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By Donald McLaughlin

INCREASING variety of interests among mining geologists is becoming more and more marked, as the frontier of their science and of its applications continues to expand. Each of the traditional lines of inquiry provides its crop of new and better defined problems, and answers to them are being found in far more precise terms than in the past as older uncertainties .are swept away with the sharper techniques and the even sharper ideas of modern geology. A glance over the assemblage of projects and publications in 1939 reveals conspicuous activity in many different parts of the front, such as the attack on the controversial question of the acid or alkaline character of ore-forming solutions, the place of mineral districts in the larger structural framework of continents, and the place of ore shoots in the local patterns of districts. Instructive comparisons are being made which cut across lines of older correlations or which reinforce them by pointing out heretofore ne-

Jan 1, 1940

By F. W. Schremp, V. L. Johnson

This paper discusses the results obtained from high temperature, high pressure filter loss studies in which field samples of clay-water, emulsion, and oil base fluids were used. High temperature, high pressure tests of some premium priced emrilsion and oil base drilling fluids show filter loss peculiarities that are not predicted by standard API tests. It is recommended that high temperature, high pressure filter loss tests be used to evaluate the performance of such fluids. Apparatus is described which proved to be satisfactory for evaluating filter loss behavior over a wide range of temperatures and pressures. INTRODUCTION The petroleum industry spends large sums of money each year on chemical treating agents for lowering filter loss and on premium-priced low filter loss drilling fluids. While it is an accepted fact that low filter loss is advantageous during drilling operations, it is questionable whether the present standard method of determining filter loss gives a reliable indication of the loss to he expected under bottom hole conditions. The purpose of this paper is to show that high temperature. high pressure filter loss tests Should be used to evaluate filter loss behavior of fluids for deep drilling. Concern over possible effects of filter loss on oil well drilling and well productivity dates back to the early 1920's. During the years 1922 to 1924, filtration studies were reported by Knapp,' Anderson2 and Kirwan." These studies were the first to be reported in the literature on this subject. No further information was published on the subject until 1932 when Rubel' presented a paper in which he discussed the effect of drilling fluids on oil well productivity. In 1935. .Jones and Babson constructed the first laboratory tester designed to study the effects of temperature and pressure on the filter loss behavior of clay-water drilling fluids. In a discussion of their investigations, Jones and Babsons stated, "Performance characteristics of a mud can he evaluated with considerable reliability by a single test at 2,000 psi and 200°F. Exact correlation between the results of performance test5 made under these conditions and the behavior of muds in actual drilling operations is of course impossible." Jones arid Babson apparently were well aware that at best laboratory tests can give only qualitative answers to the question of what is the actual behavior of a drilling fluid when subjected to deep drilling conditions. Jones' presented a paper in 1937 in which he described a static filter loss tester to be used for routine filter loss tests. This instrument subsequently was adopted as the standard APl filter loss tester. In 1938, Larsen7 developed a relationship between filtrate volume and filtrate time that is in general acceptance today. Larsen was cognizant of the danger of estimating bottom hole behavior from filter loss measurements at room temperature. He tried to predict the effect of temperature on filter loss by relating temperature effects through the temperature dependence of filtrate viscosity. This was undoubtedly an over-sirriplification of the temperature dependence of drilling fluid filter loss. In 1940, Byck" published a summary of experimental results of filter loss tests made on six representative California clsy-water drilling fluids. He concluded that "no existing method will permit even an approximate determination of the filtration rate at high temperature from data at room temperature. It is necessary to measure filtration at the temperature actually anticipated in the well, or to make a sufficient number of tests at various lower temperatures so that a small extrapolation of these data to the anticipated well temperature may be applied." Byck's findings were presuma1)ly well accepted and recognized by drilling Fluid technologists, and yet, they did not lead to wide adoption of high temperature drilling fluid filtration equipment. This is evidenced by the fact that no addition information has appeared in print on the subject since 194). Study of Byck's data shows that there was a useful consistency in them. The fluids did not show predictable losses at high temperatures, but they did line up at high temperatures in approximately the same order that they lined up at low temperatures. That is, if a fluid appeared to be a good fluid with relatively low loss at low temperatures, it would also be a good fluid with relatively low loss at high temperatures. In the last decade. the above situation has changed. The drilling fluid art is markedly different from what it was. The outstanding change, as far as the present discussion is concerned, has been the adoption of wholly new types of drilling fluids. Oil base and emulsion drilling fluids have come in to wide use. It is, therefore, necessary- to re-examine previously satisfactory generalizations to see if they are still valid. It turns out. as might have been expected. that Byck's explicit generalization. already quoted, is still true. Filter losses at high temperatures cannot be predicted from filter losses at low temperatures. However, no further generalizations are valid now. Fluids of different chemical types show different general behaviors. No longer do the fluids line up approximately the same at high temperatures as they do at low temperatures. They may line up entirely differently. Special fluids exhibiting very low loss at low temperatures may have losses as high as those of ordinary clay-water fluids at high temperatures. This fact is highly significant, because premium prices are being paid for the special fluids.

