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By Lars Rossemyr, Terkel Rosenqvist

The equilibrium Mn + 2 IiCl = MnCl2(g) + H2 has been studied at 1090°C for pure manganese and for Mn-Si alloys. For this reoction a standard free energy of Fo1363, = - 19,700 i 300 col ioas found. Combined with other thermal data, the standard free energy of the reaction Mn(s, ß) + Cl2 = MnCl2(g) was derived: Fo=- 56,140 + 9.78 T log T - 40.10 T For the formation of the various manganese silicides the following free energies were obtained. 5 Mn + 3 Si - M1z5Si3 ?F°1363 = -41,500 i 1500 cal Mn + Si - h.lnSi ?F°1363= -10,000 i 500 cnl Mn + 2 Si = MnSiz ?F°1363= -11,500 ± 500 cal In the search for a method suitable for the study of thermodynamic properties of certain alloy systems, it was found that the heterogeneous equilibrium between the alloy and a gas mixture consisting of hydrogen chloride, hydrogen, and volatile metal chlorides has considerable advantages. In addition to giving thermodynamic information about the alloys, such measurements may be used to derive thermodynamic data for the volatile metal chloride itself. The present paper gives some results which were obtained for manganese silicides and manganous chloride. Similar studies are presently being carried out for the iron silicides. The phase diagram of the Mn-Si system is rather well known,' but no information exists to the authors' knowledge about the thermodynamic properties of manganese silicides or about the chemical activities in molten Mn-Si alloys. At elevated temperature, manganese may react with hydrogen chloride according to the equation: Mn(s, ß ) + 2 HC1 = MnC1, (g ) + H2 [ 1] with the equilibrium constant The value of K, may be determined from measurements of the gas composition in equilibrium with pure manganese. When this value is used in connection with measurements on manganese alloys, the chemical activity of manganese in the alloy may be derived. Initial calculations showed that around 1000" to 1200°C the equilibrium constant K1 has a value of a few thousand, i.e., the reaction is shifted far to the right. In order to study this rather unbalanced gas composition, a flow method was used in two slightly different modifications. For all experiments with manganese silicides and for some experiments with pure manganese the apparatus shown on Fig. 1 was used. A bed of the metal or alloy was placed in a tube furnace. The refractory tube had an internal diameter of 14 mm and the bed was 75 mm long. Electrolytic manganese of high purity and silicon, 99.95 pct Si, were used as raw materials. All alloys were prepared by melting weighed amounts of the elements in a high frequency induction furnace in argon atmosphere. The melting was done in a silica crucible which was placed inside a graphite shell. The alloys were crushed to - 10 +40 mesh and analyzed chemically. Also, for the pure elements, the same size fraction was used. A controlled gas mixture of purified hydrogen and from 3 to 12 pct HC1 was passed through the bed where it reacted with manganese according to Eq. [I]. The volatile manganese chloride was collected in a condenser placed in the cooler part of the furnace tube. The gas mixture before and after the furnace was sampled and analyzed by absorption of

Jan 1, 1962

By E. G. Bailey

The bituminous coal industry faces a real problem, if it desires to retain the position in the power-generation field to which it is economi-cally entitled. More power is probably produced today for electrical energy, for steam-driven and steam-heating industries and processes, for transportation by rail, water, highway and air, collectively, than ever before, and yet the total bituminous coal production has decreased about 38 per cent, from 575,000,000 tons in 1926 to 357,500,000 tons in 1934. It is not the intention of the writer to recommend coal as a fuel for automobiles and airplanes, but rather to point to these forms of transpor-tation as being responsible in a very measurable degree for reducing the coal consumed by railroads. Petroleum products may still further reduce consumption of locomotive fuel through the extension of the use of Diesel-driven trains. Oil-burning steam-driven locomotives are replacing coal in some places, where railroads operating high-speed pas-senger trains are willing, temporarily at least, to pay a premium for the fuel, that is low in ash and produces less smoke and practically no cinders. In the navy and ocean-going passenger ships, oil is so firmly estab-lished, and has such definite advantages over coal as formerly fired, in steaming radius, in ease of bunkering, cleanliness, and reduction in firing labor, that very outstanding developments in the handling and burning of coal will be required in order to replace oil. For freighters on the Great Lakes, coal is the logical fuel, but there is great and immediate need of radical improvements in its use, else that market also may be lessened. It is not within the scope of this paper to discuss in detail bitumi-nous coal for either locomotive or marine use, but, rather, generation of power in stationary plants, consisting of electrical generating stations and that very large group of miscellaneous industrial plants, such as paper, rubber, textile, steel and other industries that use electrical, mechanical, and steam power, derived from either hydro or some form of fuel.

