important bearing on the successful operation of surface cleaning units. The most important single characteristic of both coal and its associated impurities from the standpoint of cleaning is specific gravity. Other characteristics related in one way or another to the preparation of coal are rank, petrographic composition, structure and hardness, and friability. These and still other coal properties are discussed in the first section of this chapter and impurity characteristics in the second. COAL CHARACTERISTICS RELATED TO PREPARATION Rank As a result of work done over a period of several years by committees of the American Society for Testing Materials and the American Standards Association, standard specifications are now available showing the classification of coals according to rank and quality of grade. The term "rank" expresses the degree to which the original coal-forming material has been changed by metamorphism through successive stages from peat to anthracite. Table 1 shows the classification of coals according to rank as devised by the committees of the organizations mentioned. The basic scheme of classification for the higher-rank coals is according to fixed carbon content, calculated to the dry, mineral-matter-free basis. Groups of lower rank are divided

Jan 1, 1950

By P. F. Gnirk, J. B. Cheatham

Single bit-tooth penetration experiments under static load were conducted on six rocks at confining pressures of O to 5,000 psi using sharp wedge-shaped teeth with included angles ranging from 30 to 120° In general, the force-displacement curves for all rocks exhibit an increasingly nonlinear and discontinuous behavior with decreasing confining pressure. The confining pressure at which a rock exhibits a macroscopic transition from predominantly ductile to predominantly brittle behavior during penetration vmies from about 500 to 1,000 psi for the limestones to greater than 5,000 psi for dolomite. The correlation between calculated values of force per unit penetration based on plasticity theory and experimental values is quite encouraging, even at confining pressures as low as 1,000 psi A qualitative correlation between volume of fragmented rock per unit energy input for a single bit-tooth and drilling rate for microbits appears to exist over a confining pressure range of 0 to 5,000 psi. INTRODUCTION Laboratory experiments utilizing a small-scale drilling apparatus have demonstrated that penetration rates are reduced considerably as a result of increasing the confining pressure from atmospheric to a few thousand psi?-3 This undesirable situation can, in general, be attributed to a combination of decreased efficiency of chip removal at the bottom of the borehole, increased rock-failure strength, and a possible change in the mechanism of chip generation and rock fragmentation with increasing confining pressure. To more fully understand the principles underlying the last circumstance, it is the purpose of this investigation to experimentally study the mechanism of single bit-tooth penetration into dry rock at low confining pressures and, in particular, to establish the confining pressure at which the penetration mechanism may undergo a brittle to ductile transition for various rock types commonly encountered in drilling. Confining pressure as used here refers to the differential pressure between the borehole fluid pressure and the formation-pore fluid pressure. EXPERIMENTAL PROCEDURE Using an experimental apparatus previously described: a single, sharp wedge-shaped tool was forced under a "statically" applied load into an effectively semi-in finite dry rock sample subjected to a prescribed confining pressure. To prevent the invasion of the con fining-pressure fluid into the pores of the rock sample during penetration, the exposed surface of the rock was jacketed with a layer of silicon putty.* Electrical instrumentation incorporated into the apparatus yielded a graphical plot of force on the tool as a function of penetration or displacement of the tool into the rock during an experiment. During the course of the experimentation the following conditions were maintained constant: (1) pore pressure — atmospheric (i.e., the rock was dry); (2) temperature — 75F; (3) rate of loading — essentially static (approximately 0.002 in./sec); (4) bit tooth — a sharp wedge-shaped tool loaded normal to the rock surface; (5) rock surface — smooth and flat; (6) drilling fluid — hydraulic oil; and (7) maximum depth of penetration — approximateiy 0.1 in. In addition, each experiment was performed on a different rock sample so the rock surface is free of a layer of cuttings and of any previous indentation craters. The influence of the corners of a borehole was neglected, since each rock sample was cemented inta a section of aLuminum tubing to simulate a semi-infinite body. Indentation experiments were made on a sandstone, two limestones, a marble, a dolomite and a schist with a 60&apos; bit-tooth over a range of confining pressures from atmospheric to 5,000 psi and at a constant confining pressure of 1,000 psi for a variety of bit-teeth with angles ranging from 30 to