Jan 1, 1952

By Frank T. Sisco

SHORTAGES of metals and minerals and substitution of less critical materials for those in which a virtual famine exists received detailed and frank discussion at a recent conference in Washington called by Robert E. McConnell, director of the Conservation Section, Office of Production Management. Representatives of the large engineering societies in the United States and O.P.M. department heads participated in the discussion. To open the session Mr. McConnell called upon Zay Jeffries, chairman of the O.P.M. Advisory Committee on Metal Conservation and Substitution, to summarize the present situation. Dr. Jeffries touched briefly on the status of metal shortages, which has already received considerable attention in the popular press, and said that much of the present difficulty was caused by the too-hasty substitution-without sufficient con¬sideration of the immediate conse¬quences-of metals having ordinarily a small yearly consumption, for those having a much larger annual consumption. As a result, all the alloying metals used in alloy-steel manufacture have become scarce, with the exception of molybdenum; further¬more, despite a reserve of 11,000 tons of molybdenum in this country and despite a normal consumption of only about 3500 tons and a prospective annual production rate of 21,000 tons by October, a shortage of molybdenum is possible before this war is over.

Jan 1, 1941

By Herbert H. Kellogg

Graphs representing the standard free-energy of formation as a function of temperature for 21 fluorides are presented, along with estimated values for the standard free-energy of formation of 20 atedadditional fluorides. A few of the many possible uses of these data in metallurgical calculations are discussed, including the fluorination of oxides, sulphides, metallurgicaland chlorides, and the reduction of metal fluorides. RECENT papers which have presented free-energy data for oxides, sulphides, chlorides, carbonates, sulphates, and silicates in the form of free energy vs. temperature plots,1-5 have found important uses in teaching and metallurgical development work. This method of presentation of thermo-dynamic data serves to make available in readily usable form thermodynamic constants which are scattered throughout the literature, and to show by graphical means the stability relations which exist between the compounds of a given type. It is certainly desirable to have these free-energy-temperature diagrams for as many types of compounds as are of present or potential use in metallurgical processes. Thus, even though there are but few uses of metallic fluorides in extractive metallurgy today, the potential uses of fluorine processes are of great importance and serve as the principal justification of this paper. Recent developments in the production of fluoro-carbons have resulted in vastly improved methods for the production and handling of fluorine and corrosive fluorides, with consequent reduction in costs.".' The extractive metallurgist should no longer overlook possible fluorine processes when development of a new process for a relatively high unit-price metal is being considered. In a previous paperv he author outlined in some detail the importance and use of free-energy data in metallurgical calculations and also discussed the properties of a standard free-energy vs. temperature diagram. The same method of presentation is adopted in this paper, and the reader is referred to the earlier work for explanations of the use of free-energy data. Thermodynamic Data This paper presents standard free-energy vs. temperature diagrams, Figs. 1 and 2, for those fluorides for which the major thermodynamic constants are known. In the calculations of the standard free-energy of formation (AGO), values of the enthalpy of formation at 298°K (?Ho,) were taken from "Selected Values of Thermodynamic Constants"8 most of the values of standard entropy at 298°K (S°298) were taken from "Selected Values"," but in a few cases the values given by Kelley9 ere preferred; data for the Phase changes came from "selected Values" and several of Kellley's publics- tions;0-12 and most of the specific-heat data were taken from Kelley.l0 The appendix gives a detailed list of the sources of the data. As explained in an earlier paper,6 he accuracy of some of the standard free-energy relationships is not high. An error of +1 kcal at 1000°C is expected in most of the curves of Figs. 1 and 2. The error may be as high as +3 kcal in some of the curves. Rather than attempt to estimate the reliability of each curve, the source of the data used is reported in the appendix, and the reader may compare these data with newer values as they become available. Figs. 1 and 2 fail to show values for the fluorides of many important metals. In most cases this is because the entropy of the metallic fluoride is unknown. For preliminary calculations it is often useful to have available the best estimate of an unknown datum, rather than no information at all. With this in mind, Table I lists estimated standard free-energy values for a number of important metallic fluorides not included in Figs. 1 and 2. The values reported in Table I were, calculated by Brewer et al.13 and are based on estimated entropy values. The estimated uncertainty of the values for each fluoride were calculated from the uncertainty values given by Brewer1' for ?H°, and the entropy function.

