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By Enrique Touceda

As IN the case of steel and the non-ferrous alloys in general, the use of the microscope in connection with the manufacture of malleable cast iron has proved of inestimable value to the industry. Had its use not been invoked, many facts either would not be known at all or, if suspected, would be confined to the realms of conjecture. No fairer statement could be made than that the start of real progress in the industry was coincident with the application of metallography to the product, though the full significance of this statement can hardly be appreciated except by those who not only are conversant with conditions as they existed at the time referred to, but are familiar with the character of works' practice at the present time. A few years ago, about the only test made to ascertain the physical properties of the product, t except in the case of certain plants, was the bending of a casting to destruction, not only with the object of discovering whether or not the metal was ductile, but for the purpose of inspecting the fracture. The characteristics of the fracture, if correctly interpreted, were known to be of value in locating the trouble in, castings that were inferior. In general, it was found that if a casting of medium or heavy section would bend through a wide angle before failure took place, the fracture in the majority of cases would have a black velvety appearance; while if it was held at different angles to the direction of the rays of light, it would show a change of color and an iridescent sheen. But an inferior air-furnace heat or anneal might yield castings which, if thin and consequently largely decarburized, could be bent double on themselves and still not possess the fracture described. If, on the other hand, a casting broke short, its fracture might have one of a great many different color and structural peculiarities. Depending on the cause of the trouble, such castings might have any of the fracture characteristics, of which the following is but a partial list.

Jan 2, 1920

By John Lovejoy

As the Seminole area, Seminole and Pottawatomie Counties, Okla., appears to be the chief danger zone of overproduction in the United States, it may be of interest to review the production records of the various pools which make up this area; also to dis-cuss the future prospects of these pools, together with the structurally "high" points which may develop into new pools. It is also of interest to appraise the effect of the curtailment program in this general area, which was agreed to in principle by the various Seminole op-erators at a meeting held on May 23 at the offices of W. C. Teagle in New York. There are four large pools in the greater Seminole area. They are, in the order of their importance Seminole City, Bowlegs, Earlsboro, and Searight pools. A glance at the accompanying general map of the area will show their relative situation. The detail maps show the extent and area of these prolific spots. Seminole production comes from the Wilcox sand of Ordovician age, found at a depth of 3900 to 4300 feet. Semninole City Pool:-This pool was discovered in Wilcox sand in July, 1926. By Jan., 1927, there were 123 wells completed, making 146,000 bbl. per day. The field reached its peak of 253,000 bbl. per day the last week of Feb., 1927, with 211 completions and a per well average of 1200 bbl. On July 4 there were 304 wells completed, producing 102,000 bbl., with a per well aver-age of 336 bbl. per day. This pool will cover an area of approximately 3500 acres. It has produced approxi-mately 38,000,000 bbl. to. July 1. Estimates of total ultimate production are around 55,000,000 bbl. or somewhat better than 15,000 bbl. per acre. Some of the individual leases have already yielded 30,000 and 40,000 bbl. to the acre. Bowlegs Pool:-This pool shows 175 drilling wells and 131 completions making 180,000 bbl. per day, with an average per well production of 1380 bbl. It appears that this pool will develop into nearly as large an area as Seminole City. The wells, however, do not give up