Jan 1, 1935

VARYING in thickness and in number from place to place, coal seams in the Canadian Rockies also range in pitch from nearly horizontal to vertical, sometimes with overturns. Over the entire coal-bearing area there are considerable differences of rank in coals of the same geological age, and there are marked differences in ash content and washability characteristics. Correlation of seams at mining operations within a few miles of each other has often proved impossible. These factors influence mining methods, and, of course, production results. The oldest coal formations of western Canada are of Lower Cretaceous age, as the carboniferous sediments are marine and contain no coal. Coal is also present in formations of Upper Cretaceous and Tertiary ages. The rank of coal varies from semianthracite in some operations in the Kootenay and Luscar formations of the Lower Cretaceous in the Rockies to lignite in the Tertiary fields of the Saskatchewan prairies. Fig. 1 shows the general extent of the formations.

Jan 8, 1954

By A. W. Jenike

A theory of gravity flow of bulk solids like ores, concentrates, coal is outlined and an example of design for unobstructed flow is given. Mass-flow and plug-flow patterns are defined and related to the geometry of the bin. The effect of these patterns on segregation, first in-first out flow, and caking is described. This paper is a report on the results from the AIME sponsored project "Flow of Bulk Solids" which was carried out under the author's direction at the Utah Engineering Experiment Station, University of Utah, during the period 1956-1962. The theory has been applied to the design of numerous industrial storage plants. A QUANTITATIVE METHOD OF DESIGN FOR FLOW There is hardly an industry which does not store and handle solid materials in bulk form. When the volume of the solids is large, gravity is invariably relied upon to cause the solids to flow out of storage, through channels and chemical reactors. Such materials as ore, coal, cement, flour, plastics, clay, soil, to which a general term of bulk solids is applied, flow by gravity or are expected to flow by gravity in thousands of installations and by billions of tons annually. The chemical and process industry depends on gravity flow of solids in process and out of storage. Mining relies on gravity flow in block-caving, in ore passes, as well as in storage and loading bins. Agriculture uses gravity flow in elevators, in feed plants, and in farm silos. In practice, satisfactory gravity flow is seldom attained. Such problems as doming, piping (rat-holing), lack of live capacity, segregation, deterioration in storage, harass industry. In spite of the universality of these problems, until recently, there has been no theory of solids flow, no method of predicting how a solid would behave, and how the channel, bin, or hopper should be designed. In the late nineteen forties and early fifties, the theory of plasticity came of age and simultaneously the computer became widely available. These two factors permitted the development of a theory of flow of bulk solids. The work was conducted during the years 1953-1961. In conjunction with the development of the theory a method to measure the flowability of solids was also developed1-7 and the theory was ap-plied to the design of ore pockets, storage plants,16 chemical reactors and adsorption columns. A comprehensive report of this work is given in a previous work." THEORY OF FLOW The most important question which a theory of flow has to answer is: what conditions need to be satisfied for a given solid to flow uniformly and without obstructions through a channel? First of all, the following observations are made:

Jan 1, 1967

By B. M. Larsen, K. Heindlhofer

THIS paper describes a relatively simple electrical apparatus that, through the close analogy between the flow of heat and of electricity, enables one to solve quickly and with satisfactory accuracy many complex problems in heat flow. This device, developed in 1935, has proved especially useful in the solution of certain practical problems relating to the design and efficiency of regenerators for an open-hearth furnace or coke oven, yielding within a few hours information that would take weeks or even months to acquire by mathematical1.2 or experimental3 methods of comparable accuracy. Its description now is prompted by growing interest in such analogues, as shown by several recent papers.4.5 The analogy between flow of heat and of electricity appears to have been recognized first by Maxwell who, in his famous Treatise on Electricity and Magnetism (1881) says: The analogy between the theory of the conduction of electricity and that of the conduction of heat is at first sight almost complete. If we can take two systems geometrically similar, and such that the conductivity. for heat at any part of the first is proportional to the conductivity for electricity at-the corresponding part of the second, and if we also make the temperature of any part of the first proportional to the electric potential at the corresponding point of the second, then the flow of heat across any area of the first will be proportional to the flow of electricity across the corresponding area of the second. .. Thus, in the illustration we have given, in which flow of electricity corresponds to flow of heat, the electric potential to temperature, electricity tends to flow from places of high to places of low potential, exactly as heat tends to flow from places of high to places of low. temperature He noted, however, that this analogy is restricted: ... there is, however, one remarkable difference between the phenomena of electricity and those of heat. Suspend a conducting body within a closed conducting vessel by a silk thread, and charge the vessel with electricity. The potential of the vessel and of all within it will be instantly raised, but however long and however powerfully the vessel be electrified, and whether the body within be allowed to come in contact with the vessel, or not, no signs of electrification will appear within the vessel, nor will the body within show any electrical effect when taken out. But if the vessel is raised to a high temperature, the body within will rise to the same temperature, but only after a considerable time, and if it is then taken out it will be found hot, and will remain so till it has continued to emit heat for some time. The difference between the phenomena consists in the fact that bodies are capable of absorbing and emitting heat, whereas they have no corresponding property with respect to electricity. According to this statement the application of the analogy would be limited to problems of steady flow that do not involve heat-capacity effects. In spite of this

Jan 1, 1945

By F. H. Kihlstedt

THE Larap iron deposits, 125 miles east of Manila, are the biggest high-grade iron deposits in the Philippines, and have in seven years produced nearly 4 million tons of 6o per cent ore. Magnetic surveying followed by churn and diamond drilling cheaply developed a score of million tons. The ore zone is a wedge of metamorphic rocks in fresh, Miocene sediments overlain by agglomerates, which seem to have filled a river valley eroded in the sediments. A mild overthrust of the competent agglomerates crumbled the shale in front. Solutions gradually turned it into more competent hornfels and deposited pyrite, then magnetite and pyrite in the pores. As the temperature rose large bodies of magnetite with some pyrite were deposited by replacement and in open cavities in tensional areas of overthrust shears. At still higher temperature magnetite and calcium-magnesium silicates formed other bodies in similar cavities, and finally the thrust zone was invaded by syenite porphyry, causing high-temperature alteration products. Possibly, as temperature abated, more high-grade ore was deposited. The complicated faulting indicates dynamic, chronological and spatial changes of mineralization rather than zoning in a static system. Noncommercial copper, molybdenum and some gold accompanied the iron mineralization. In the thirties the Philippines gained a justified reputation as a country of considerable mineral wealth. Traces of Chinese workings show that these earliest travelers and traders had in a small way exploited the latent gold resources in the Islands. The Spaniards continued this for centuries, but did not succeed in establishing any steady mining industry. Modern technology was required to get it started. The rapid development in the last decade before the war got its impetus from several financial factors, the return to sugar growers of previously collected taxes, the influx of Spanish capital during the civil war in [ ] Spain, the influx of Chinese capital when the Japanese started their "China incident," and others. Directly or indirectly much of this capital reached the mining industry; in particular, gold mining. Out of the turmoil of an exceptional mining boom emerged a sufficient number of good and well managed gold properties to send the production to a level above that of any single state in the United States at the time. Other ore deposits besides those of gold also received their share, and for a country without any heavy industries at

Jan 1, 1946

By S. Paul Lindau

THREE years ago it was decided by the management to granulate the matte that is produced in the smelter of the St: Joseph Lead Co. at Herculaneum, Mo., thereby doing away with a large amount of labor in handling the matte and in subsequent crushing. On Mar. 1, 1915, the granulator was put in operation and up to Jan. 1, 1916, 18,735 tons had been, granulated. The four blast furnaces have a daily output of about 280 tons of pig lead and 100 tons of matte assaying about 11.0 per cent. Pb. It is expected that projected improvements in roasting methods will eliminate more sulphur from the charge, and cut down the matte-fall, to about one-half of the present figure. The blast furnaces are tapped into movable forehearths or settlers, 6 ft. by 4 ft. by 22 in., the slag overflowing into 27-cu. ft. slag cars which are hauled to the clump by electric locomotives. Previous to the adoption of granulation, the matte was tapped from the forehearths into small slag pots which were dumped after cooling. The matte cakes were broken with sledges, and transported to the crushing plant for fine crushing and screening. Here the matte was reduced to ¼ -in. size before being fed to the roaster bins.. A Wedge and a Holthoff mechanical furnace are used for preroasting before sintering on the Dwight and Lloyd machines. The matte is returned to the furnaces as an iron flux until the .gradually accumulating copper content reaches about 7 per cent., after which it is put aside to be concentrated in a small copper blast furnace, the resultant high-grade matte-being sold. When the matte does not settle readily from the slag, two settling devices are often used, the second one being a large catch-pot, which gathers any matte that may overflow from the forehearth, the slag then overflowing from the catch-pot into the slag cars. When full of matte, the catch-pot is removed, allowed to cool, and the contents broken and crushed.