Jan 1, 1952

By Richard Hamburger

Calculating machines permit the use of the more rapid cotangent and semigraphic solutions of plane triangulation. The results of these methods are as accurate as those of other methods. Simple adjustment of the net, and ease of calculation encourage more complete field work. Errors in field work or in computation are easily localized.

Jan 1, 1950

By D. W. Brunton

Discussion of the paper of D. W. Brunton, presented at the Spokane meeting, September, 1909, and published in Bulletin No. 33, September, 1909, pp. 837 to 855. WILLIAM' KENT, New York, N. Y.:-The Institute may congratulate itself on the opportunity of reading the splendid address of President Brunton. It is au admirable summary of the progress that has been made in the mining and metallurgical arts in recent years. The paper rightly give's the chief credit for this progress to the aid which has been rendered to these arts by the advances in mechanics, chemistry, and electricity. It is notable that most of the headings in Mr. Brunton's address refer to the work of the mechanical engineer, the electrical engineer, and the chemist, rather than to that of the specialist in mining-operations. It seems that. the most successful mining engineer of the present day is the one who makes the most intelligent application of the inventions and designs of engineers and others who are not directly engaged in mining. A tabulation' of the headings of the address, grouped as below, shows this most clearly. Work of the Mechanical Engineer-Rock-drills, hoisting-machinery, tramming, pumping, ventilation, dredging, sampling, concentration, briquetting, fume-recovery. Work of the Electrical Engineer-Electric machinery for hoisting, pumping, tramming, lighting and signaling, electric . transmission, electric smelting. Work of the Chemist and Metallurgist-Explosives, chlorination, cyanidation, roasting, lead-smelting, and copper-smelting. Work of the Geologist-Economic geology. Work of the Mining Engineer-Mine-mapping, surface-mining, timbering, tunneling; and planning and supervision of the work in general. The mining engineer of the present day, who is in responsible charge of a large plant, finds his chief work not in doing