Jan 8, 1927

By S. Grinsfelder

Although wildcatting was hampered by the general overproduction and low price of crude, several developments, worthy of note in the history of the petroleum industry in the Rocky Mountain region, were made in 1927. This district records production from six new fields, two of these having been heretofore productive of gas. Deeper pay horizons were found in two other oil fields. In order to facilitate transportation from fields, six new oil pipe lines were completed or in the course of construction at the end of the year, and one line is proposed for 1928. Four gas lines were completed, one was under construction, and one was proposed for 1928. The total production in 1927 in the Rocky Mountain district was 29,591,379 bbl.,' a decrease of 7,771,991 bbl., or 21 per cent., fro111 the previous year. This was occasioned by natural decline and the general curtailment of production and drilling. A review of the development by states follows. Colorado Production from horizons in the Morrison and Sundance at Craig and at Ilrs Dome, and the bringing in of the deepest producing well in the Rocky Mountain district on North McCalluin anticline (Waltlrn) in Jackson County are the outstanding developments for the year in Colorado. In March the Midwest Refining Co.'s Parkinson 21 SD, SW SE, Sec. 22 T p. 4 N R 92 W, Iles Domr, Moffat County Colorado, found gas in sands in the Morrison estimated at 15,000,000 cu. ft., and at 3242 ft. an oil sand was encountered in the Sundance. Initial production from this horizon was 2575 bbl. in this well. This structure previously was only productive of water in the sands of the Dakota group but has been producing shale oil from horizons in the Benton. The second well completed by the Midwest Refining Co., No. 18 SD in Sec. 23 was also productive of gas in the Morrison and made an initial of 300 bbl. from sands in the Sundance. By the end of the year three other wells wrrc nearing the completion stage but none of them indicate that they will be as big producers as the discovery. To date the productive area has

Jan 1, 1928

By L. E. Wemple

Previous to 1915, zinc refining had not become a general practice among the zinc smelters in the United States. Such refining as had been carried on was confined chiefly to remelting very high-leaded zinc, such as third-draw metal from the retort furnaces, and slab dross, and hard spelter from galvanizing pots. In this remelting operation, the lead and iron were settled out and the refined spelter obtained graded fifth class, ie., Prime Western. Owing to the presence of lead in most zinc ores, the bulk of the spelter produced by direct smelting is of this Prime Western grade. Careful selection of ores of low lead content gave purer grades of spelter, z.e., Brass Special and Intermediate; and smelters which could secure ores carrying practically no lead produced high-grade spelter. Thus, in general, the grade of spelter produced by any smelter was predetermined by the purity of the ore it could obtain. The needs of the warring nations of Europe for enormous quantities of cartridge and other high-grade brass resulted in such a demand for the purer grades of spelter that the available supply of lead-free and low-lead ores could not produce the quantity required. Prime Western grades went begging, so to speak, while high grades sold at times from 5 to 15 c. per pound over the Prime Western market. The great demand, coupled with the wide market margin, which permitted the inherent costs and losses, resulted in the conversion of the lower grades into higher grades by processes of refining. These conditions also accentuated the development and size of the electrolytic plants, which were being worked out at the time this increased demand for pure grade of metal occurred. The electrolytic process, where available, produces a higher grade of spelter from impure ores than does the fire process; a large portion of those impurities in the ore, which by the distillation process would be carried into the spelter, are removed in the leaching of the ores and the purification of the solutions. The refining process, adopted at a number of smelters for the purpose of converting low-grade spelter into grades suitable for bras4 was that of redistillation.

Jan 1, 1918

By Leland Wemple

PREVIOUS to 1915, zinc refining had not become a general practice among the zinc smelters in the United States. Such refining as had been carried on was confined chiefly to remelting very high-leaded zinc, such as third-draw metal from the retort furnaces, and slab dross, and hard spelter from galvanizing pots. In this remelting operation, the lead and iron were settled out and the refined spelter obtained graded fifth class, i.e., Prime Western. Owing to the presence of lead in most zinc ores, the bulk of the spelter produced by direct smelting is of this Prime Western grade. Careful selection of ores of low lead content gave purer grades of spelter, i.e., Brass Special and Intermediate; and smelters which could secure ores carrying practically no lead produced high-grade spelter. Thus, in general, the grade of spelter produced by any smelter was pre-determined by the purity of the ore it could obtain. The needs of the warring nations of Europe for enormous quantities of cartridge and other high-grade brass resulted in such a demand for the purer grades of spelter that the available supply of lead-free and low-lead ores could not produce the quantity required. Prime Western grades went begging, so to speak, while high grades sold at times from 5 to 15 c. per pound over the Prime Western market. The great demand, coupled with the wide market margin, which permitted the inherent costs and losses, resulted in the conversion of the lower grades into higher grades by processes of refining. These conditions also accentuated the development and size of the electrolytic plants, which were being worked out at the time this increased demand for pure grade of metal occurred. The electrolytic process, where available, produces a higher grade of spelter from impure ores than does the fire process; a large portion of those impurities in the ore, which by the distillation process would be carried into the spelter, are removed in the leaching of the ores and the purification of the solutions. The refining process, adopted at a number of smelters for the purpose of converting low-grade spelter into "grades suitable for brash was that of redistillation.

