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By J. E. Hilliard, H. E. Cook

It is shown that for systems having a miscibility gap the spinodal composition (c,) in the vicinity of the critical temperature (Tc) is related to the equilibrium composition (c,) by where cc is the critical composition. This expression is exart for the limit T — Tc and is a good approximation down to (T/Tc) - 0.9. If the miscibility gap meets the composition of the pure components THE recent theoretical treatment by cahn1,2 on spinodal decomposition of solid solutions has revived interest in methods of estimating the chemical spinodal, * i.e., the locus on a binary phase By use of the appropriate expression, the spinodal can be drawn on the Phase diagram almost by inspection with an accuracy comparable to that of lengthy calculations in which a free-energy function is fitted to the phase diagram. Satisfactory agveemenf is also obtained with spinodals comPuted from experimental free-energy curves. where G is the Gibbs free energy of the homogeneous solution and c the atomic fraction of component 2, the derivative being evaluated at constant temperature (T) and pressure (P). (These subscripts will hereafter be omitted from the partial derivatives.) If experimental measurements of G as a function of c and T are available in a single-phase region above the spinodal, then these can be extrapolated to obtain a series of metastable free-energy isotherms in the two-phase region, and from these isotherms a series of spinodal compositions can be calculated. Because the value of is very sensitive to experimental errors, an elaborate analytic procedure is required for

Jan 1, 1965

By R. M. Goldhoff, J. W. Spretnak, R. Speiser

IT has been observed by Grange and Garvey' that the homogenization of boron-treated steels could lead to complete elimination of the hardenability effect caused by boron. The experimental conditions leading to this conclusion involved the heating of steel specimens with and without boron at 2350°F for 24 hr. To prevent oxidation and decarburization, the specimens were encapsulated under vacuum in silica tubes. This observation of permanent deterioration of boron effect was noted in both a 0.63 pct plain carbon steel and a 0.25 pct C low alloy steel, both of which had been treated with ferroboron and homogenized at 2350°F for 24 hr. In another series of boron-treated steels which had been homogenized for shorter times, the effect was to reduce, but not completely eliminate, the boron effect. Under these circumstances, it was presumed that longer heating times would cause permanent deterioration of the boron effect in this series of steels also. Since the characteristic grain boundary constituent could not be formed in any of these steels after homogenization, it was concluded that possibly boron was being converted into an ineffective form through chemical combination resulting from prolonged heating at high temperatures. Assuming the validity of this observation, a series of experiments to establish the relationship between temperature of homogenization and kinetics of deterioration was contemplated. Initially an attempt was made to reproduce the results just described. For this purpose commercial lots of AISI 8640 and AISI 86B40 steels were used. The analyses of these steels appear in Table I. Hardenability evaluation was on the basis of the hardness of normalized sections. Grange and Garvey' pointed out that these steels are air hardening to some extent and such a technique can be used. For these tests the specimens were held for 20 min in a salt bath at 1600°F and then cooled in still air. Several evacuated silica capsules containing pairs of the test steels were made up and heated for 24 hr at 2350°F. A number of failures occurred among these capsules, but evaluation of the specimens successfully treated indicated a complete deterioration of the boron effect. However, examination of the surface of the treated specimens showed that some reaction, probably with the silica tube, had taken place, since none of the specimens was bright. One further test was made at 2350°F for 12 hr, using a pair of specimens wrapped in tantalum foil prior to encapsulation. These specimens appeared bright after treatment, and their hardenability evaluation showed that no deterioration had taken place. Since these steels are extremely sensitive to de-boronization at high temperatures and particularly at long times of holding, the experimental observations raised some doubt as to the real occurrence of the permanent deterioration effect. To resolve this question an experiment was undertaken in which the high temperature portion of the treatment was completed in vacuum. For this purpose a molybdenum wound resistance furnace capable of maintaining good vacuum was used. All the pertinent accessories to this furnace were machined from molybdenum stock in order to withstand the high temperature involved in the experiment. With this equipment a temperature of 2400 °F was obtained and held under a pressure of 5x10-" mm Hg for 24 hr. A specimen of each of the two test steels was suspended in the furnace and both were heated simultaneously. Temperature was measured with a standardized Pt—Pt-13 pct Rh thermocouple, whose millivoltage at 2400°F was extrapolated from the standardization equation, good up to 2200°F. The complete evaluation of these specimens is shown in Table 11. The hardness values attained by each steel after normalizing, both before and after the prolonged high temperature treatment, remain the same. A microscopic study of the decomposition products present in the microstructures of specimens at various points in the heat treatment correlated with the hardness values observed. It seems that no permanent loss of boron hardenability effect occurs, at least in these Grainal-treated steels, when deboronization is circumvented. Acknowledgments This work was conducted under the sponsorship of the Aeronautical Research Laboratory, Wright Air Development Center, under Contract No. AF 18(600)-94, and their support and permission to publish is gratefully acknowledged. A note of thanks is also extended to the Republic Steel Corp. for supplying the materials used in the work. References ' R. A. Grange and T. M. Garvey: Factors Affecting the Harden-ability of Boron Treated Steels. Tro.ns. ASM, 1946, vol. 37, p. 136.