Jan 1, 1966

By R. B. Yerxa, C. F. Green, H. O. Hofman

MASSACHUSETTS INSTITUTE OF TECHNOLOGY, In refining copper, the metal is melted down in a reverbera tory furnace in a more or less oxidizing atmosphere and then further subjected to an oxidizing smelting in order to eliminate the common impurities, most of which have a stronger affinity for oxygen than has copper. In these operations some of the copper is oxidized to cuprous oxide and dissolved by the metal bath. When the quantity of dissolved cuprous oxide has reached about 6 per cent, the metal is said to have been brought to " set-copper." A button-sample will show a depressed surface and, when broken, a single bubble at the apex of the depression; the fracture will be brick-red and dull. It is essential to carry the oxidation to this point in order to know that the impurities have been oxidized as far as it is possible under the given working-conditions. Nearly all the cuprous oxide of the set-copper is now reduced to the metallic state by poling, when "tough-pitch" copper will be obtained. A button-sample will show a flat surface. Upon breaking, it will be found that the former bubble has disappeared and that the fracture has become rose-colored and shows a silky luster. The quantity of cuprous oxide allowed to remain in the copper will vary with the impurities still present in the metal and with the degree of pitch that it is desired to reach. It is essential for the general physical and the mechanical properties of the resulting copper that such impurities as arsenic, antimony, bismuth, lead shall be present in the oxidized state, as they are

Jan 1, 1904

The General Electric Co., in cooperation with the Montana School of Mines and under a research grant from the Anaconda Co., is presently experimenting on a new non-explosive method of breaking rock with radio-frequency electrical power. The method is known as electrothermal forcing. It must be understood that present equipment has not been designed to perform primary blasting functions. Its conceived use will be restricted to small pieces of rock too large to pass through a chute or grizzly. However, even this use is still far in the future. Experiments to date have been limited mostly to rock smaller than 18 in.

Jan 11, 1961

By C. H. Jr. Herty

IT Is well known that manganese will desulfurize molten iron through the formation of manganese sulfide, which, being only slightly soluble in the metal, rises to and enters the slag where it remains as such (mixer slag) or is converted partly or wholly to calcium sulfide (basic open¬hearth slag). The reaction by which manganese sulfide is formed is Mn + FeS = MnS + Fe. This reaction is generally considered to be reversible, although McCance1 states- that such is not the case. The experimental work was carried out to confirm the results of Rohl2 as to the reversibility of the reaction. Six trials are herein considered. In each 200 grams of electrolytic iron free from manganese and sulfur were melted in a pure zirconia crucible in a carbon resistance electric furnace. To the melted iron in runs 2, 3 and 4 metallic manganese and manganese sulfide were added to give 1, 2 and 4 per cent. manganese respectively, with 0.50 per cent. of sulfur in each. In runs 5, 6 and 7, metallic manganese andiron sulfide to give the same proportions of manganese and sulphur as in runs 2, 3 and 4, were added. The melts were held molten in the furnace for an hour and then cast into small ingots.

