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By R. T. Walker

GROUND waters-hot or cold-containing small amounts of the more common earth acids, such as carbonic acid, silicic acid, hydrogen sulfide, sulfurous acid and sulfuric acid, have only a very limited "solvent effect on dominantly siliceous rocks, whether of igneous or sedimentary origin, but in limestone they often form extensive cavities; and such "limestone caves" are the only openings of considerable size and continuity in rock formations that do not owe their existence directly and almost wholly to dynamic action. Limestone caves such as are developing at the present time must have been formed in all past geological ages in which limestone beds existed and where suitable conditions for the development of such caves prevailed; hence it would seem a reasonable expectation that, in the course of geological history, a certain number of ancient limestone caves must have been utilized as channels for the passage of mineralizing solutions, during portions of their course, at least, and that, in consequence, orebodies must have been deposited in such caves. Such a conception is not novel; it was proposed many years ago, but its possibilities, as explaining certain types of ore deposits, have been rather lost sight of in the development of the theory of the metasomatic replacement of rocks by minerals. It is the purpose of this article to assemble evidence to show that many of the orebodies found in limestone beds have been deposited in pre-existing caves; to discuss the criteria whereby such orebodies can be distinguished from others which have been formed along fissures and fracture zones traversing limestone, by the more common method of metasomatic replacement, analogous to orebodies in other formations; and to describe certain orebodies-particularly the "ore channels" of the Tintic district, Utah-as illustrative of the principles discussed. Limestone caves may be divided into two classes: those formed by cold, descending surface waters, which emerge again at some lower elevation as cold springs; and those formed by hot, ascending waters of deep origin or circulation, which attain the surface as thermal springs. Although these two classes are similar in many respects, there are certain characteristic and inherent differences whereby they can usually be distinguished.

Jan 1, 1928

By William Priestley

IN THE manufacture of gun forgings and other steel parts that, in service, are subject to sudden high stresses and shocks, it is most desirable to use steel possessing the greatest toughness and ductility possible without sacrifice of strength. In order to obtain this condition, it is necessary to procure steel that shows the highest possible elongation and reduction of area without lowering the tensile strength and elastic limit. Proper heat treatment of the steel can control this condition within certain limits. When heat treatment has failed to produce the desired results, metallurgists have used steels containing molybdenum, zirconium, vanadium, chromium, tungsten, etc. The purpose of this paper is to describe a method by which these desired physical properties may be procured-by the elimination of certain impurities that inherently exist in steel made by the open-hearth process, and without the use of expensive alloys. DESIGN OF GUN FORGINGS In the manufacture of gun forgings, a certain elastic limit is fixed by the designer, and the walls of the gun are made of the proper thickness, allowing a suitable factor of safety for the high stresses and sudden shocks that occur during gun firing. The elastic strength of the gun is about 1.4 times the stress set up at any point along the bore of the gun during firing with the maximum powder charge.

Jan 12, 1921

By GUY C. RIDDELL, Donald M. Liddell

THE electronic arts today constitute the outstanding development in the field of rare metals, if not indeed in the arena of scientific progress at large. The year 1930 may become known as the year in which the electronic tube took hold of the wheels of industry; it is the year in which the tube's emancipation from the art of communication was proclaimed. The little tube which made a $500,000,000 industry out of a vacuum has now been applied to mining, manufacturing, transportation, chemistry, and other industries. Not many appreciate the extensive utility that e1ectroni.t tubes have already found in transportation, where they control the speed and security of express trains, as well as operate traffic lights on important highways-in the case of the Detroit-Windsor bridge counting the traffic and instantly turning the reports into the superintendent's office some distance away. In an Ohio steel mill, ten-ton ingnts 'rash back and forth through the rolls, reversed by their own shadows. The vacuum tube also starts, stops, and levels, fast passenger elevators.