Jan 10, 1916

By Alfred H. Bell, George V. Cohee

In 1939 Illinois produced 94,302,000 bbl. of oil—almost three times the amount of oil produced at the peak in 1908, when development in the southeastern Illinois field was at its height (Fig. I). It represents nearly a fourfold increase over the 24,075,000 bbl. produced in 1938 (Table 6). This rapid increase in oil production in Illinois is largely due to development in the Salem and Louden fields (Table I). During 1939 daily production for the state increased from 135,000 to 332,572 bbl. A notable increase in production for 1940 is expected as a result of the drilling of the Devonian limestone in the Salem and Centralia fields,

Jan 1, 1940

By Alfred H. Bell, George V. Cohee

In 1939 Illinois produced 94,302,000 bbl. of oil—almost three times the amount of oil produced at the peak in 1908, when development in the southeastern Illinois field was at its height (Fig. I). It represents nearly a fourfold increase over the 24,075,000 bbl. produced in 1938 (Table 6). This rapid increase in oil production in Illinois is largely due to development in the Salem and Louden fields (Table I). During 1939 daily production for the state increased from 135,000 to 332,572 bbl. A notable increase in production for 1940 is expected as a result of the drilling of the Devonian limestone in the Salem and Centralia fields,

Jan 1, 1940

By W. A. Cole, E. L. Derby, J. F. Wolff

Exploration of Lake Superior iron ores is done principally by drilling. The soft iron ores are churn drilled and the harder ores are diamond drilled. The churn drill used is the Mesabi type and its operation should be described as "water jetting." The drill rods are washed down by the combination action of the water jetting from the bit at the lower end of the rods and the churning motion given the line of rods. The water, which is forced down through the rods, comes up between the wash rods and the casing, bringing the choppings to the surface. It is caught in three or more barrels, each of which has a stoppered hole 8-10 in. from the bottom. These barrels are successively filled, allowed to settle, and drained to the hole, until the desired depth is drilled. The sediment from each barrel is transferred to a settling tub in which it is allowed to settle; the water is then drawn off and the wet sample is collected and dried. The number of barrels used depends on the character of the ore. For example, when drilling sandy ores, all the wash water is caught and settled for the proper length of time without refilling any of the barrels. Thus, the sediment held below the stoppered hole in any one barrel is not disturbed. The casing is kept as near the bottom of the hole as practicable to prevent the caving of the hole from jeopardizing the sample. While the casing is being driven down and the hole is being washed clean after casing, the return water is not run into the sample barrels. In exploratory work in the harder formations, where the diamond drill is used, the sample comprises both core and cuttings. The care given in handling and preserving the core depends on the importance that may be attached to certain characteristic strata in different formations. The following instructions for the care of core samples are issued by the Ogle-bay Norton Co. for diamond drill work done for them on the Gogebic Range of Michigan:

Jan 1, 1925

By Robert H. Richards

Jan 1, 1897

By R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-C and Fe-Ni solid-solution alloys has been investigated at 25°C. It is found that the rate of solid-solution strengthening is dependent upon the strain at which the yield stress is measured, the macroyield stress being much more concentration-dependent than the microyield stress. In fact the addition of nickel does not lead to any increase in the microyield stress of iron. The primary effect of increasing the carbon or nickel content is to increase the slope of the stress-strain curve in the microyield region; this effect has been correlated, by means of transmission electron microscopy, with a decreased ability of the dislocations to cross-slip. It is concluded that the Mott-Nabarro theory is a good description of true solid-solution hardening in these and other iron-base alloys. A.LL theories of the solid-solution strengthening1-4 indicate that the flow stress of an alloy increases both with solute concentration and "misfit" between the solvent and solute atoms. The functional relationship between strength, solute concentration, C, and misfit depends upon the particular theory. Mott and Nabarro1,2 and Schoeck and Seeger3 both predict a linear increase in strength with concentration, while Fleischer4 indicates that the strength should be proportional to C1/2; there are in the literature experimental observations to support both these compositional dependencies.1'8 The experimental evidence used to support the theories is the change in macroscopic yield stress (strain, e, = 10-3) with composition. However, recent investigations have revealed that solid-solution strengthening in a Cu-Al single crystals7 and in Fe-V polycrystal-line" alloys depends upon the strain at which the flow stress is measured; a flow stress in the microplastic range (e = 10-6 to 10-5) is much less concentration-dependent than the macroyield stress. Since the theories of solid-solution strengthening are concerned in particular with the stress to move a dislocation in a dislocation-free matrix, they should only be compared with microyield-stress data; it will be shown that in a material deforming homogeneously the microyield stress (e = 10-6) is approximately the stress to move through the matrix those dislocations which have been nucleated by stress concentrations such as particles or grain boundary ledges.9-11 In contrast, the macro-yield stress is more complex in that it is affected by several phenomena: dislocation multiplication, dislocation interactions, and the ease of propagating slip across grain boundaries. For example, it is experimentally observed that when long-range order12'13 or solute effects10 restrict cross alip the grain boundary

Jan 1, 1967

[Officers and Committees of the Society of Petroleum Engineers 1 Officers and Staff of the AIME 2 Officers of AIME Sections Predominantly Petroleum in Membership 3 Society of Petroleum Engineers By-Laws 5 Alphabetical List of Members 9 Geographical List of Members 110 List of Members by Companies 127 Advertisers' Index 137]

Jan 1, 1961

By S. R. Goodman, Hsun Hu, R. S. Cline

The quenching technique has been used to study phase relations in the composition area 2FeO.SiO2-FeO-SiO2-MnO.Si02-ZMnO.SiO2 of the system iron oxide-manganese oxide-silica under strongly reducing conditions such as exist in a gas mixture consisting of equul parts of carbon dioxide and hydrogen. Liquidus and solidus temperatures of most mixtures in the composition area studied are in the range of 1173° to 1345°C. EQUILIBRIUM relations existing among the oxides of iron, manganese, and silicon are of particular interest in two areas of steelmaking: slags and ingot inclusions. Mixtures of these oxides represent about 90 pct of the slag in the acid steelmaking process, and so dominate the chemistry of the whole refining process. These constituents also play an important role in the early slags existing at the time of the "lime boil" in the basic open hearth process. If these slags are liquid, they "wet" the lumps of lime rising from the bottom of the bath, and react with them. A liquid slag rich in CaO is then formed at the very beginning of the refining. Because the temperature is still low, all conditions for a good dephosphoriza-tion are fulfilled at this stage of the operation. Metal deoxidized with ferromanganese or silico-manganese is likely to contain, as inclusions, phases made up from among the oxides of iron, manganese, and silicon. A knowledge of stability relations existing among the phases present in this system, therefore, enables one to predict the hardness of the inclusions encountered. Moreover, because the shape of the inclusions in steel has a profound influence on the physical properties of the metal, it is important to establish whether or not the oxidic material is present as liquid or crystalline phases during heating and rolling of the steel (-1150 to 1350°C). A knowledge of melting relations in synthetic mixtures of iron oxide, manganese oxide, and silica will give a clue to these problems. Methods for determining such relations and the results obtained are described iln this paper. I) PREVIOUS WORK A number cf previous studies have dealt with the three "binary"* systems bounding the system iron oxide-mangar,.ese oxide-silica. The system iron oxide-silica was studied by Bowen and shairerl in 1932. Their data were obtained by equilibration of mixtures in contact with metallic iron. Phase relations for the system iron oxide-silica ill atmospheres of different oxygen pressures car1 be derived from data on the system FeO-Fe2O3-SiO2 as determined by Muan.2 The diagram shown iri Fig. l is a section of this system in an atmosphere of CO2 and H2 in ratio 1:l. The system manganese oxide-silica has also been the subject of several investigations. Most of the early studies suffered from a lack of proper control of the atmosphere under which the equilibrations were carried mt. Phase diagrams for the system at two well defined levels of oxygen pressures have been determined recently. Glasser3 determined stability relations in an atmosphere consisting of carbon dioxide and hydrogen in ratio 5:1, diagram Fig. 2, and Muan4 studied phase relations in the system in air.