Jan 11, 1917

By Barry D. Lichter, Pierre Sommelet

High-temperature heat contents of InAs and GaAs were measured over the temperature range 400°K to temperatures above the melting points using a di-phenyl ether drop calorimeter. Smoothed values of the thermal properties have been derived and tabulated at even temperature interuals . The heats of fusion of InAs and GaAs were determined as, respectively, 8790 ± 200 and 12,590 ± 300 cal per g-atom at the respective melting points of 1210º ± and 1513º ± 1°K, yielding entropies of fusion of 7.26 * 0.16 and 8.32 ± 0.20 cal perºK per g-atom, respectively. A general discussion of the thermal properties of III-V com-pounds is given. THE low-temperature heat capacities of InAs and GaAs have been determined by Piesbergen.1Using a dynamic temperature modulation technique, Miller2 has determined the heat capacities of the compounds as well as GaSb and Ge between room temperature and 650°K; however, it has been observed that values determined by drop calorimetry for GaSb3 and for germanium4 are consistently about 5 pct lower than Miller's results. Cox and Pool10 report values for the heat content of InAs and GaAs and the heat of fusion of InAs. No value for the heat of fusion of GaAs appears to have been previously reported. This paper reports results of high-temperature heat content investigations of InAs and GaAs measured in the range 400" to above 1500°K employing a diphenyl ether drop calorimeter. These results, together with our previous results on III-Sb compounds3 as well as heat-content measurements5 of solid InP and Gap, are used in a general discussion of these compounds. EXPERIMENTAL PROCEDURES High-purity samples of the compounds, stoichio-metric to ±0.1 at. pct, were supplied in the form of crushed crystal fragments by Dr. Carl Thurmond of the Bell Telephone Laboratories. The sample preparation, description of the calorimeter, and details of the heat content measurement have been previously described.3 Samples were sealed in evacuated silica capsules and suspended by a Pt-Rh wire in a Pt-wound vertical tube furnace, heated to temperature

Jan 1, 1970

By J. L. Walter

Tungsten ingots with and without small amounts of aluminum, silicon, and potassium were prepared by conventional powder-metallurgy techniques and hot-rolled to 0.001-in.-thick sheet. The ingots were rolled three different ways: I) initially cross-rolled, then straight-rolled; 2) straight-rolled, and 3) straig-ht-rolled, then cross-rolled. Total reductions were 99.8 pct. Samples of the sheet were annealed, in vacuo, at temperatures from 1200" to 2200°C. Substructures and textures were determined by transmission electron microscopy and X-ray diffraction. The doping agents were found to form particles of mullite (Al,Si,O,,) which, on rolling., appear to form strings of particles aligned parallel to the rolling direction. These strings of purticles are associated with an increase in the recrystal-lizution temperature from 1400°C for undoped sheet ThE addition of small amounts of aluminum, silicon, and potassium to tungsten has a profound effect on the grain structure of drawn and recrystallized wire.'" The grains generally do not occupy the entire cross section of the wire and have lengths many times the wire diameter. The grain boundaries are, in general, nearly parallel to the wire axis and have long ''fingers" projecting one into the other as may be seen in Fig. 1, a longitudinal section of recrystallized doped wire. When unsuitable additions or no additions are made or the wire is not sufficiently reduced during draw- to 2000°C for doped sheet. The particles also limit lateral grain growth while allowing growth parallel to the rolling direction. This results in the formation by primary re crystallization of large highly elongated grains of specific preferred orientation. The undoped sheet recrystallized to small equiaxed gains. The preferred orientations of the large grains were determined from axis density plots to be (113) (691). (0i3) (362), (116) (304) types for the initially cross-rolled then straight rolled material. These orientations are similar to the orientations of the large elongated grains in doped and heavily drawn tungsten wire. The nucleation of the large grains appears to occur by recovery of certain of the polygonized regions of specific orientation, followed by strain-induced boundary migration.