Jan 1, 1910

By Ogden Tweto

The Leadville district, on the west flank of the Mosquito Range in central Colorado, has produced silver, zinc, lead, gold, and minor metals valued at $512,000,000. The ore deposits are in a sequence of dolomites and quartzites, Cambrian through Mississippian in age and about 500 feet thick, which is extensively intruded by porphyry sills, dikes, and plugs of Tertiary age. The sedimentary rocks and sills dip about 15°E and are broken by many faults, which are predominantly of nearnorth trend and downthrown to the west. The ore deposits are principally blanket or manto replacement deposits, but in the eastern part of the district many veins occur also. The replacement deposits are largely confined to three dolomite units in the stratigraphic sequence. Of these, the uppermost or Leadville Dolomite is the most productive. Most ore bodies are on the underside of porphyry sills and, particularly, beneath sills that occupy unconformities. Many replacement bodies have vein roots or branch from veins. The veins occupy faults and are productive mainly in the section of quartzites and dolomites and included sills. The primary ores consist principally of pyrite, marmatitic sphalerite, and galena but locally contain chalcopyrite, silver minerals, bismuth minerals, and gold. Principal gangue minerals are manganosiderite and jasperoid. The ore deposits have a crude zonal pattern centered around an intrusive center at Breece Hill, which evidently influenced ore deposition thermally. The ore deposits were oxidized to depths of several hundred feet in Miocene time. Bonanza ores mined in the early days were characterized by cerussite, cerargyrite, and embolite. Later, zinc carbonate ores were identified and mined on a large scale. The Leadville district is a complexly faulted and intruded area at the intersection of major fault systems trending N20°W and N15°E in the Mosquito Range. The intensely fractured area evidently localized igneous intrusion and subsequent mineralization. Ore solutions rose on many of the faults in the area, presumably from the same source as the porphyry magmas. Movement on these faults continued into the Pleistocene, displacing ore bodies, oxidation zones, Pliocene sediments, and glacial deposits.

Jan 1, 1968

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

By R. R. Sayers

THE South African Mining and Engineering Journal recently pointed out that no satisfactory solution of the question of compensation for silicosis can be arrived at by placing further liability of an inequitable nature upon the mines. There are at present 35 scheduled mines liable to contribute to the annual levy of $800,000 and provide for the net outstanding liability of $6,400,000. Several of these mines have, as yet, not been able to set aside sufficient funds against their out- standing liability to the Compensation Fund. The gold producers declare that the gold mining industry today is passing its zenith, and that the production of gold will decline, with a consequent lessening of the spending power of the mines, which in about ten years will be reduced to a great extent unless encouragement is given for the opening of new mines. It is during this period of decline that the mines will be required to meet the large burden already created by miners' phthisis. In England the Workmen's Compensation Act, 1925, was extended to industries involving exposure to asbestos dust.

Jan 1, 1931

By Philip B. Bucky

WITH the exhaustion of the sections of iron ore bodies amenable to opencut mining the iron ore miners raise the question: "How can we mine the extensions of these ore bodies in depth with the same costs as obtained in opencut work?" This question brings to the fore the relationship between mineral exploration and research on mining procedures. The iron miners must either find new de? posits amenable to their known methods of mining or develop new mining methods for deep deposits. It is understood that the oil companies will spend $30,000,000 next year in the search for new oil fields. How much the metal mining companies will spend in the search for new ore bodies is unknown, but without doubt the amount will run into several millions of dollars. If the mining companies that concern themselves with metals, nonmetallics, and fuels will set aside a substantial sum for fundamental and applied research in mining methods, they can not only lower their costs but increase their reserves thereby. Any increases in mining efficiency automatically result in increased ore reserves at no cost.

Jan 1, 1947

By T. Sterry Hunt

Jan 1, 1882

By Roscoe W. Stensrud

Marcona Mining Company operations are located 500 kilometers south of Lima, Peru, on the Pacific Coast, at approximately 15º-22' latitude south and 75º-11' longitude west. The terrain is sandy rolling hills ranging from sea level at the coast and rising sharply (escarpment) to an elevation of 800 meters at the mine area. The climate is arid and windy with a moderate year-round temperature, ideal for a year-round mining operation. San Juan, a new and modern community of 14,000 inhabitants and developed by Marcona, houses the working forces and their families.