Jan 1, 1931

By Alfred E. Hunt

The application of the color-method for the estimation of manganese in iron and steel, based upon the depth of the characteristic purple color of permanganic acid, was first made in this country, the writer thinks, by one of the members of the American Institute of Mining Engineers, Mr. Samuel Peters, in 1874, at the laboratory of the Bay State Iron Company, and was published by him in the Chemical News. The method is credited to him in the new edition of Crooke's Select Methods. The principle of oxidizing manganese with peroxide of lead, or other oxidizing agents, and determining the amount of manganese from the color of the purple permanganic

Jan 1, 1887

By J. B. Caine

THE investigation outlined in this paper was carried on at the plant of the Sawbrook Steel Castings Co., Lockland, Ohio. EFFECT OF TEMPERATURE In the study of the effect of temperature, heats were made with the Sawbrook company's standard practice, using multiple slags, the only difference' being that the heats were tapped at two temperatures; one group between 2960° and 3040°F and the other group between 3200° and 3250°F. Slags were weighed throughout the heat at each slag change and after the heat was poured. Only the significant slag weights, those of the total slag and the finishing slag, have been reported.

Jan 1, 1947

By Ralph H. Sweetser

N Greenup and Carter counties, in the northeastern part of Kentucky, are the remains of many old charcoal furnaces built and operated during the period from 1818 to 1892. They were all included in what was called the Hanging Rock district. In the summer of 1930 I visited ten of these old blast furnaces, as follows:

Jan 1, 1931

By K. V. S. Sastry, V. P. Mehrotra

A laboratory investigation was carried out to study the influence of asphalt, bentonite, and corn starch binders on the pelletization kinetics of coal fines and on the quality of the resulting pellets. Pellet quality was evaluated in term of the compression strength, impact resistance (drop test), abrasion resistance, and resistance to severe weather conditions. The amount of binder addition did not significantly influence the pellet growth kinetics. However, the pellet quality varied markedly depending upon the type and the amount of binder wed. Experimental results are explained on the basis of the mechanism of interaction between the coal particles and the binders. Of the three binders tested, corn starch proved to be the best in all respects but for the resistance to water penetration. Finally, a combination of corn starch (imparting strength) and asphalt emulsion (imparting resistance to water penetration) was found to yield the best quality coal pellets.

Jan 1, 1983

By David R. Maneval, Sylvester Lemezis

All acid mine drain waters, regardless of source, share certain characteristics; but they do differ in exact chemical composition, degree of acidity, and total solids content. Any serious program to treat such waters must recognize these differences and apply to each specific case the technique which offers the best promise of each specific case the technique which offers the best promise of technical and economic success. The Pennsylvania Dept. of Mines and Mineral Industries has originated and funded studies of many different treatment means. Neutralization with lime is now being used on 200 different polluted streams in Pennsylvania, and multistage flash evaporation has been selected for a particularly large and troublesome outfall near Wilkes-Barre, Pa. A 5 x 106 gpd plant for this latter site is now being designed by Westinghouse Electric Corp. which developed a concentration process based on multistage flash evaporation as part of the State's research program.

Jan 1, 1973

By W. E. Wrather

The overproduction of crude oil in 1927 has received such widespread publicity, both within and without the industry, and the several factors which have brought about this situation are so thoroughly agreed upon by everyone, that it is unlikely the writer will in this brief review be able to contribute anything new. The entire story of low prices and demoralization revolves around two flush districts, Seminole and West Texas— the actual. performance of Seminole and the potential threat of West, Texas. The sustained production of California has been a contributing factor to this situation also. It seems reasonably certain that Seminole and West Texas will together dominate the industry during 1928, with Seminole probably destined to drop into second place, as additional pipe lines are completed into West Texas to care for its rapidly expanding production. It now appears inevitable that the production of 1928 will equal or exceed that of the past year, depending solely upon the rapidity wit,h which it is possible to market West Texas crude, and the degree of restraint which operators are willing to impose upon themselves in holding proved reserves of oil underground. Adversity has cultivated the growth of a promising spirit of cooperation which has accomplished practical results both at Seminole and in West Texas. Cooperation among oil producers has long been ardently hoped for, but prior to the past year it has never been effective on an important scale. The interests both of the industry and the public at large can best be conserved by cooperation in controlling production, and the widespread acceptance of this idea has paved the way for a more rational policy in the immediate future Production BY Major Districts The domestic production of the United States during 1927 amounted to 894,43.5,000 bbl. (Bureau of Mines), an increase over 1926 of approximately 128,000,000 bbl. California succeeded in maintaining its position of the past four years at 230,000,000 hbl. In 1923 with the Los Angeles