Jan 2, 1925

By G. L. F. Powell

g samples of Cu-20 wt pct Ag alloy have been mdercooled to a maximum of 197°C by melting under a slag of commercial soda-lime glass in a vitreous silica crucible. No grain refinement of the primary copper was observed in samples undercooled to the maximum of 197°C. When the samples contained a small amount of oxygen, the copper dendrites were partially recrystallized at undercoolings greater than 97°C. In previous papers&apos;-3 reporting the grain structure of undercooled silver and copper, it was observed that grain refinement was dependent on both undercooling and oxygen content. Grain refinement occurred in undercooled silver when the degree of undercooling exceeded the range 153" to 175"C, while in Ag-0 alloys (0.12 wt pct) fine equiaxed grains were exhibited when undercooling was greater than 50°C. Similarly, copper samples undercooled as much as 208°C displayed fan-shaped growth from a single nucleation site, while the grain structure of Cu-O alloys (0.08 wt pct) was fine and equiaxed at undercoolings larger than 150°C. Thus the presence of oxygen greatly reduced the undercooling at which grain refinement occurred. It was also observed that the change in grain size resulted from recrystallization and was not due to an enhanced nucleation rate in the liquid-solid transformation. It is possible that the influence of oxygen on recrystallization is due primarily to its presence as a solute element. walker4,&apos; reported that, although a grain size change did not occur in pure nickel until the undercooling exceeded 150°C, small grains were observed in samples of Ni-Cu alloy solidified at small and large degrees of undercooling. Jackson et al.6 suggested that the fine grained structure of the Ni-Cu alloy resulted from the melting off of dendrite arms during recalescence. This remelting process may occur in alloys as a result of segregation during freezing which causes a variation in liquidus temperature from point to point within a dendrite. It was therefore decided to undercool copper with a metallic alloying element to ascertain whether the presence of a metallic solute would have a similar effect to oxygen in inducing grain refinement. A Cu-Ag alloy was chosen, since both metals had been shown to behave similarly on undercooling. The alloy Cu-20 wt pct Ag was selected since the eutectic constituent outlines the initial growth form of the primary copper, so that the as-frozen grain structure is not obscured if subsequent recrystallization occurs. This paper describes the results of undercooling experiments carried out with Cu-20 pct Ag samples undercooled to a maximum of 197°C and the effect of oxygen content on the grain structure of the undercooled samples. EXPERIMENTAL Melting was carried out in a small cylindrical resistance furnace using "fine" silver granulate and oxygen-free high conductivity copper. The procedure adopted was to melt the required quantity of silver in air in a clean vitreous silica crucible for approximately 15 min, freeze, and add granulated commercial soda-lime glass to form a complete surface slag cover, after which the sample was melted and frozen several times to reduce the oxygen content. The glass slag cover was approximately 3 in. thick. Pieces of copper (=50 g) were added to the crucible until the required quantity to make 350-g samples of alloy had been charged. Each piece was added quickly to the crucible which was held at a temperature slightly above the melting point of silver. The piece was quickly pushed beneath the glass to minimize oxidation and any oxide coating usually decomposed before the piece had settled down into the silver. After the full quantity of copper had been added, the melt was stirred with a silica rod to hasten homogenization and a Pt/Pt 13 pct Rh thermocouple enclosed in a vitreous silica sheath inserted for temperature measurement. Heating and cooling curves were recorded on a potentiometric chart recorder fitted with a zero suppression unit. The milli-voltage range of the recorder was adjusted so that temperatures could be read to 1°C. Heating and cooling curves were taken every hour until three consecutive readings gave the same solidus-liquidus range, consistent with the solidus-liquidus range for this alloy composition by reference to Hansen and Anderko.7 Metallographic examination of samples frozen at this stage, failed to show any variation in composition from bottom to top of the ingot. Consequently, it was considered that the melt was homogeneous at this stage and undercooling experiments were then car-