Jan 1, 1968

By Raymond Mancha

WHEN calculating the pressure-volume characteristics of projected mine-ventilat-ing circuits by orthodox methods, certain basic assumptions are required in order to employ the various available empirical data. It is assumed, for example, that the mine air is an incompressible fluid subjected to isothermal flow, an assumption suffi-ciently accurate for practical purposes since pressure and temperature differentials are small throughout the average circuit. A more erroneous assumption, however, is that all air is accounted for as it travels throughout the mine. No attempt is usually made to evaluate stopping leakage as it occurs; instead, the air volume required at the last crosscuts is assumed to enter the mine, travel the vari-ous intake air courses intact, sweep the workings and travel out by the return air courses to the point or points of exit from the mine. Actually, there is a leakage of air from intake to return at every stopping, the quantity of this leakage depending upon the tightness of the stopping and the pres-sure difference across the stopping. Unfortunately, a lack of empirical data and knowledge of the condition of individ-ual stoppings makes an exact analysis of underground stopping leakage impossible. Generally, leakage is most severe through the old stoppings outbye the circuit. These are also subjected to higher pressure differ-ences than the newer inbye stoppings. Therefore the circuit air volume diminishes at a decreasing rate progressing from out-bye to inbye the circuit.

Jan 1, 1940

By John H. Hollomon

IN a recent paper,1 a very early suggestion by Ludwik2 concerning the nature of the mechanical behavior of metals has been reexamined and extended. In essence it was [ ] suggested that there exists, at least under certain conditions, a mechanical equation of state; that the stress required for flow depends upon the instantaneous values of the strain, strain rate, and temperature, and not upon their past values. It is proposed that under these circumstances the stress does not depend upon past history of these variables, but is like the temperature of a gas that depends only upon the I instantaneous values of the pressure and volume. This notion has not been applied to present day studies of metals, though it is especially applicable to the study of creep. It is the purpose of this paper to analyze the significance and possible range [ ] of applicability of this idea and to deter- mine how it influences the accepted ideas concerning creep. STRESS-STRAIN RELATIONS It is well known that the stress-strain curves of metals are influenced by both strain rate and temperature. For a fixed strain rate and temperature there is associated with each metal a stress-strain curve. If either the strain rate or temperature is changed a new stress-strain curve will be characteristic (Fig. I). A much more general relation between the effects of the sevariables is possible, however. Consider the stress-strain curves of Fig. I determined at

Jan 1, 1946

By S. L. Crouch, C. Fairhurst

The general term "coal mine bump" refers to the sudden and violent failure of in-situ coal. Coal bumps occur in most countries where coal is worked by underground methods. They are related to geological factors and mining techniques. Coal bumps can be characterized as unstable releases of energy associated with yielding that occurs with progressive mining. Unstable releases of energy occur when the coal is able to absorb less energy than is released by the surrounding rock mass during the yielding process. At any stage of mining, the amount of excess energy so released is governed by the mining geometry, the overburden stress, the elastic properties of the rock mass, and the stress-strain characteristics of the seam material. If the coal in the vicinity of the working face is crushed, the peak abutment pressure occurs at some distance into the intact portions of the seam, and mining takes place in essentially destressed coal. With subsequent mining, additional yielding occurs, excess energy may be released, and the peak stress is again shifted into the solid. This process continues until the mining geometry is such that the zone of peak stress is effectively surrounded by yielding coal, at which point it can be anticipated that further mining will produce dramatic redistributions of stress and be accom¬panied by large releases of energy. On this basis, the differences between several alternatives for mining a given block of coal may be pronounced.

