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By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By H. J. Struth

Gasoline is undoubtedly of major importance not only to the petroleum refiner but to the producer. To study the economic aspects of gasoline is, in a measure, a constructive effort to solve the problem of overproduction not only for the refiner but for the entire petroleum industry. After all, the prime object of producing crude petroleum is to supply motor fuel and lubricants to nearly 25,000,000 American motor vehicles, not to mention the increasing demand for these products abroad. Since gasoline furnishes the chief source of revenue to the refiner, it follows that this important product should veritably become recognized by all branches of the petroleum industry as an almost infallible index of day to day requirements of the producer and the refiner. A careful study of gasoline statistics over the past decade or more reveals that there is a definite correlation between world-wide gasoline requirements and the demand for crude petroleum, as well as all other petroleum products. This leads the writer to the conclusion that gasoline is literally the economic yardstick of the entire petroleum industry. Control of Operations That the refiner has begun to recognize the urgent need for controlling his operations is evidenced by the results of the past three years. Unfortunately, it is a difficult problem to convince the refiner that he cannot run crude in excess of the demand for gasoline, without incurring a consequent decline in the market value of this and all other products of distillation. Undoubtedly, he still has much to learn in this respect. Few commercial products have enjoyed such phenomenal growth in demand as has gasoline, and, at the same time, few products have failed, as has gasoline, to reap financial benefit from the popular demand for a national necessity. Perhaps this unprecedented demand was responsible for the overextension of retining facilities, which resulted in the excesses of recent times; at any rate, as the demand for gasoline grew by leaps and bounds, so the refining industry continued to increase its capacity for

Jan 1, 1929

By H. Ries

SPECIAL sands are those that are employed for special purposes. They have a limited use, as compared with sands for concrete and plaster. The sands discussed in this chapter are those used for foundry purposes, glass manufacture, filter beds, abrasive purposes, sandblasting, engine sand, sand for sheet asphalt, and furnace sand. These sands are almost invariably high in silica, consisting chiefly of quartz grains. In some-for instance, glass sands-freedom from ingredients other than silica, such as iron oxide, is important. Certain grades, like filter sand, require rather careful sizing, and in foundry sands the bond, usually clay, is important. One deposit may sometimes be used to supply several grades or types of sand by appropriate methods of screening and washing. The special sands discussed here are usually obtained from deposits of unconsolidated material but sands high in silica are derived occasionally from soft sand- stones that can be disintegrated easily. Requirements are not the same for all uses, and, while certain properties may be demanded, there are no officially adopted standard tests except for foundry sands. FOUNDRY SANDS Definition-Foundry sands include those siliceous sands that are used to make the forms for casting metals. If these are employed for making molds, they are known as molding sands; if for the cores that form the hollow spaces in the casting, they are called core sands. Naturally bonded sands are those containing a variable, though not usually large, amount of clay, which serves as a bond. Synthetic sands, now much used, represent an artificial mixture of sand with usually fire clay or bentonite. Core sands may be bonded with oil, cereal binders, resin, pitch, or other materials. The foundrymen apply the term "sharp sand" to one that is free from bond. Properties-The important properties to be tested at room temperature are texture or fineness, permeability, strength, deformation, and flowability. Those tested at elevated temperatures are compressive strength, expansion and contraction, sintering point, and durability. More attention probably has been given to research on the properties

Jan 1, 1949

By H. M. Chance

The present value of most coal properties resides largely in the cod remaining to be mined, which thus constitutes the most important asset. The object of this paper is to discuss methods commonly used in computing the value of minable coal. To distinguish clearly between such coal values and the values of other property, the several kinds of property values should be divided into classes; so as to avoid the unintentional omission of items of importance. Value op Coal Reserves Judicial decisions prescribe, and appraisers commonly accept, current sales value as the preferred means for determining the value of transferable property. With few exceptions a property is worth the sum that can be realized from its sale by a willing seller to a willing buyer, a sale in which compulsion urges neither party, and between whom there is no community of interest to fix a value; or it is worth at least as much as a responsible buyer will offer for it. Actual sales of like property or bids from responsible buyers for the property, or for substantially like property, are the best established methods for determining values. Only in the absence of such sales or bids can valuations by other methods be entertained, and only for reasons of weight can sales values be set aside. Valuation Based on Royalties Sales of coal in the ground, as customarily carried out through lease under royalty agreements, are therefore the most trustworthy means available for determining the value of coal reserves. The constantly rising value of high-grade coal in the United States can most readily be shown by the increasing royalties per ton that can be obtained for such coals under leasehold. The rising value of land containing such coal can also, of course, be proven by the price at which such properties are actually sold as compared with prices obtainable for lands containing coal of the same grade in the past. It is exceedingly difficult, however, to establish values by the prices paid for coal