Jan 1, 1957

THE transformation, in a sample of levitation melted iodide titanium, has been studied with a Leitz hot-stage microscope. The specimen was etched in HF:HNO3: glycerine, (1:1:2) giving a structure shown in Fig. 1, and was then heated at approximately 5OC per min. At 870°C (±5OC) the etching product disappeared, the a-grain boundaries showed in relief, and some new grain boundaries (presumably of ß) appeared (Fig. 2, see arrow). Some evidence of ß-grain growth is indicated by the apparent longitudinal movement of a ß-grain boundary shown in Figs. 2 and 3 (see arrows). The specimen was later heated to 1000°C and then cooled at 2°C per min. At 845°C rumpling of the surface was first noticed, Fig. 4, and continued at constant temperature. The photomicrograph reproduced in Fig. 5 was taken 6 sec after Fig. 4, at 845°C. Fig. 6 shows the structure after cooling to room temperature. The room-temperature structure, showing a rumpled surface has been observed by previous investigators.' These structures presumably indicate a sheer transformation ß - a, athermally nucleated, but capable of isothermal progression.

Jan 1, 1960

By C. C. CONCANNON

POTASH is an essential. It is necessary as an ingredient in fertilizers or as a plant food, and certainly one of the great problems, and one of increasing gravity, is the maintenance of agricultural fertility that we may have adequate food supplies. When one thinks of potash one thinks of Germany. The first and most important deposits of soluble potash salts were found in Germany, and it was through Ger- man research and the application of a highly developed knowledge of chemistry that the value of these deposits was recognized and appreciated in the field of agricultural fertilization. The Germans knew that they had something of great value in their potash resources, not only because of the advantage derived from the extensive use of it in their own intensive farming operations at home, but also because of the pressing need for it on the part of other countries. Appreciating the economic value of this in international trade, they fostered the industry to the fullest extent and devoted much attention to well organized propaganda designed to bring out the essential need for potash of German origin throughout the world. Thus every one came to believe that potash was an essential commodity of only German origin and as such it held an extraordinary position in world trade prior to 1914.

Jan 1, 1926

By AIME AIME

WITH a brilliance undimmed by hard times, the annual dinner on Wednesday evening, Feb. 17, was a complete success. More than 600 members, friends and ladies gathered early and filled the anterooms of the grand ballroom of the Commodore Hotel, while the president's reception was in progress, and then at the sound of the gong and with the music of the orchestra, rising above the happy din of conversation thronged to their seats at the tables. Following the "potage Ambassadeur"-probably to eliminate a very real hazard-the usual toy balloons appeared and a gay and lively scene, punctuated by multitudinous explosions, ensued, as the hundreds, of variously colored spheres bounced yon and hither until their gaseous existence was ended on the glowing end of a cigar or cigarette. On the speakers' dais sat C. E. Beecher, Chairman Petroleum Division; J. Vipond Davies, representative of A. I. M. E. on the Alfred Noble Prize Committee; Corbin T. Eddy, Alfred Noble Prize recipient; A.' S. Tuttle, Vice-president American Society of Civil Engineers; W. C. Mendenhall, Director U. S. Geological Survey; George C. Bateman, representing the Canadian Institute of Mining and Metallurgy; Paul D. Merica, Institute of Metals lecturer and Chairman James Douglas Medal Committee; Champion Herbert Mathewson, James Douglas Medalist; Robert E. Tally; retiring President; G. Temple Bridgman, toast-master; Scott Turner, incoming President; F. W. Bradley, William Lawrence Saunders Medalist; Fred Searls, Jr., Chairman William Lawrence Saunders Gold Medal Committee; Arthur Notman, President Mining and Metallurgical Society of. America; Robert J. Grant, Director U. S. Mint; Landon F. Strobel, Chairman New York Section; Howard Scott, recipient of Robert W. Hunt Prize; George. B. Waterhouse, Chairman Robert W. Hunt Prize Committee; F. M. Becket, Chairman Iron and Steel Division; Ora E. Clark, recipient of the J. E. Johnson, Jr., Award; Richard Peters, Jr., Chairman J. E. Johnson, Jr., Award Committee; E. C. Bain, Howe Lecturer; Sam Tour, Chairman Institute of Metals Division; and H. Foster Bain, Chairman. Charles F. 'Band Foundation Committee. ' Each was heartily applauded when introduced by Mr. Bridgman, as was Mrs. Tally, who also made a bow. The toastmaster made graceful reference in introducing Mr. Strobel, to the large part the latter had taken in planning the meeting.