Jan 1, 1970

By William Hurst

Muskat&apos;s depletion performance equation is here derived considering the expansion behavior of the reservoir hydrocarbon system and a simple fractional-flow equation. This nietkod of derivation leads logically to the two extensions that follow. The first of these is concerned with gravity segregation in a depletion-drive reservoir. The second is concerned with including an empirically determined tern? for water influx in the performance equation. The more general equation for gravity segregation when there is a primary gas cap and empirically-determined water influx is stated for completeness. These equations have been found useful in reservoir performance calculations in Eastern Venezuela. A discussion on the methods of solving these equations follows, and considers firstly the effect of taking finite intervals in the numerical integration, and sec-ondly, methods of incorporating the time functions involved in segregation in with the expansion behavior. The paper concludes with a brief general discussion on further extensions to the depletion performance equation. INTRODUCTION The two fundamental sources of energy by which oil is produced from a reservoir result from pressure depletion inside the boundaries of the reservoir and fluid encroachment across the boundaries of the reservoir. The wells in either case form low pressure outlets through which oil and gas may be produced by the expansive force of the reservoir fluids and associated encroaching fluids. When the reservoir pressure is higher than the bubble-point pressure of the oil, so that there is no free gas in the reservoir, these expansive forces are the only ones available for the production of oil. However, when the reservoir pressure is less than the bubble-point pressure of the oil, free gas is vaporized as the pressure falls. With both oil and free-gas phases present, the additional forces of gravity and capillarity may operate on the gas-oil system, as they have previously operated on the oil-interstitial water system. Gravity tends to segregate the free gas from the oil due to their density difference. Capillarity opposes and eventually balances gravity as the more extreme free gas and oil saturations are reached, preventing the independent move- ment of free gas until it is above a certain saturation, and the independent movement of oil when it is below a certain saturation. The type of depletion performance equation chosen for predicting the future performance of a reservoir depends on the amount of past history available. When the reservoir is somewhere past the halfway mark in depletion, some form of decline curve is often used. With less past history, material balance equations which incorporate empirical factors based on the past performance are often used. When, however, the amount of past history is small, the Muskat depletion performance equation will usually be used. The distinguishing feature of this type of equation is that empirical factors based on the over-all or macroscopic reservoir behavior are almost or entirely absent. Each parameter affecting the reservoir performance is ascribed an independent set of values based on measurements made on laboratory samples; that is, incorporating microscopic empirical factors. In establishing Muskat-type depletion performance equations, it is necessary to consider the reservoir as consisting of a number of associated blocks, in each of which the saturations and pressures may be considered uniform, and in each of which all substances have uniform pressure-volume characteristics. Thus, a primary gas cap can usually be considered as one block and an aquifer as another. Gravity segregation may be negligible for practical purposes when the rock and oil properties are adverse and/or the dip or thickness of the reservoir is too small. In this case the whole oil leg may be considered as one block, except in very large reservoirs. In very large reservoirs the fluid and rock properties may vary enough, particularly in the dip direction, for it to be necessary to divide the oil leg into a number of blocks, in each of which the relevant quantities may be considered uniform. When gravity segregation of the oil and free gas is not negligible, it is necessary to consider the space occupied by the initial oil leg as divided into two blocks, a secondary gas cap and an effective oil leg, in each of which saturations may be considered to be uniform. The total volume of these two blocks is thus constant, but the secondary gas cap grows continuously at the expense of the oil leg. Muskat1 derived depletion performance equations for the basic case of an oil reservoir with closed boundaries and without segregation, and for the case of an oil

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy&apos; has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as &apos;idea1 gases,&apos; and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called &apos;ideal&apos; behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By J. B. Nau

A short time ago some interesting experiments concerning a new steel-making process in the open-hearth furnace were made by the writer at the Croton magnetic mine, N. Y.