Jan 1, 1927

By H. J. Struth

A glance into the immediate future of the refining industry, and a retrospective view of 1929, cannot fail to emphasize the need for effective measures of control of refinery still runs. With oil producers alert to the need for control of the crude supply, it has become more than ever necessary for refiners to complete the movement toward stabilization by concerted determination to maintain still run schedules within the limitations prescribed by the demand for gasoline. The outlook for continued growth in the demand for gasoline appears to be well sustained by a preliminary survey of requirements for 1930. In fact, it is apparent that the industry will be assured of a market for gasoline that will aggregate in volume at least 472,000,000 bbl. this year. This indicates a gain in total demand over 1929 of about 9 per cent. or about 4.6 per cent, less than the gain recorded during 1929 over 1928, which amounted to 13.6 per cent. Despite the indicated increase in gasoline demand this year, it is apparent that little, if any, more crude will be required than last year. This is shown in Table 1, presenting estimates of gasoline demand and probable crude requirements for 1930. Table 1.—Preliminary Survey of 1930 Gasoline and Crude Run Requirements Millions of Barrels Doniestic gasoline demand................................... 397 Foreign gasoline demand..................................... 75 Total indicated demand...................................... 472 Natural gasoline content..................................... 53 Net gasoline from crude...................................... 419 Imported gasoline........................................... 13 Net gasoline required from refineries.......................... 406 Indicated excess stock Dec. 31, 1929........................... 10 Maximum protluction required................................ 396" At 40 per cent. gasolitlc recovery, this represents a maximum crude converson of 990,000,000 bbl., or a daily average for the ycar 2,712,000 barrels. Year after year, the refining branch of the petroleum industry has been found guilty of running crude to stills greatly in excess of normal requirements, causing frequent periods of market depression. A review

Jan 1, 1930

By G. L. Kothny

DEVELOPMENTS of well-surveying instruments, coring and core orientation, were in an advanced state when drilling for oil began-these developments actually originated with the mining industry.1 Surveying of oil wells was not generally used in the United States until Alexander Anderson2 disclosed that the majority of wells drilled with rotary tools were crooked, with average horizontal drifts of about 516 ft. for holes 5000 ft. deep and about 793 ft. for holes 6000 ft. deep. This disclosure brought about the development of many additional instruments for surveying oil wells during the progress of drilling and after their completion. Surveying of boreholes, during the process of drilling at regular depth intervals, became a standard practice in the petroleum industry. Some producing states even established laws making check surveys mandatory, during drilling and under certain conditions also after completion. The surveying of boreholes also brought about changes and improvements in drilling practices. It provides information for the guidance of the hole while drilling, and for plotting the course as the work progresses, enabling the driller to take corrective measures immediately and with the least expense. The reasons for drilling straight holes are too well recognized to warrant any full discussion of them here. Straight holes are less costly to drill, because [ ] they reach the object on the shortest course. Table I shows the horizontal drift and loss in vertical depth for various angles of inclination. It is not surprising, therefore that many drilling contracts for oil wells today limit the drilling contractor to a maximum inclination off the vertical of 2° or 3°. In the mining industry the reasons for drilling straight holes are still more serious. A crooked hole may miss an ore body underground or provide incorrect information regarding an ore body. TYPES OF SURVEYING INSTRUMENTS The surveying instruments used in oil-well drilling may be classed in two types: I. Inclinometers, recording inclination only.

Jan 1, 1946

By G. L. Kothny

Developments of well-surveying instruments, coring .and core orientation, were in an advanced state when drilling for oil began—these developments actually originated with the mining industry.' Surveying of oil wells was not generally used in the United States until Alexander Anderson2 disclosed that the majority of wells drilled with rotary tools were crooked, with average horizontal drifts of about 516 ft. for holes 5000 ft. deep and about 793 ft. for holes 6000 ft. deep. This disclosure brought about the development of many additional instruments for surveying oil wells during the progress of drilling and after their completion. Surveying of boreholes, during the process of drilling at regular depth intervals, became a standard practice in the petroleum industry. Some producing states even established laws making check surveys mandatory, during drilling and under certain conditions also after completion. The surveying of boreholes also brought about changes and improvements in drilling practices. It provides information for the guidance of the hole while drilling, and for plotting the course as the work progresses, enabling the driller to take corrective measures immediately and with the least expense. The reasons for drilling straight holes are too well recognized to warrant any full discussion of them here. Straight holes are less costly to drill, because they reach the object on the shortest course. Table I shows the horizontal drift and loss in vertical depth for various angles of inclination. It is not surprising, therefore that many drilling contracts for oil wells today limit the drilling contractor to a maximum inclination off the vertical of 2° or 3O. In the mining industry the reasons for drilling straight holes are still more serious. A crooked hole may miss an ore body underground or provide incorrect information regarding an ore body. Types of Surveying Instruments The surveying instruments used in oil-well drilling may be classed in two types: I. Inclinometers, recording inclination only.