Jan 1, 1962

By J. P. Witherow

The blast-filmace plant of the Crozer Steel and Iron Company was built under contract by Witherow & Gordon, of Pittsburgh, Pa. The furnace is 70 feet high by 16 feet bosh, tunnel-head 12 feet 8 inches, and hearth 9 feet in diameter. The columns are 20 feet high above furnace level, below which they extend 2 feet. The shell is 23 feet diameter at bottom and 19 feet at top. The plate iron is 3/8 inch at bottom, and tapers to 1/4 inch, the top ring being 5/16 inch.

Jan 1, 1884

By Sylvan Z. Beer

The factors that determine the yield and crystal size in the two-temperature synthesis of A lp were examined. Low yields and small crystals were associated with low temperatures and pressure. Attempts to grow large crystals in the critical and supercritical region of phosphorus were unsuccessful. Crystal size increases markedly at elevated temperatures. Crystals grown at temperatures as high as 1450° C fluo-resced, under uv excitation, at energies close to the estimated band gap of about 2.4 ev, while crystals grown at lower temperatures tended to fluoresce in the red region of the spectrum. Those grown in the supercritical region showed no ALP fluorescence. Heating the high-temperature-grown ALP under vacuum greatly increased its fluorescence efficiency and moved the emission peak to higher energies. I HE III-V compounds, with few exceptions, have been prepared by the two-temperature method. In its classic form this technique is applicable to closed systems where at least one of the components, in this case the column V element, is a liquid or a solid with a high vapor pressure. One advantage of this method over flow systems is in its simplicity. In addition, because it is a closed system, it can, under the circumstances to be described later, be run at higher pressures of the volatile species than in flow systems. In instances where the III-V compound is soluble in the parent III metal to about 1 mol pct or higher, solution growth can be made to take place by slow cooling. This, for instance, is one way in which single-crystal GaP1 and Inp2 have been grown. Initial attempts to synthesize and grow A1P by this technique were not too successful; the yield was low and the crystals obtained were exceedingly small. The conditions required for improving the yield and growth by this technique were, therefore, sought. Two obvious conditions which could be controlling were examined. These were the temperature of the aluminum and the pressure of the phosphorus. The range of temperatures studied extended from about the melting point of aluminum, 660° to about 1450°C. The latter is dictated by the vapor pressure of aluminum which reaches about 1 Torr at that temperature and the limitations of the materials of construction as described in the next section. The pressure range of interest covers from below 1 atm to above the critical pressure of phosphorus, 82.2 atm. EXPERIMENTAL The Temperature of Aluminum as a Variable. A series of experiments were run in the conventional two-temperature manner. All refractories and quartz were dried by heating at 800° to 900° for a minimum of 24 hr, and usually much longer, before use. The aluminum

Jan 1, 1969

By C. E. Sims

THE carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example,, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath. The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner without reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature. For the carbon-oxygen reaction C + 0 [=] CO this is expressed simply as [ ] where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1947

By R. Littlewood

The concepts of "redox potential" and "oxide-ion activity" are suggested as measures of the fundamental slag properties of interest to the extraction metallurgist. Thermodynamic data for single oxides are presented graphically in these terms and a method of expressing desulfurization of steel in electrochemical terms is indicated. The application of the theovy to mixtures of oxides (slags) is discussed and the redox potential is shown to provide a link between all the redox equilibria in a slag-metal system. In particular, the redox potential of the slag, its basicity, and the oxygen partial It is now generally recognized that slags are mixtures of polymeric anions of silicates, aluminates, phosphates, and so forth, neutralized by cations. However, conventional thermodynamic treatments of slags have almost always been in terms of activities of the pure component oxides (e.g., SiO,, CaO, A1203, and so forth), which are known not to exist as such in slags. While this type of empirical treatment is perfectly acceptable and provides a rigorous and self-consistent way of considering thermodynamic properties, it can give little guide to the structure of slags, since its very nature ig- pressure are closely connected. Direct deternzination of these by electrode-potential measurements is possible. Literature calculations of ion activities in the system Ca0 -Fe0-SiO,/molten iron are used to evaluate redox potentials, which are shown to correlate with data on sulfur partition in the system. In addition to its application to equilibrium conditions, an electrochenzical approach to slag-metal reactions might provide a basis for new methods of studying the kinetics of these reactions and for plant-control instruments in the pyrometallurgical industries. nores such complications. Recently, the thermodynamic properties of some slags have been successfully interpreted in terms of activities of anions of varying degrees of complexity. (While these have been successful curve-fitting exercises, there is no direct implication that the anions used in the models are necessarily the ones which actually exist in slags.) The success of these ionic thermodynamic treatments is encouraging but a complete picture of slag structure is still a long way off. What is needed is a complete knowledge of the values of stability constants for all reactions in slags of the type:

Jan 1, 1965

By W. N. Lacey, R. H. Olds, B. H. Sage

Samules of liquid and gas were obtained from the primary separator of a well in the Paloma field. The volumetric properties of the samples and of six systematically chosen mixtures of the samples were experimentally determined at 100°, 190°, and 250°F. at pressures up to 5000 lb. per sq. inch. From these data the influence ,of pressure and temperature upon the composition and specific volume of the bubble-point liquid and of the retrograde dew-point gas was established, The formation volumes and gas-oil ratios of the rnixtures investigated were calculated on the basis of the plant-product oil, which is defined as the isobutane and less volatile portion of each mixture. The results are presented in graphical and tabular form. The volumetric behavior of the mixture corresponding to that produced by the well at the time of sampling was determined for 235ºF., the reported reservoir temperature, by graphical interpolation of the experimental data with respect to composition and temperature. The results indicate that the well-production mixture probably existed as a gas at its retrograde dew point under the conditions of temperature and pressure believed to prevail in the producing zone at the time of sampling. The effect upon the phase behavim occasioned by the omission from the well-production mixture of certain components of intermediate molecular weight was investigated. In the first case, all of the isobutane and 11-butane, and substantially all of the iso-pentane, were removed from the mixture of trap samples corresponding to the well production. In the second case, all the propane, isobutane and n-butane, and substantially all of the isopentane, were removed. Both modifications led to considerable increases in the retrograde dew-point Pressure at 235ºF.; an increase of 558 lb. Per sq. in. above that of the unmodified well-production mixture in the first case, and an increase of 1208 lb. Per sq. in. in the second. It was concluded that the material? remaining after the removal of certain components of intermediate molecular weight could not be injected back into the reservoir in the saqe proportion in which they were produced without entailing appreciable loss of liquid material through condensation within the formation. Introduction Under the usual conditions of production practice, petroleum arrives at the surface of the earth in a physical state considerably different from that in which it existed in the underground reservoir. The relative rates of production and the properties of oil and gas measured at surface conditions do not constitute, in general, even a qualitative description of the fluids existing in the reservoir. The estimation of reserves and the attainment of optimum efficiency with regard to rate, quantity, and cost of production require accurate data concerning the physical properties of petroleum throughout large changes in pressure and temperature. Many schemes have been devised for predicting the behavior of propane, as it is encountered in nature? but the experimental work upon which these predictions are based has not, for the most part, been extended to the higher pressures that occur in practice, nor do these methods permit, as yet, the estima-

Jan 1, 1945

THE turn of the century was marked by the appearance of a series of greatly important pieces of research that became the foundations of modern physical metallurgy. It is, of course, some- what misleading to ascribe the growth of a science, or a branch of engineering, to the work of a few men, as it is to write history generally in terms of great men, for this approach neglects back- ground development, and tends to overemphasize the importance of immediately subsequent events; the correlative and steady growth of the basic sciences added to the resources of the new science of metals--developments in basic science .years later were to appear in their application to metal systems. Yet it is useful to emphasize the importance of these relatively few pieces of research. THE PHASE RULE The work of Willard Gibbs on heterogeneous equilibria, which included the derivation of the phase rule, was published obscurely in the journal of the Connecticut Academy.30 Unearthed by the German physical chemists (evidently by van der Waals, to use Ostwald's phrase, "aus dem staubigen Fundort"), its importance to the study of alloys was pointed out by Jüptner31 and by Le Chatelier; its application to polycomponent systems, and to metal systems in particular, was developed by Rijn van Alkemade (1893), by Le Chatelier;8a and especially by Roozeboom (1899-1900). The work of Raoult on the depression of the freezing point by solutes led to the study of the phenomenon in amalgams and shortly to metal systems. Work was done, by Roberts-Austen and others, on the initial freezing temperatures of binary alloys-the liquidi, data applicable to Raoult's work. Van't Hoff in 1890 had pointed out

Jan 1, 1948