Jan 1, 1975

By Paul Sterling

The general impression regarding the preparation of merchantable anthracite is that it is confined to a colossal, grimy structure, called a " coal-breaker." This name is a misnomer; for the desired result is not to break the coal, but to prevent its being broken. Preparation may be said to begin at the face of the chamber, with the mining and loading of the coal. Local conditions vary, not only ill the same field or basin, but also in the same mine, so that there is no fixed empirical rule governing the method of blasting or cutting coal. Tests should be made, when possible, to determine the explosive, or the mechanical coal-cutter, which will produce the largest percentage of what are locally known as " lump " and " prepared sizes " of anthracite. The prepared sizes are those mostly consumed for clomestic purposes. All other sizes might be called by-products of the anthracite industry; for they are not especially desirable, being the degradation resulting from the mining and handling of a brittle or laminated material. Being low in volatile combustible matter, anthracite burns most successfully when nearly of a uniform size, permitting the easy passage of air through the voids. This accounts for the large number of sizes into which the coal is separated. Table I. gives the various sizes, the diameter of ring over and through which each size is made, and the usual purpose for which it is employed.

Jan 1, 1912

By Donald F. Saunders

Means and relative standard deviations were calculated for eU, eTh, K, and their ratios for aerial gamma-ray spectral data in 29 quadrangles at 1:250,000 scale. Known or suspected uraniferous provinces were characterized by: 1) Higher eU, eTh, and K means (due to generally higher radioelement concentrations); 2) Higher relative standard deviations for eU, eU/eTh, and eU/K (reflecting the presence of local uranium enrichments); and

Jan 12, 1979

By Dennis J. McCarthy

TAX TREATMENT OF EXPLORATION AND DEVELOPMENT EXPENSES Exploration Expenditures General Principles. Exploration expenditures are expenses incurred within the United States or the Outer Continental Shelf for the purpose of ascertaining the existence, location, extent or quality of any deposit of ore or other mineral. Section 617 of the Internal Revenue Code permits a taxpayer to elect to deduct these expenditures currently. In default of election, exploration expenditures must be capitalized and included in the basis of the mineral property for purposes of determining cost depletion. Entitlement to Deduction. In order to qualify for current deduction, exploration expenditures must be incurred prior to the commencement of the development stage, i.e., when mineral deposits are shown to exist in sufficient quantity and quality to reasonably justify commercial exploitation. Generally, expenditures for geological and geophysical investigations, reconnaissance, surveying, testpitting, trenching, drilling, driving of exploration tunnels and adits and similar types of work constitute exploration expenditures if incurred prior to the commencement of development. However, expenditures to further delineate the extent and location of an existing commercially marketable deposit are not exploration expenditures. Exploration expenditures may be incurred from within a producing mine to ascertain the existence of what appears to be a different ore deposit. Expenditures for property which is subject to an allowance for depreciation are not deductible under §617. However, depreciation properly allowable on assets used in exploration is an exploration expenditure. Election to Deduct Exploration Expenditures. The election to deduct exploration expenditures is made by deducting these expenditures in the return for the first taxable year for which such treatment is desired. The election applies to all properties of the taxpayer. Once the election is made all exploration expenditures, in the year of election and thereafter, must be deducted, unless the election is revoked with the prior consent of the Commissioner. The Tax Equity and Fiscal Responsibility Act of 1982 (TEFRA) made substantial changes in the treatment of exploration expenditures. For exploration expenses incurred after 1982 and before 1984 by a corporation, the amount currently deductible is limited to 85% of the expenditure. The remaining 15% must be capitalized and recovered over a five-year period. Although exploration costs capitalized under this provision are not part of the basis of the property for cost depletion purposes, investment credit may be claimed with respect to these expenditures. Further changes have been added by the Tax Reform Act of 1984 with respect to expenditures made after 1984. The Act reduces the amount of otherwise currently deductible costs from 85% to 80%. Additionally, it limits the availability of the investment credit for capitalized mineral exploration costs to deposits located in the United States. TEFRA also allows individuals a special method of recovery under which exploration expenditures may, at the election of the taxpayer, be amortized ratably over a 10-year period beginning with the year in which the costs are paid or incurred. If taxpayer does not use this method, the excess of the exploration expenditures actually deducted over the amount that would have been deducted if 10 year amortization had been elected is an item of tax preference subject to the alternative minimum tax.