Jan 1, 1892

By W. B. Agocs

IN August 1954 a low altitude test geophysical survey was made in the Green Pond area of Morris County, New Jersey, with a Gulf Research and Development Co. Model II total magnetic field variation magnetometer mounted in a Sikorsky S-55 helicopter. The test was made in this area to compare the results of a high precision, very low altitude magnetometer survey with an existing ground magnetic survey in this area having known magnetite concentrations, so that the method could be used in areas of difficult access for the detailing of airborne magnetometer anomalies of interest in place of ground surveys. The load capacity of the Sikorsky S-55 permitted installation of a recording scintillation counter so that a radioactivity survey would be made simultaneously with the magnetometer survey. The area surveyed is located at approximately 41°00&apos;N and 74o28&apos;W, just south and east of the town of Green Pond, N. J. The outstanding topographic feature of the region is Copperas Mountain, a well defined ridge, maximum elevation 1222 ft, which runs the entire length of the survey. The lowest point in the survey, 810 ft, is in the extreme eastern corner. Topography of the area is shown in Fig. 1. The three major rock units outcropping in the area are all metamorphic: the Pochuck gneiss, which has been divided into two metamorphic facies; the Byram gneiss; and the Green Pond conglomerate. The relative ages of the Pochuck and Byram formations, both pre-Cambrian, are in doubt, but it is believed that the Pochuck is the older of the two.&apos; The Green Pond conglomerate is Silurian.&apos; Distribution of the outcrops and mine locations is shown in Fig. 1. Two facies of the Pochuck gneiss can be distinguished locally—the Copperas Mountain and Kitchell members. The Copperas Mountain member is a hornblende gneiss, and all the mines and prospects in the area are in this unit. The Kitchell is a quartz-plagioclase feldspar gneiss. The Byram gneiss is a relatively nonresistant valley formation which is high in the potash feldspar. The Green Pond conglomerate is a well indurated quartzite-conglomerate which forms the Copperas Mountain and the Green Pond Mountain&apos;s ridge to the north. It overlies the gneisses with a strong angular discordance that may be a fault. The geologic structure of the Green Pond area is relatively uncomplicated. The foliation planes of the gneisses dip steeply to the southeast, and the Green Pond conglomerate dips steeply to the northwest. Additional faulting in the area is indicated at the contact between the Kitchell member of the Pochuck and the Byram along the base of the topographic spur extending to the southeast from Copperas Mountain. The magnetite mines of Pardee, Winter, Davenport, Green Pond, Copperas, and the Bancroft shaft are described by Bayleyl and Stampe2.&apos; The ore is in the Copperas Mountain member of the Pochuck gneiss. The magnetite veins are 10 to 50 ft wide and up to 300 ft long, dipping to the southeast at angles ranging from 40" to 75". The locations of these mines are shown in Fig. 1. Dip Needle Survey: The dip needle survey shown in Fig. 2 was taken from a U. S. Bureau of Mines Report of Investigations." The figure numbers below the local, individual map area outlines refer to the figures in the aforementioned reports which were not contoured. The area of the dip needle survey was confined almost exclusively to the outcrops of the Pochuck gneiss. The separation between survey profiles was 100 ft and the distance between stations on the profiles was 25 ft in highly anomalous zones to 100 ft in magnetically flat areas. A total of 16 1/2 miles of traverse was surveyed over an area of approximately 1/2 sq mile with 2050 stations. The magnitude of the magnetic anomalies is difficult to determine due to the lack of information concerning the type of dip needle used and the procedure followed in making the dip needle survey. This latter would include the method of "zeroing" the dip needle and the procedure of reading at the stations, whether on the swing or statically. Calibrations made of the Gurley dip needle, Lake Superior type, show a static sensitivity of 385 gamma per degree in the range from —25" to +35o, corresponding to a variation in the total field of —9600 gamma to +13500 gamma in a total field of 57000 gamma, inclination 72". The sensitivity increases to 16 gamma per degree from a deflection of 60" to 76", and from 76" to 172" the sensitivity decreases continuously to a low of 260 gamma per degree. From the above it may be seen that it is difficult to assign an arbitrary sensitivity for the dip needle used on this survey. However, an estimated value of 100 gamma per degree may be assigned. On this basis, the majority of the magnetic anomalies, whose deviation is +20°, would be 2000 gamma. Locally, west and northwest of the Pardee mine the magnetic anomaly is +50°, or 5000 gamma; in the Green Pond mine area deviations of +75" are observed that would correspond to anomalies of 7500 gamma. The areal extent and width of the dip needle magnetic anomalies is comparable to profile and station spacing. Hence it is concluded that part of the detail may be due to control, and the probable cause of the magnetic anomalies is at or near surface exposures of magnetite concentrations in the form of veinlets and disseminations whose locations correspond to the local magnetic anomalies. On the basis of the magnetics, none of the magnetite concentra-