Jan 1, 1932

By Robert T. DeGavre

The $650 million financing for Into Ltd.'s Soroako nickel project is a story worth telling-not only because the project itself represents a significant achievement but also because there are certain important lessons that can be derived from our experience in financing the project. A critical appraisal of the methods and successes in the financing plan is presented in this article, in light of goals which Inco sought to achieve. A technical assessment of the project is not included, since Inco Ltd. has submitted a series of papers on this subject at the International Laterite Symposium as part of the 108th Annual Meeting of AIME in February 1979. Progress in developing and financing the project is encapsulated in the accompanying project factsheet.

Jan 3, 1979

By E. H. GRAFF

PREPARATION of mechanically loaded coal in mines where seams contain considerable impurities is a subject that requires careful consideration before machines are installed, unless provision is made at the tipple for its preparation. Conditions vary a great deal in the different seams, so much so that a mechanical loader may be unsuccessful in one seam and yet the same machine may make good in another where conditions are different. The effect of impurities in the coal seam on mechanical loading will also vary according to the thickness of the seam. In thin seams impurities will be more difficult to remove than from thick seams, as will appear later. For the past several years the New River Co. has done considerable experimenting with loading equipment and during this process has changed from one machine to another.

Jan 1, 1926

By R. W. Vieth, S. A. Bradford

THE orientations of tetragonal tin crystals are commonly examined by either the transmission Laue method or the back-reflection Laue method. The predominant planes and zone axes of the pattern are plotted on a Wulff net and indexed by measuring the angles between planes and directions. The problem of identifying the Laue spots has been approached in several different ways. Nicholas 1 tabulated interplanar angles for ten planes but did not relate the angles to permutation of indices or sign. A table of angles between adjacent planes and of angles between adjacent zones was published by Chandrasekhar and veal.' These tables are very helpful, provided the film shows all the low-order zones that occur within about 20 deg of each other. Frounfelker and Hirthe's compilation3 of angles between the (001) plane and twenty-nine other planes is useful for the indexing, only if the (001) spot can be found on the film. For all but the simplest orientations, however, more information is needed to index the diffraction spots. Standard stereographic projections, such as those published by Bicelli, 4 provide part of the information required. By their nature, these projections show the positions of only a few zone axes. In the tetragonal system many low-order zone axes are not normal to the planes having the same indices. Consequently, planes and directions can have entirely different positions on a stereographic projection. For example, the [011] zone axis is 33 deg from the normal to the (011) plane. The crystallographic orientation usually has to be deduced from a combination of the predominant zone axes and a few low-order planes that appear on the film. In addition to a standard stereographic projection of the planes, a stereographic projection of the directions is needed. Such a projection can be constructed from the angles given in Table I. To provide more information about angles between planes and directions, we have calculated interplanar angles up to (332) and angles between planes and directions up to [332] on an IBM 1620 computer. The angles are differentiated according to permutations of sign and indices. Those doing research on tin single crystals are welcome to request a copy of these tables from the authors.