Jan 1, 1985

By D. H. Davis

There are two general types of oil flotation processes, froth and bulk-oil. In froth flotation, the coal concentrates are removed in the form of a froth or foam composed of air, liquid, and solids. Mechanical or pneumatic agitation of a coal slurry with suitable frothing agent causes a selective action of the bubbles to the coal particles which are carried to the upper portion of the pulp in the flotation cell; the refuse is wetted by the water and does not rise with the froth, but goes out as tailings. The other type of flotation process, bulk-oil, consists of thoroughly mixing the slurry or pulp with 30 to 50 pct of its weight of oil. The coal agglomerates with the oil and drops to the bottom of the cell while the refuse is wetted by the water and is carried away in suspension. The concentrate granules may be screened and drained to 12 to 15 pct moisture. The minus 200 or 300-mesh is very effectively treated by this process. The Trent process is a bulk-oil type which has been used for coal cleaning on a commercial basis, but its use has been discontinued in this country. Froth flotation of bituminous coal should be subdivided into two distinct fields: (I) separation of a dry coal product such as recovered from an aspiration system; (2) separation of a minus 48-mesh slurry such as produced from a thickener in a wet cleaning plant. The capacities, performance, and general operating characteristics are very different in these two fields. The recirculated slurry in a washery becomes oxidized and is much harder to treat than a dry dust. It is difficult to clean a slurry containing an appreciable percentage of plus 48-mesh without also floating some high-ash clays minus 200-niesh in size. On the other hand, while working with an aspirated dust, good results have been obtained in floating coal as coarse as 3/16-in. Because of the relatively low capacity of flotation machines as compared with conventional fine-coal cleaners .and because of the greater quantity of reagents required to float coarse coal, there is usually no point in considering flotation on bituminous coal for anything coarser than approximately 48-mesh. In some coal-cleaning plants, good separations are being made down to 80 or even 100-mesh by a less expensive system of coal cleaning than flotation. The Pittsburgh Coal Co. carried out extensive tests on laboratory batch machines and on small units of both pneumatic and mechanical agitation types from 1930 to 1935 and have operated six, eight, and then twelve mill-size mechanical subaeration cells from 1932 to 1944 This paper will deal with some of the operating phases and results of coal-flotation practices as derived from this experience, and more specifically with the flotation practice at the Champion No. I preparation plant. The experience gained from the research and initial experimental work contributed greatly to the successful operation of the mill-sized flotation units at Champion.