Jan 1, 1928

By R. D. Pehlke, J. V. Gluck

A study was made of the effect of small additions of metallic solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450o to 650°C. The experimental measurements were made in a multielectrode galvanic cell using. a fused LiCl-KCl electrolyte. The activity of zinc in binary solution exhibited a strong positive deviation from Raoult's law and obeyed Henry 's law to at least 0.050 mole fraction. The ternary addition of lead, gallium, or indium increased the activity of zinc. Cadmium or tin additions slightly decreased the zinc activity. Copper, mercury, silver, or antimony caused moderate decreases, while gold strongly decreased the zinc activity. The results are expressed in terms of Wagner's interaction parameter ejZn and a second-order cross-interaction parameter. The interactions for copper, gold, silver, and antimony showed a linear dependence with reciprocal absolute temperature, while the other interactions were essentially independent of temperature over the experimental range. Since tin and antimony decreased the zinc activity, the hypothesis of a purely periodic variation with atomic number was rejected. A semiquantitative explanation was possible with a free-electron model when relative electronegativities were used to express changes in the electron/atom ratio caused by the solute addition. Random solution and quasi-chemical models correctly predicted the majority of the interactions for which binary data were available to apply them. A knowledge of the thermodynamic interactions in liquid (and solid) metallic solutions is of considerable theoretical and experimental interest in the formulation of quantitative thermodynamic relations for metallurgical processes. The approaches to defining the interactions may be either phenomenological (i.e., "What mathematical function adequately describes observed behavior and permits extrapolation to new situations?") or theoretical, such as a specific model

Jan 1, 1968

By Frederick Beckett

WIDESPREAD experimentation has been conducted in recent years to devise a means of preventing intergranular corrosion in austenitic chromium-nickel steels of the 18 per cent chromium-8 per cent nickel type. Additions of titanium to these steels have been used commercially to overcome this difficulty, as advocated by Krupp of Germany, and the latest literature reference concerning improved details of this method is the article by Bain, Aborn and Rutherford.1 Extensive work by the present authors has shown columbium also to be a particularly valuable agent for inhibiting intergranular corrosion. This paper does not deal with steels that are largely or wholly aus-tenitic ; it is limited to a discussion of the results obtained through the use of titanium and columbium in plain high-chromium steels. For many years titanium has been used commercially by some steelmakers as a cleanser, and to a lesser extent as a hardener, but then in greater per-centages. The results of the work to be described disclose that titanium and columbium in proper proportions act as effective softeners in the high-chromium steels. It is well known that chromium intensifies the hardening effect of carbon in steel; it imparts pronounced air-hardening properties within a rather wide range of chromium content; it provides increased ductility in steels of given strength and hardness; and it enhances resistance to corrosion and oxidation at elevated temperatures to a marked degree. However, in applications requiring a combination of some of these valu-able properties great hardness is frequently a detriment rather than a merit. When the objective is a soft and ductile steel having optimum corrosion resistance, the producer strives for a carbon content as low as commercially practicable.