Jan 1, 1967

H. M. HOWE, Bedford Hills, N. Y.-One wonders, whether it might not be well to check, by a rather simple and direct way, the inferences that would be drawn from this investigation. Suppose we quench, in these various liquids cylinders of steel, selecting material that is not likely to split in hardening, and then examine their cross-sections micro-scopically. If the cylinder is of any size, you will find a series of concentric bands, a very hard band, a softer band, and a hard band-but it seems that here would be a way of checking the inferences from the cooling curves by comparing these waves of hardness obtained in similar speci-mens quenched in different liquids. One would think that there would be great promise in that way. One's first thought is to quench similar pieces of steel, similarly heated, in different liquids and determine their hardness. I suppose many of us have tried that. We then meet the-difficulty that it is not the most rapid cooling that gives the greatest hardness. There is an intermediate rate of cooling that gives maximum hardness so that you can not by any simple method as that check this cooling method. But it seems possible

Jan 12, 1919

Discussion of the paper of WALTER 0. SNELLING, presented at the New York meeting, February, 1915, and printed in Bulletin No. 100, April, 1915, pp. 695 to 704. A. F. LUCAS, Washington, D. C.-Are the results of the experiments in practical operation? WALTER 0. SNELLING.-There have been no large-scale operations up to the present. The necessary conditions of temperature are easily arranged for, but the required condition of pressure, 800 lb., is not so simple a matter. The company has been working on this problem, and at the refinery in Oklahoma work of this kind is now being carried on. The way in which an ordinary still will leak at 50 lb., and more at 100 lb., leaves some doubt in the mind of many as to what can be clone at a continuous working pressure of 800 lb. On the other hand, the fact that they are making ammonia abroad by a method which employs higher pressures and temperatures than anything involved in this method, leads me to believe that the difficulties, which will undoubtedly arise when this is attempted on a commercial scale, can be overcome. WILLIAM N. BEST, New York, N. Y.-Is there any change in the calorific value of these oils?

Jan 5, 1915

.MAX ROESLER, Firmeza, Oriente, Cuba (communication to the Secretary?).-It is substantially admitted by all who have recently been in touch with these deposits that the orebodies lie in the fine-grained dark-green rocks, called diorite by most writers and diabasic by myself. The three points of disagreement concern the agency of included limestone blocks as causes of deposition, the agency of the

Jan 5, 1917

R. Culver, Colorado School of Mines I appreciated Professor Starfield's presentation, because his approach to blasting research reflects my feelings that a lot of practical work can be done toward making short-term advances that can be used by the blasting industry. We should not forget this in our attempt to obtain solutions to such idealized problems as a mathematical theory of cratering. The blasting industry would like very much to have the efficiency of the basic blasting processes improved from the range of 20 percent up into the range of 50 percent. And many of these problems should be approached and attacked in the laboratories. Blasting research at the Colorado School of Mines for the past two or three years has been aimed at improving the pre-splitting process, because we feel it will become increasingly important to the construction industry. We have attempted to develop a unified theory of how pre-splitting works; and the more we investigate, the more variables we find. We may never obtain an entirely satisfactory theory of pre-splitting, but we have developed a tentative explanation. One of our first conclusions was that we are making very poor use of the explosive in current pre-splitting practice. But to appreciate this we must first consider how pre-splitting works. A series of parallel boreholes are loaded with low density charges which are detonated simultaneously. (Delayed detonation has been tried, but most people agree that simultaneous detonation is best, and this is what we found.) Stress waves traveling out from each borehole interact with the stress waves from the two adjacent boreholes influencing the direction of the fractures that occur and propagate from each borehole. It has been suggested in private communication with Mr. Wilbur Duvall of the U. S. Bureau of Mines, that the fracture between the adjacent boreholes is a result of the net particle velocities above and below the pre-split plane which tend to set up a net tension along the pre-split plane. Regardless of what the exact mechanism is that causes the fracture to propagate from one borehole to the next, we know that it, in general, relies upon an interaction of the stress waves. However, if there is a large compressive stress normal to the pre-split place, it can practically eliminate any possibility of obtaining the desired pre-split by preventing the desired fractures from getting started. Aside from obtaining a fracture along the pre-split plane, the other major aim of pre-splitting is to minimize the fracturing that occurs around the borehole. We do this by drilling a large hole and putting a small charge in the middle of it. This results in a badly decoupled charge which is very inefficient; most of the energy is used in compressing the air in the borehole. Out of discussions about how pre-splitting works, we decided that perhaps there was some other explosive geometry which would make more efficient use of the explosive, and result in optimizing the pre-splitting process. Starting in the laboratory with small plexiglas blocks, we found that a fully-coupled explosive charge of 5 grains/in. of PETN gave random fractures extending about I in. from the borehole. A 1/4 in. plexiglas plug fit into a 1/4 in. hole in a similar block with the same fully coupled charge gave random fractures extending out only about 1/2 in. due to the energy absorbed in fracturing the plug. If the plug was split longitudinally but otherwise using the same geometry, it was possible to drive a fracture about 2 in. in either direction from the borehole, with an even smaller amount of fracturing around the borehole.