Jan 11, 1968

By R. M. Bird

FEW persons outside of the foundry trade have any conception of the great variety of sands now regularly specified and furnished, nor of the differences in foundry practice frequently resulting from apparently minor changes in sands. Conditions in each locality where the sands are mined and prepared necessitate special equipment designed to perform the work efficiently. The description that follows of the foundry sand producing operations is typical of the areas in New York and New Jersey, and particularly refers to the operations of the George F. Pettinos Co.

Jan 1, 1926

By P. Chiotti, J. T. Mason

Ther?nal, X-ray, metallographic, and vapor pressure data were obtained to establish the phase diagram and standard free energy, enthalpy, and entropy of formation for the compounds in the Sw-Zn system. Four compounds, SmZn, SmZn2 , SmZn4.s, and SmZn8.5, melt congruently at 960°, 94Z°, 908°, and 940°C, respectively. The cornpounds SlnZns, Sm3Znll, and SnzZn7.3 undergo peritectic decomposition at 855", 870°, and 890C, respectively. Another compound of uncertain stoichiometry, SmZn11, undergoes peritectic decomposition at 760°C. Four entectics were observed with the following compositions in weight percent zinc and eutectic tenzperatures in degrees Centigrade: 12 pct, 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. An allotropic transformation and a composition range were observed for the SmZnz compound. The transfor)nation varies from 905" to 865°C as the zinc content increases from 16.0 to 48.5 wt pct, respectively. The free energy of formation of the compounds at 50PC varies between -15.9 kcal per mole for SmZn to -51.1 kcal per mole for SmZn,.,. Corresponding enthalpies vary between -19.2 to -78.3 kcal per mole. The ther-modynamic properties for the liquid alloys are described by the relations: A search of the literature revealed very little information on the Sm-Zn system. Chao et al.&apos; as well as Iandelli and palenzonai have reported the structure of SmZn to be cubic B2 type and Kuz&apos;ma et al3. have reported the structure of -sm2zn17 to be of the Th2Ni17 type. The purpose of this work was to establish the phase diagram of this system, to determine the zinc vapor pressure over the solid two-phase regions of the SYstem, and to calculate the thermodynamic properties of the compounds. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in this investigation were Bunker Hill slab zinc 99.99 wt pct pure and Ames Laboratory samarium. Analysis of the samarium by chemical, spectrographic, and vacuum-fusion methods gave the following average impurities in ppm: Nd, <200; Eu, <100; Gd, <100; Y, <50;Ca, 225; Ta, 400; Mg, 10; Cu, ~50; 0, 175; H, 20; and N, 15. The elements Fe, Si, Cr, Ni, Al, and W were not detected. The samarium was received as sponge metal and was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys with zinc contents up to the Sm2Znl, stoichio-metry. At higher zinc contents the grain boundaries of the tantalum containers were penetrated by the alloy and the containers failed during prolonged annealing. About 25 g of massive zinc and samarium sponge were sealed in tantalum crucibles equipped with thermocouple wells. These crucibles were in turn sealed in stainless-steel jackets. All closures were made by arc welding under an argon atmosphere. The samples were equilibrated in an oscillating furnace and in some cases were given various heat treatments in a soaking furnace. After appropriate heat treatment the steel jackets were removed and the alloy subjected to differential thermal analysis. The apparatus was calibrated against pure zinc and pure copper and found to reproduce the accepted melting points within 1°C. Alloys were subsequently subjected to metallographic examination and those of appropriate compositions were used for X-ray diffraction analysis and for zinc vapor pressure determinations. The vapor pressures were determined by the dewpoint method. Both the differential analysis and dewpoint measuring apparatuses have been described in earlier papers.4, 5 All alloy samples were etched with Nital (0.5 to 3 pct nitric acid in alcohol) except the samarium-rich alloys. These more reactive alloys were electro-polished in a 1 to 6 pct HClO4 in methanol solution at -700c at a potential of 50 v. EXPERIMENTAL RESULTS Phase Diagram. The results of thermal analysis are indicated by the points on the phase diagram, Fig. 1. Eight compounds and four eutectics were observed. The composition of the compounds and their melting or peritectic temperatures are given on the phase diagram. The four eutectic compositions in wt pct zinc and eutectic temperatures in % are: 12 pct,- 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. The stoichiometry of the most zinc-rich compound is still uncertain, but is very likely either SmZnll or SmZnlz. However, to simplify the presentation which follows it will be referred to as SmZnll. As shown on the phase diagram the phase regions for some of the samarium-rich alloys have not been unambiguously established. A sample of pure samarium was observed to transform at 924°C and to melt at 1074"C, in good agreement with corresponding val-