Jan 1, 1933

By H. M. Fisher, R. E. Snow, S. C. Sun

SEVERAL constructive and fundamental studies have been made in the analysis of data obtained from experiments carried on with batch ball and rod mills. The operating characteristics of ball milling in small continuous circuits have also been appraised. It is from these analyses that some of the theories of comminution have been developed. Relatively few studies of continuous rod milling have added significantly to the fundamental concepts, because seldom have they yielded sufficiently consistent results. Perhaps they have been too limited in their scope. Careful control of the variables in batch grinding is simple compared with that encountered in a continuous operation. This factor alone has discouraged many investigators. Occasionally results of systematic changes made in industrial rod mill circuits have been published, but usually the data are sketchy and are restricted because of the unwieldiness of the equipment used. The work, in general, has not been comprehensive; nevertheless it has provided empirical relationships that have bridged the gap between postulate and practice so that by proper manipulation of formulae, a mill designer can anticipate mill size and power requirements.14 Although operating variables of a small continuous mill are not so easy to control as with the batch mill, with present day devices, and with careful experimental work, consistent results can be obtained. Nearly four years ago, in the Process Laboratory, Allis-Chalmers Mfg. Co. began a systematic study of the effects of several variables upon the performance of the pilot rod mill. A mill was built in the laboratory to provide the versatility required for the proposed study. It was constructed in sections so that it could be operated, with a few modifications, as a rod mill 30 in. x 8 ft or 30 in. x 4 ft. The discharge end of the shell was flanged so that either an end peripheral discharge or an overflow discharge could be installed. Thus the performance of at least four types of mills could be studied merely by changing the type of discharge or the length of the mill shell. The grinding experiments were designed so that a study could be made of the way in which the mill speed, feed rate, and pulp density influenced the performance of both overflow and end peripheral discharge rod mills. Four sets of experimental data were collected from the four mill arrangements. The mill in each set of experiments was fed at four rates of feed depending on the length of the mill, at four pulp densities, and at five percentages of critical speed. Electrical and mechanical controls were in- stalled to regulate all these independent variables, and auxiliary devices were used to verify the precision of the controls at each point. The dependent variables used to quantify the experiments were the reduction ratio and the hew surface area produced as calculated from sieve analyses. These were incorporated with the energy factor by the calculation of both the new surface produced per unit of energy and the Bond work index.' Rod wear, as a dependent variable, was not studied because of the short period of operation for each run. Exclusive of repeat runs, each set of experiments yielded 80 products, and the total study at least 320 products, all of which were quantified. With the operating information collected, these data presented a bewildering accumulation. Statistical analysis has been invaluable in unraveling the confusion and in presenting a means of establishing the nature and the magnitude of the significant variables. Data presented in this paper are those from the 30 in. x 4 ft end peripheral discharge rod mill, Fig. 1, when limestone was ground at feed rates of 1000, 2000, 4000, and 5000 lb per hr, at pulp densities of 50, 60, 70, and 80 pct solids, and at mill speeds of 50, 60, 70, 80, and 90 pct of the critical speed. These 80 tests have all been run at least twice, and occasionally a third time, to prove that the data obtained were reproducible. The techniques of operation and the methods of quantification of results are described in the following pages and the results analyzed statistically to show the significant variables. The variables are plotted to show the relationships that exist. A massive dolomitic limestone from Waukesha Lime and Stone Co. was used for feed during these experiments because of its availability and its tex-tural uniformity. This limestone analyzed 28.7 pct CaO, 21.0 pct MgO, 6.0 pct SiO2, 0.4 pct A1²O³, and 0.3 pct Fe²O³ and had a loss on ignition of 44.1 pct. It had a rod mill grindability at 14 mesh of 9.6 grams per revolution from which a work index of 13.9 was calculated. The ball mill grindability at

Jan 1, 1955

By Ellsworth Daggett

The ore smelted in the Winnamuck furnace during the year 1872 consisted, for the most part, of oxidized ores from the Winnamuck mine, only sixty tons of outside ore (from the Spanish mine) having been smelted. The latter, like the principal Winnamuck ore, was oxidized or so-called carbonate ore. There was mixed with these oxidized ores three hundred to four hundred tons, or 7 to 10 per cent. of galena, some of which was mined with the oxidized ore, while a part was mined separately from the lower portion of the mine, and afterwards mixed with the ore, with a view of preventing the formation of deposits of metallic iron in the furnaces. The average assay in silver of all the ore handled was 51.46 oz. per ton, most of it existing as chloride of silver. The lead contents were 34.98 per cent,, all, or nearly all, in the form of carbonate of lead. The relative amount of silver is not at all constant, the best silver ore often being poorest in lead. The predominant gangue was silica, several determinations of which have been made on representative samples, yielding in three such samples 26, 38, and 58 per cent. silica, the latter test being ore containing but little lead. The average contents in silica are about 35 per cent., with 6 to 7 per cent. sesquioxide of iron, and small quantities of alumina and lime. Mechanically, the ore was very fine, and so thoroughly disintegrated that it presented few distinguishing characteristics, rendering sorting or separating of ore from waste difficult, and often impracticable. Experiments on a small scale have been tried, with a view to separate the silica by washing; but these were unsuccessful, as the finest slime, requiring a long time to settle in still water, contained a large amount of silver; and on a careful sizing and washing of the sands and coarser parts, the silver contents were found to be less dependent upon specific gravity