Jan 1, 1967

By Ray W. Ballmer

"For his leadership in developing and managing large, complex, and technically innovative mines, particularly the outstanding and successful Bougainville mine and for his lecture, 'The Moving Targets of Mine Development '. " Recipient of the 1981 D. C. Jackling Award

Jan 1, 1982

By AIME AIME

BEGINNING Thursday, July 16, the National Broadcasting Co. is broadcasting from 6:30 to 6:45 p.m., over its nationwide network and possibly also by short wave a series of eleven radio programs dealing with the contributions of engineers to the prosecution of the war. The series is being arranged and sponsored by a committee of representatives of the national engineering societies, R. L. Sackett, chairman. The committee began its deliberations before Pearl Harbor and had scripts under way on blackouts, bombs, and damage to structures. The declaration of war emphasized the importance of the proposed radio program. The National Broadcasting Co. and the Office of Civilian Defense enthusiastically endorsed the committee's proposal and have been generous in their help and approval of scripts so far submitted. Controversial matters are included in the broadcasts and changes will be made when requested by O.C.D. up to the minute that a program goes on the air. In this way the latest and authoritative information will be given.

Jan 1, 1942

By A. B. Young

THERE were produced in this country in 1923 probably in the neighborhood of 12,000 or 13,000 tons of refined and crude arsenic, by far the greater portion coming as a by product of smelting operations. Early this year copper smelters were producing arsenic at the rate of about 425 tons per month and lead smelters at the rate of 7;0 tons per month. During the entire eighteen years prior to 1919, there were produced in the United States only 47,000 tons of arsenic, which amounts to only 25 per cent. of the present output. The great increased demand has come about through the augmented use of arsenates as insecticides and arsenates as weed killers. In an extract from "Mineral Resources of the United States" on "Arsenic in 1922," Messrs. Heikes and Loughlin say, "The minimum possible demand for arsenic in 1923 was estimated at the end of 1922 to be about 13,000 tons, including 2000 tons for plate glass manufacturers, 3000 tons for lead arsenate, 3500 tons for calcium arsenate, 1500 tons for weed killers, 1200 tons for Paris green, 1000 tons for sheep dips and 750 tons for proprietary mixtures. More recent information, however, indicates twice as great a demand for calcium arsenate." The latter has found great use in the last three or four years as a weapon to combat the boll weevil pest of the southern cotton belt. ~t the present writing refined white arsenic is being quoted on the New York market at from 13)d c. to 1455 c. per Ib., while the average price during the eighteen-year period just mentioned was 4.8 c.