Jan 1, 1949

By G. W. P. Rengstorff, L. E. Olds

High purity molybdenum ingots containing controlled amounts of a single impurity element (oxygen, nitrogen, or carbon) were prepared. These ingots were tested for ductility by bending test specimens at various temperatures. The relationship between the plastic behavior of the ingots and their chemical composition has been determined. MANY proposed applications for molybdenum require ductility at or near room temperature. At the present time, it is possible to obtain wrought molybdenum with considerable ductility only if special fabrication techniques are used to control the grain structure. Starting with are-cast or powder metallurgy ingots, the usual methods for obtaining ductility rely on fabrication procedures that result in fibered microstructures in the finished product. Recently, it has been found that the ductility of either powder metallurgy or are-cast molybdenum can be improved by uniform recrystallization of the metal to a very fine equiaxed grain structure.' The need for a fibered or a fine grained structure may limit the practical usefulness of molybdenum. For example, welding. which may be used in fabricating the metal, generally produces coarse grained structures that lead to brittleness. This applies, certainly, to currently available commercial molybdenum. Although commercial molybdenum is brittle when the grains are coarse, it has been shown experimentally that fine grained structures are not always essential for ductility. For instance, as-cast molybdenum with a coarse columnar grain structure is ductile if it is sufficiently pure.' Because high purity cast molybdenum has good ductility even when coarse grained, it is probable that the brittleness in coarse grained commercial molybdenum is caused by the impurity content of the metal. Although the general effects of impurities on the cold ductility of molybdenum have been known in a qualitative manner for some time, no quantitative evaluation of these effects has been available. The present investigation was made in order to determine more accurately the effects of oxygen, nitrogen, and carbon on the cold ductility of cast molybdenum. Oxygen has long been known to be detrimental to ductility, although the minimum amount which will embrittle molybdenum has been open to speculation. Parke and Ham" showed that ingots with oxygen contents above 0.003 pct could not be forged. Maringer and Schwope have described the embrittle-ment of molybdenum wire by oxygen. A discussion on the effects of heat treatment on the distribution of oxygen in molybdenum has been given by Perry, Spacil, and Wulff." Although nitrogen would also be expected to have harmful effects on ductility, no extensive work has been done previously to determine whether this is so. However, Tury and Krausz" found that wires presumably with less than 0.007 pct N were brittle. Carbon is added to commercial cast molybdenum for deoxidation. Parke and Ham" have shown that molybdenum containing as much as 0.06 pct C could be forged if the oxygen was kept below 0.003 pct. Also, Bruckart and others' found that the room temperature ductility of sintered molybdenum improved with carbon contents up to 0.84 pct. However, Rengstorff and Fischer' found that residual carbide particles in cast molybdenum apparently had an unfavorable effect on room temperature ductility.

Jan 1, 1957

By G. Thodos, R. B. Grieves

A method has been developed for the accurate calculation of the cricondentberm and cricondenbar temperatures of multicomponent hydrocarbon mixtures of known composition. The mixtures may contain any number of components including paraffins and isoparaffins, olefins, acetylenes, naphthenes and aromatics. This approach is based upon the mole fraction of the low-boiling component in the mixture and graphically presents the ratios of the cricondentherm and cricondenbar temperatures to the pseudocritical temperature as {unctions of a boiling-point parameter. The only requirements are the critical temperature, normal boiling point and the approximate vapor pressure behavior of each component. For mixtures of more than two constituents a stepwise calculation procedure is necessary where the pseudocritical temperature is based upon the critical temperature of the pure low-boiling component and upon the actual cricondentherm or cricondenbar temperature of the mixture of all the remaining higher-boiling components. From an analysis of 22 binary systems (123 compositionsl, the average deviation of calculated cricondentherm temperatures from reported values is 0.87 per cent, based on degrees Rankine; and for 10 multicomponent mixtures containing from three to six components, the average deviation is 0.98 per cent. From an analysis of 18 binary systems (104 compositions) the average deviation of calculated cricondenbar temperatures from reported values is 0. 79 per cent; and for 15 multicomponent mixtures, 1.47 per cent. Equations, derived from the graphical relationships, are presented which enable rapid calculations for both binary and multicomponent systems. INTRODUCTION With the increasing tendency towards the use of high pressure processes, the need for an accurate method of calculation of the properties of a multicomponent hydrocarbon mixture in the critical region is becoming more essential. Critical region phase relations are also significant in gas condensate reservoirs, for which a knowledge of the fluid phase boundaries and regions of retrograde condensation make it possible to evaluate optimum operating conditions. The possibility of liquefaction in the underground structure may be established, and information on the feasibility of the use of repressurizing may be determined. A typical phase diagram for a multicomponent hydrocarbon mixture is presented as Fig. 1. This figure also shows the regions of retrograde behavior encountered by following lines AB and AC. If accurate methods of calculating the temperatures and pressures at the critical, cricondentherm (maximum temperature) and cricondenbar (maximum pressure) points of multicomponent hydrocarbon mixtures of known composition were available, it would be possible to estimate closely the entire phase diagram of any mixture. Several methods have been presented in the literature for the estimation of the critical temperatures and pressures of multicomponent mixtures containing all types of hydrocarbons and including the fixed gases.4-8,21 Considering the cricondentherm and cricondenbar points, the work is more limited. Etter and Kay5 have developed rather complex equations for