By Walter W. Bradley

FOR a number of years up to the economic setback of the 1929-1931 period, the greatest proportional advances in the mineral industries in California were made among the substances in the nonmetallic groupings, particularly among the so-called industrial minerals and the salines. During the past year or two, although these have not regained the stride that marked their progress in the preceding decade, we can still record, -some new developments. California produces annually between 55 and' 60 different minerals on a commercial scale. Of these, some 40 to 45 comprise the "structural," "industrial," and "salines" materials as grouped in the reports of the State's Division of Mines. Barite-The barite deposits of California were described in Report

Jan 1, 1935

By William B. Heroy

During 1932 no important changes occurred in the position of Africa as a producer of petroleum. The progress of development and production in each of the areas of interest is described below. Egypt The producing fields of Egypt are Hurghada and Gemsa, located on the west short of the Red Sea, and Abu Durba in the Sinai Peninsula. Most of the production is obtained from the Hurghada field, chiefly from beds of Cretaceous age. To the end of 1930 the Hurghada field had produced 2,831,751 tons of petroleum. The Gemsa field, discovered in 1909, reached its peak of production in 1914, when 88,000 tons were produced. Of late years the production has greatly declined. Total production of the field to the end of 1930 is 182,870 tons. The total production of Abu Durba to the end of 1930 is 7069 tons. The production of Egypt for recent years is as follows: 1928, 269,324 tons; 1929, 271,520; 1930, 281,997 (1,996,000 bbl.); 1931, 288,260 (2,038,000 bbl.); 1932, 253,182 (approximately 1,790,000 bbl.). Mozambique The operations of Inyaminga Petroleum Ltd., which was engaged in drilling in the colony, have been suspended. Angola Drilling operations in this colony, conducted by Companhia de Petroleo de Angola under a concession from the Portuguese Government, were continued. A test well drilled at Cacoba, about 60 miles southeast of Luanda, to a depth of 5651 ft. was not a commercial producer. A second well was being drilled in the vicinity at the end of 1932. Morocco Until last year the search for petroleum in Morocco was in the hands of several private companies but during 1932 the National Office of Liquid Fuels of the French Government took an active interest in the develop-

Jan 1, 1933

By Richard Moldenke

The author discusses some economic conditions which have made the career of the cast-iron pipe industry in the United States a checkered one. He next describes the two new developements in the manufacture of cast-iron pipe-both along the lines of centrifugal casting. The advantages and disadvantages of both processes are presented in some detail. Finally, statistics on the production of pipe in the United States at the present time are given, as well as the plants-and their capacities-so far as these are situated in the South. No SINGLE branch of the foundry industry has been brought to a production basis of huge tonnage, low manufacturing cost, and producing material of a remarkably high quality, as has the making of cast-iron pipe. The pipe shop is an excellent illustration of the fact that repetition work in specialties leads to mechanical equipment and manipulation that lower production costs to an. astonishing degree. Hence cast-iron pipe, in dull times, has been sold at a few dollars a ton over the selling price of the pig iron used. On the other hand, these same pipe, shops make fittings .of many varieties, and in much smaller quantities, where the cost is high, and when pipe may be sold, say, at $50 a ton, the fittings on the same shipment will be sold for nearly double that price. The history of pipe-making, in the United States, is a checkered one the mortality of plants is high and, from the nature of the industry, plants must be large to live. In spite of the fact that the best processes must be used to turn out this rather strict specification material, pipe is easy to make and a pipe plant is more of a tonnage mill than the really high-class specialty foundry it should be. Every time, therefore, that the demand for pipe is strong new shops spring up, only to close when the demand has ceased, but the financial damage to the more permanent plants has been done. Both the South and the North have had abundant experiences of this kind, and when recently a northern Public Service Corporation gave its order to France, the pipe plants thus adversely affected were content to have this occur rather than see-a plant started to supply the surplus demand.