Jan 1, 1968

By C. H. Mathewson

UNFORTUNATE evasions of metals specifications recently brought to public attention through news items and editorials have caused executives of at least two great corporations to set up defensive procedures and to re¬affirm the patriotic purpose and conscientious effort of their plants in this battle of production. Whatever the exact conditions affecting these cases, in which the public interest has been safe-guarded by vigorous action, my reaction to such offenses in general is a feeling that they arise from the pressure and limitations that afflict our overextended war effort and that inevitably there will be more of them, doubtless more and more expertly conceived and less and less subject to detection as simple faked, or substituted analyses or tests. To the ladies, who doubtless are already beginning to ac¬quire a sense of painful resignation to a dry technical talk, may I say that the cookbook is full of specifications which customarily are varied within rather wide limits but it is generally recognized that the proof of the pudding is in the eating without regard to its exact composition or some scientific evaluation of its texture.

Jan 1, 1943

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 John S. Alexander

By MARSHALL D. DRAPER

THERE are said to be about 150 operating companies in Kotchiu, most of these being small, corresponding in degree to lessees in western mines in the United States. Of the total number there are probably forty large companies having their own smelting plants equipped with one or two furnaces, slag crushing plant and other accessory equipment. A few plants, not more than ten, do custom smelting. There are in all about fifty smelting plants in Kotchiu. With little variation, the equipment and methods are the same. The plant usually consists of two furnaces, one being in operation while the other is being relined 01- re- paired. An adjoining house contains one or more of the large buffalo-drawn Chilean mills for crushing slag. A few houses for the working coolies, with more pretentious ones for the owners, complete the establishment, the whole being surrounded by a compound wall 8 ft. high.

Jan 1, 1931

By Cyril Stanley Smith

ARCHEOLOGISTS, by use of the terms Bronze Age and Iron Age, indicate that metals have in the past determined the character of civilization. The relatively simple discovery by a primitive metallurgist that the addition of tin to copper both facilitated the production of castings and increased the durability of the product enabled hunter, warrior, and housewife alike to do things never dreamed of before. Similarly, the smelting of iron and the discovery of hardening methods greatly changed the arts of peace and war. Discoveries of low-melting-point alloys for joining and for making household utensils, and perhaps the adornment of a feminine form by sparkling precious-metal jewelry, have at times changed the destiny of a country. Bronze cannon, the cast and wrought iron Watt engine, copper transmission lines, and aluminum alloy aircraft, are cases of particular metals making possible the realization of an improved engineering design. Perhaps of the greatest influence of all upon civilization was the development of type metal. The rapid increase in the rate of dissemination of knowledge dates from the day that the technique of the pewterer was utilized in making rapidly reproducible and accurately sized letters for printing. It was not movable type, but metal type that was important, for metal castings could be made of identically the same shape and size at an enormous rate, and possessed excellent inking and wearing characteristics.

Jan 1, 1946

By E. W. Rouse

THE year 1936 has seen rehabilitation of many plants which had been closed or severely curtailed. The Steptoe smelter of the Nevada Consolidated Copper Co. has been transformed by a rearrangement of the flow of material and utilization of mechanical handling to a maximum. The Phelps Dodge Corp. reports the construction of newer and better reverberatories at the Copper Queen smelter, and of particular interest, a single high-pressure waste-heat boiler placed directly over the uptake. There has also been a complete reconstruction of the smelter at the Laurel Hill plant of the Nichols Copper Co.

Jan 1, 1937