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

AS a portion of a general study of liquid-metal thermodynamics, high-temperature galvanic cells were used to study the effect of added dilute solutes on the activity of zinc in dilute solution with molten bismuth in the range 450° to 650°C. 1,2 The cells were of the type The experimental procedures have been described previously.1 In the course of studies conducted in the bismuth-rich corner of the systems Bi-Zn-Au and Bi-Zn-Cu, marked discontinuities were observed in the electromotive force-temperature relations for a number of the experimental compositions. Above the discontinuity temperatures, the relations, which were linear, exhibited slopes similar to the binary alloy of the same mole fraction zinc, as shown in Figs. I and 2. Below the discontinuity temperatures, the slopes were markedly different, but the relations remained linear. In general, as the amount of the third eletnent was increased, the slope of the lower portion of the relations tended to become less positive. The slopes of electromotive force-temperature relations reflect the entropy of mixing of zinc and, therefore, the occurrence of a discontinuity marks the transition between two different equilibrium situations involving the solution of zinc. A number of other investigators3-5 have used such observations to determine liquidus boundaries in binary alloys. Since the upper portions of the ternary electromotive force-temperature relations of this study had the same slopes as the binary alloys, the discontinuities are interpreted as marking the transition between the single-phase liquid region and the underlying two- and three-phase regions. Reference to the Zn-Bi equilibrium diagram6 confirms that the binary alloys were single-phase liquids at the experimental temperatures. Fig. I shows the electromotive force-temperature relations for the alloys containing Bi-Zn-Au and Fig. 2 shows similar relations for the Bi-Zn-Cu alloys. In the lower portion of each figure, the temperature of the discontinuity is plotted vs the mole fraction of the added solute at the various levels of zinc concentra- tion. Cross-plots from these curves at constant temperature permitted the construction of the partial liquidus surface isotherms shown in Figs. 3 and 4.

Jan 1, 1967

By John F. Elliott, David L. Schroeder

SURFACE depletion can be a significant source of error in the use of the effusion method for determining the thermodynamic properties of alloys, particularly in the case of solid alloys.' However, as yet this problem has not been treated quantitatively by experimentalists in the field.1-3 The method necessitates diffusive transport of material out of the source alloy to obtain a relevant measurement. The general character of the system is shown in Fig. 1. The diffusive flux (nD) at the alloy surface is equal to the effusive flux (nE): where D is the diffusion coefficient of the diffusing substance, C is its concentration, X is the distance from the surface into the source alloy, p is the density of the alloy, and AS is the actual available surface of the alloy. The concentration of the diffusing substance at the surface is CS, and Here fE is the Clausing factor, AE is the area (sq cm) of the orifice, y is the activity coefficient of the substance in the alloy, PO is the vapor pressure (Torr) of the pure substance, M is the molecular weight of the effusing species, and T is the absolute temperature. The differential equation for diffusive transport in the source alloy is Fick's second law. Its solution is dependent on the geometry of the source alloy. Two boundary conditions must be established to obtain the proper solution, the first being Eq. [1], or its equivalent. The solutions for several important forms of the source alloy are considered below.

Jan 1, 1967

W. M. Courtis, Detroit, Mich. (communication to the Secretary) : Having made a rapid examination of the deposits described in this paper, I am not inclined to generalize confidently concerning its geological relations. But, since an analysis furnished by me has been included in the paper, it may be of further use to give the results of other samples and analyses. I give, therefore, a table of analyses by different parties, showing the average from surface-specimens:

Jan 1, 1901