Jan 1, 1924

By A. H. Cottrel

SINCE metallurgy exists to provide strong, tough, engineering materials it must inevitably be perpetually concerned with the problem of brittle-ness. The steel-making industry was created because chemically unrefined iron is brittle. The steel-working and alloy-steel industries exist partly because hardness and ductility are mutually exclusive qualities in structurally unrefined steel. Yet, in spite of these immense industries, the brittle failure of steel ships hulls, bridges, pressure vessels, and pipelines, is still a contemporary problem. In fact, brittleness is a normal property of most solids, including metals and alloys, at low temperatures. Only face-centred cubic metals are commonly ductile at the lowest temperatures, and even here exceptions are known.'," Expensive are-melting processes. under inert gases or vacuum, have been developed to overcome brittleness in titanium, zirconium, columbium. and molybdenum. Polycrystal-line zinc, magnesium, and uranium have little ductility at room temperature. Beryllium, chromium, and tungsten have even less; similarly for antimony, bismuth, germanium, silicon, intermetallic compounds, and metallic carbides, nitrides, silicides, and borides. Oxides and other ceramics would be ideal creep-resistant materials but for their extreme brittleness when cold, and great efforts have been made to overcome this problem by mixing ceramics with metals. In fact, the traditional use of the name metallurgy for what is really the science of engineering materials is a recognition that most non-metallic solids have so far been precluded, by their extreme brittleness, from use as major structural materials in mechanical engineering. Most of what we know about brittleness in metals has come from studies of structural steel, and it is this material that shall mainly be considered. The things we have learned from it have a wider application, at least to other body-centred cubic transition metals, although the extent to which similar ideas can be applied to hexagonal metals and other materials is not yet clear. Fracture and Plastic Deformation The theoretical breaking strength of an ideal solid, about E/10 where E is Young's modulus, has been approached reasonably closely in experiments on fibres. But large specimens break at much lower stresses. For example, brittle cracks in large structural steel assemblies have been observed to spread catastrophically at speeds of 6000 ft per sec under stresses of about 10,000 psi, i.e. about E/3000. There are two sources of weakness; stress concentrations, and chemical agents in grain boundaries or on crack faces that lower the surface energy y of the material. Although we shall deal mainly only with the first of these, much of the discussion is also applicable to the second when different values of y are used. Griffith's well-known formula p = [ 2Ey/p(1 - v2)c]1/2 [1] gives the smallest tensile stress p able to propagate an atomically sharp surface crack of length c or interior crack of length 2c through a thick plate (compared with c) of elastically isotropic material of

Jan 1, 1959

By Clemens Jones

A FORM of apparatus for volumetric determinations which shall possess the features requisite for the constant use of potassium permanganate, is a very desirable fixture in a well-appointed laboratory. Expedients to economize time and insure accuracy are generously employed for various other reagents, while the permanganate seems to have been consigned to the use of an ordinary burette, and a black bottle of the standardized solution. But the introduction of new, methods dependent on the permanganate, and the urgency of technical requirements where it has long been indispensable, require a revision of practice more scientific and convenient. The apparatus designed by the writer for the laboratory of the Thomas Iron Company at Hokendauqua, Pa., is so simply contrived and works with such entire satisfaction that a description of it may be of use. It may be prefaced that the characteristics of a suitable device offer some mechanical difficulties when combined in a continuous appliance. The burette, B (50 C.C. to 1/10 c.c.), shown in Fig. 1, consists of the graduated tube proper and an arm, E, fused to it below the 50 c.c. mark. At its top are rubber connections with the blast-aspirator, shown in the cut (Fig. 2) of the front view. By means of an extra stopcock, D, connection through E is established with the reservoir F. The burette is clamped Securely to a slide, C, which is counterpoised and moves freely on guides between two parallel sides, L, suitably

Jan 1, 1887

By Ernest F. Burchard

A Reconnaissance of the manganese- and chrome-ore deposits of Cuba was made by the writer, as a representative of the U. S. Geological Survey, in company with Mr. Albert Burch of the Bureau of Mines, under instructions of the Secretary of the Interior, in the spring of 1918. The Cuban Government courteously detailed Sr. E. I. Montoulieu, a mining engineer connected with the Treasury Department, to act as escort and associate throughout the work on the island. The object of the study was to obtain authentic information for use of the United States Government as to the location, character, quantity, and availability of the manganese- and chrome-ore deposits in Cuba. Accordingly, the work comprised examination of such deposits as seemed to be of promise, without regard to stage of development, with a view to a determination of the quantity and quality of ore likely to become available for shipment during 1918 and 1919, and of the tonnage of ore in reserve. Wile it was possible to visit most of the deposits that seemed to be of promise, there was not sufficient time to visit all that were brought to our attention, some of which may have merit. Moreover, the necessity for paying particular attention to the ore deposits and the mines precluded the possibility of making more general studies of the geology of the region, and of making satisfactory collections of country rock and of fossils, and so for other details as to the geography and geology of Cuba the reader is referred to the report by Hayes, Vaughan, and Spencer.l Mr. Burch returned to the United States about 10 days in advance of the writer, who continued, in company with Sr. Montoulieu, investigations of reported deposits in Pinar del Rio, Matanzas, and Santa Clara Provinces. On his arrival in Washington, Mr. Burch submitted to the Director of the Bureau of Mines a summary of the results of the work to date. Later the writer published, as Press Bulietin 190. 380 of the U. S. Geological Survey, a statement concerning the chrome and man-

Jan 1, 1920

By Morris Muskat, J. M. McDowell

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By J. M. McDowell, Morris Muskat

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949