Jan 1, 1956

By D. R. Wieland, H. T. Kennedy

The object of the work reported here was to determine the content of elemental sulfur in gaseous methane, carbon dioxide, hydrogen sulfide, and in mixtures of these gases, at pressures and temperatwes encountered in natural gas reservoirs. Sulfur content at equilibrium is reported for pure methane, carbon dioxide, hydrogen sulfide, and on three binary mixtures of each of the three pairs of gases at pressures of 1,000, 2,000, 3,000, 4,000, 5,000 and 6,000 psia and at temperatures of 150°, 200° and 250°F. In addition, the sulfur content of three ternary mixtures at the same temperatures and pressures are reported. The results indicate that the sulfur content is higher in the gases at higher temperatures and pressures. The content is highest in hydrogen sulfide, intermediate in carbon dioxide and lowest in methane. INTRODUCTION At ordinary pressures and temperatures, the concentration of a nonvolatile material, such as sulfur in a gas at equilibrium, is a function of the vapor pressure of the material and is independent of the nature of the gas. As the pressure and temperature increase, the gas assumes some of the properties of liquids, including the power to dissolve other liquids and solids, to an extent dependent on the nature of both the gas and the material dissolved. At equilibrium, the content of sulfur in the several gases considered here may thus be considered as solubilities which are fixed for a given composition of gas, temperature and pressure. The study of the solubility of elemental sulfur in gases is of interest because sulfur is sometimes present in reservoirs producing natural gas and must be present in the vapor phase. Upon reduction of pressure and temperature, the sulfur precipitates from solution in the reservoir and in the tubing and fittings. Due to the fact that the greatest pressure drop in the reservoir is around the wellbore, the volume of sulfur precipitated will be greatest in this locality and can cause a substantial reduction in the permeability of the formation in this area. As the natural gas flows up the tubing string, the pressure and temperature are further decreased, causing further sulfur precipitation. If the volume of free sulfur is large and remedial measures are not taken, complete plugging of the tubing can occur. Knowledge of the content of sulfur as a function of composition, temperature and pressure will enable the operator to determine what changes in pressure and/or temperature are necessary to keep the sulfur in solution. If the sulfur solubility is large and can be controlled, the operator may desire to produce the well at a high wellhead pressure and temperature and reclaim the sulfur at the surface. The high solubility of sulfur in hydrogen sulfide (5.6 per cent by weight at 5,000 psi and 200°F) suggests the feasibility of recovering sulfur by injecting this gas into sulfur-bearing reservoirs and expanding the produced gas to precipitate out the sulfur. The present project was designed to measure the solubility of sulfur in carbon dioxide, methane, hydrogen sulfide and mixtures of these three gases at various temperatures and pressures. These gases were the major constituents of the gas well where plugging by sulfur was encountered. A study of the published literature shows no data on the solubility of sulfur in any gas, although Hannay and Hogarth,&apos; in 1880 reported that it was soluble in carbon disdlide above the critical temperature of carbon disulfide. EQUIPMENT AND PROCEDURE Fig. 1 shows the layout of equipment employed to bring gases to equilibrium with sulfur and to isolate the quantity of sulfur contained in a known volume of gas. Pure gases were measured in the charging bomb at known temperatures and pressures and displaced into the reservoir bomb to make up the desired mixtures. When equilibrium was achieved

By Lawrence K. Nordell

This paper reviews practices used In the selection and sizing of belt conveyors and stacker systems commonly used in crushing and grinding plant facilities. Historical and modern methods of sizing this equipment are presented. The new methods Include: 1) probability theory applications for establishing component reliability, 2) "Monte Carlo" simulation techniques used in evaluating alternative system designs and in establishing service factors and corresponding availability Indices of each system, 3) quantifying the system and component operating characteristics using computer assisted modeling tools simulating rigid body and elasto-mechanic behavior for starting and stopping large and/or complex belt conveyors.

Jan 1, 1982

By Frederick Laist

About six years ago the Anaconda Copper Mining Co. decided to investigate the possibility of extracting zinc from the ores of certain mines in the Butte district. These ores are of a complex character and contain so much iron and lead that the concentrate contains only 33 to 35 per cent. zinc. Investigations showed that while a high-grade concentrate could not be obtained by ordinary methods, such as tabling and magnetic treatment, a fair grade could be made by the Horwood process. In this method, the concentrate resulting from the flotation of all of the sulfides is given a light roast and this calcine is subjected to flotation in the presence of a large amount of sulfuric acid; the resulting concentrate contains most of the zinc and a residue contains most of the iron. The fact that the lead, copper, and silver are divided approximately equally between the zinc concentrate and the iron residue and the large consumption of acid, which ranged from 50 to 100 lb. (22 to 45 kg.) per ton of concentrates, were serious objections to this plan. The zinc recovery, moreover, was low, as a considerable percentage invariably accompanied the iron. While a profit might be made on the ores by the use of this process, it was thought that other and more promising methods might be devised. After carefully studying the field and doing some laboratory work on various processes that had been suggested, it was decided that the electrolysis of sulfate solutions was the most promising. We soon found, as have other investigators, that the only way to obtain a good zinc deposit is to have the electrolyte free from all metals more electronegative than zinc, such as copper, cadmium, lead, arsenic, antimony, etc. Arsenic and antimony are particularly injurious, causing very poor current efficiency and small yield per horsepower when present in amounts so small as almost to defy detection—1 mg. or less per liter. A pure zinc is soluble only with difficulty in sulfuric acid; an impure zinc dissolves very readily. Electrolytic zinc deposited from pure solutions is, of course, extremely pure and dissolves only about one-fiftieth