Jan 9, 1924

By Newell Alford

FORECASTS of future timber consumption in soft-coal mining are handicapped by; the lack of adequate experience records for estimating properly the timber requirements of the industry. Data were obtained from plants where records are kept or from operators who collected the information and to these were added FIG. 1.-GROWTH OF POPULATION IN UNITED STATES, FROM PEARL'S ?BIOLOGY OF DEATH." composite figures for the continental United States in 1905 and 1919 1 and for central and. Western Pennsylvania and for Illinois in 1922.2 The result, representing slightly over 928;000,000 net tons, is shown in Table 1. Some of the companies furnishing data were unable to segregate the timber into classes of use but for those who did, Table 2 shows the board feet of posts and cross bars used per ton of coal mined and the, percentage of the total timber consumed that was used in roof support. The wide variation in amounts of timber per ton of coal mined is the result of

Jan 5, 1924

By Heber Cole

THE gypsum industry of Canada, like all others connected with the construction business, has felt the full effect of the depression during the past few years, and sales of its products have been greatly curtailed. The year 1934, however, saw a decided turn for the better and a gradual but steady improvement is noticeable in all its branches. In many ways the depression has been a blessing in disguise to the gypsum industry; during the years from 1926 to 1930, demand increased so rapidly that companies were forced to expand and often new apparatus and machinery were placed in operation regardless of expense, or plants already existing were taxed to their limit and forced to keep running with the minimum amount of repairs. The depression, therefore, has really given the industry what might be called a breathing spell, in which it has had time to take stock of its position, to reduce its costs of production, to devote more serious attention to the quality of its products, and to con-solidate its operations into a smooth working whole, which as conditions improve will enable it to meet the demands of the trade with more varied products of a quality hitherto unattained. Progress in the gypsum industry, however, has not been confined to the years of the depression, for some of the greatest advances occurred under the spur of increased demand for its products by the building trade. The purpose of this paper is to review briefly some of the out-standing trends in the development of the gypsum industry in Canada during the past 10 or 12 years.

Jan 1, 1935

By Thomas T. Read

Readjustment of the industrial world to a peace basis after more than 4 years of war will involve many fundamental and far-reaching changes that cannot as yet be clearly foreseen or definitely provided for. Such problems may be subdivided, in the vocabulary of war, into those involving material and those centering about personnel. Of the two, the latter group is the more difficult and obscure, as the factors involved are less clearly understood and the methods to be followed are not yet tested and standardized. When it is said that the market is weak, stocks large, and demand light, every business man understands clearly what is meant and what course he should adopt to adjust himself, so far as possible, to such conditions. But when it is said that the rapid spread of Bolshevism in Europe is a danger to industrial organization in this country, it is difficult to have any assured sense that all that the statement may mean is clearly understood or that the means to be followed to meet such a situation are definitely known. Since Bolshevism is primarily a mental phenomenon and since the rupture it brings about in industrial organization should be prevented, if possible, it is my purpose to restrict this discussion of the activities of the Committee on Industrial Organization to some of its mental aspects, as the chairmen of the sub-committees, from their special knowledge of their own fields, can best set forth recent progress in the lines with which they are especially concerned. The first requisites of success in industrial organization, as in the biological organism of which it is the social counterpart, are unity of purpose and coordinated activity. Typical good and bad examples of this' are the relative parts that the United States and Russia have played in the great war. These two factors are primarily mental, and it is not difficult to view the mental aspects of all problems of industrial organization as the most important ones. Unless we can attain unity of purpose and coordinated activity in industry, the provision of comfortable homes at reasonable rent, the assurance of steady work at good wages, the elimination of industrial accidents, and provision against want in old age or in case of disability will have brought us no nearer to our real goal.

Jan 1, 1919

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' 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 'idea1 gases,' 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 'ideal' 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