Jan 1, 1921

By J. R. Stack, H. H. Alexander

Prior to 1915, numerous attempts were made to treat tin concentrates in the United States, but for various reasons they were unsuccessful. Tin ore is said to have been found in nearly every state, but none of the deposits has proved to be of commercial importance. An annual output of a few hundred tons in Alaska is the only domestic production; hence any considerable production of tin in the United States must be from foreign ores. The most promising occurrence of tin was found in the Black Hills, S. Dak.; in the early development stage, it was called the Cornwall of America. Associated with the tin is tungsten The story is told that an exceedingly fine specimen of the Black Hills ore was sent to England to encourage stock promotion; the desired effect was produced until a skeptic chipped off a small piece, which the analysis showed to be wolframite. First Attempts at Smelting One of the first promising attempts at tin smelting in the United States was made by R. T. White at Bayonne, N. J., in 1903. Mr. White, after spending some time in England studying the methods of tin smelting, organized a company called the International Tin Co., and erected a plant to treat tin concentrates from the Straits of Malacca. About the time the plant was completed, the English Government placed an export duty of 40 per cent. ad valorem on tin concentrates exported to other than British smelters, which duty made it impossible to operate this plant so the enterprise was abandoned, As this export duty is still effective, the only source of tin-ore supply for the United States is the Bolivian concentrates. Bolivian Tin Concentrates Unlike the alluvial placer deposits, nearly all Bolivian tin occurs in lode deposits and some of the highest grade ores contain only a small

Jan 1, 1924

NEW MEMBERS The following list comprises the names of those persons who became members during the period Sept. 10, 1916, to Oct. 10, 1916. BLOOMFIELD, EDWIN CHARLES, Min. Engr., 1012 Standard Bank Bldg., Vancouver, B. C., Canada. BRINGS, HENRY, Min. and Met. Engr., Chief Engr., and Geol., Mollet-Mesrine, 1212 Mills Bldg., El Paso, Texas. CHASE, MARCH F., Vice-Pres., Commercial Acid Co., 1906 Boatmens Bank Bldg., St. Louis, Mo. CUMMINGS, ALVIN M., Asst. Mine Supt., Witherbee, Sherman & Co., Inc., Mineville, Essex Co., N. Y. DOUGLASS, GEORGE M., Genl. Safety Inspector, Amer. Smelt. & Ref. Co. 120 Broadway, New Fork, N. Y. EMRICH, CLARENCE T., Chief Chemist, Old Dominion Copper Min. & Smelt. Co., Box 1163, Globe, Ariz. GARDANIER, SUTTER ALBERT, Assayer, Mgr., Douglas Assay Co., Douglas, Cochise Co., Ariz.

Jan 10, 1916

By J. King Hoyt

IN both Sweden and England rapid progress is being made in metallurgical development, and the steel industry in both countries is distinctly on the mend. There has been some industrial trouble in Sweden in the iron mines and the wood pulp mills, but at the same time all the steel works have a sufficient stock of pig iron and ore to continue their operations for many months to come. Consequently the strike, unless long protracted, will not affect the output of steel in Sweden. Several of the steel manufacturers in Sweden, most notably Forsbacka and Sandviken, have been very suc-cessful recently in securing large orders, particularly from the continent, for ball-bearing steel, both hollow and solid. Whereas some years ago they ran into-se-rious competition with the German mills, the quality of the steel from these Swedish mills is such that they are now firmly established, and are selling some of the lead-ing manufacturers of bearings on the Continent, as well as automobile manufacturers. The secret of their success seems to lie in a better selection of ores, in more careful control of blast-fur-nace operations and better equipment. Rule of thumb in steel making is taboo, and strict reliance is placed on the laboratory. They are constantly experimenting, and metallurgists and chemists are sent to different countries for study and investigation. In their native ores they have, of course, a unique advantage in pos-sessing iron ores extraordinarily free from phosphorus. At Forsbacka, they are not content with the ordinary chemical analysis of the ingot; but also test the physical properties, as well as make metallographic investiga-tions for slag inclusions, segregations and oxides. In both England and Sweden they watch the nitrogen con-tent of the steel very carefully, a feature which does not appear in the ordinary analysis. In testing carbon, they do not use the color test, but employ an electric .induction device.

Jan 7, 1928