Jan 1, 1949

By R. Norman Orava

The strain-mte behavior of. the tensile yielding and flow characteristics of arc-cast polycrystal-line molyhdenum of pidrity > 99.97 pct was investigated in the range 10-6 to 10-1 sec-1 at 243o, 293o, and 373oK for two grain sizes, 0.027 and 9.098 mm. For 0.998 mm, the strain-mte dependence of the lower yield stress can be described by a straight line of the jowl a, = a + 0 log e over the whole range of strain rates examined. However, for 0.027 mm, the data fit several consecutive linear relationships of the above form. The previous association of these different linear regions with different rate -controlling mechanisms is questionable for molyhdenzdm. The senlilog strain-rate dependence of the yield stress is consistent with Hahn's model for yielding when the stress dependence of the mobile dislocation density, pr, is taken into account. Since p', from rate -cycling experirnents, is found to be relatively insensitive to stress for single crystaIs, the obserzied log-log dependence of their yield stresses is also in agreement with the model. A correction for the stress dependence of p' changes the activation oolurrze for yielding from a zero to a more realislic inverse function of stress where the Peierls mechanism is believed to be rate-controlling. The gmin-size dependence of the lower yield stress is not a monotonic junction of strain rate. RECENT experimental evidence' has revealed that the strain-rate dependence of the tensile lower yield stress, a,, of commercially pure ni- obium and tantalum tested at room temperature can be described by several consecutive semilog relations of the form: sv =a + ß log € [1] where i is the applied strain rate and a and 0 are constant Over only relatively small ranges of strain rate. Three linear regions were found for niobium and four for tantalum. Each linear region was interpreted as being associated with a different rate-controlling mechanism on the basis of the current

Jan 1, 1964

By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956

An experiment substituting pneumatic crawler drills for large-diameter rotary rigs in overburden stripping operations has indicated significant bit cost savings for Perry and Hylton Coal Co., Beckley, W. Va. The test was conducted in the Egeria Mountains (part of the Appalachian Range), where about 30 m (100 ft) of overburden consisting of hard, seamy sandstone and shale must be removed to recover a 560-mm (22-in.) vein. Perry and Hylton operates ten surface mines and is presently developing three more for start-up in the near future. The company follows a progressive policy toward ecological concerns, incorporating a self-imposed systematic mining and reclamation program for mined lands which leaves the landscape in a suitable condition for further development by local communities.

Jan 6, 1976

By Earle J. Klohn

Mining operations have been carried out in British Columbia since the time of the first settlers in the area. The early developments were mainly small volume, high-grade operations, producing small quantities of tailings wastes. In these early days the nearest stream was a logical first choice for tailings disposal. Where streams suitable for accepting the tailings were not available or where streams crossing the International Border could not be used for this purpose, the nearest convenient land site was selected for storing the tailings. Old tailings waste piles exist at many locations in the Province and are readily evident, for example, in the Princeton and Hedley areas. Figs. 1 and 2 are photographs showing the present condition of two of these old tailings dams. [ ]

Jan 1, 1972

Raymond Weir Smyth, born Nov. 3, 1888, was the son of Herbert Weir Smyth, professor of Greek Literature at Harvard University. He graduated (A. B.) from Harvard in 1909 and later pursued advanced studies there in chemistry and in metallurgy. He held the position of metallurgist for the American Steel and Wire Co. at Worcester, Mass., and also for the Steel and Tube Co. at Youngstomn, Ohio. For a time he was inspector of munitions for the British Government and stationed at the Railway Steel and Spring Co. at Latrobe, Pa. For a short time, in 1917, he was Inspector of Ordnance for the U. S. Government, and the following year, having entered the U. S. Naval Reserve Force, he was ordered in a similar capacity to the Midvale Steel Co. In September, he removed to the Navy Yard, League Island, Philadelphia, to train for the obligatory minimum of six months' sea duty. There he contracted influenza, which was followed by pneumonia, from which he died, September 27, at the Navy Yard Hospital. Captain Braxton Bigelow* Captain Braxton Bigelow was the son of Major John B. Bigelow, U. S. A., retired, and grandson of the late John Bigelow, author, and Minister to France under President Grant. Captain Bigelow graduated

Jan 1, 1920

Raymond Weir Smyth, born Nov. 3, 1888, was the son of Herbert Weir Smyth, professor of Greek Literature at Harvard University. He graduated (A. B.) from Harvard in 1909 and later pursued advanced studies there in chemistry and in metallurgy. He held the position of metallurgist for the American Steel and Wire Co. at Worcester, Mass., and also for the Steel and Tube Co. at Youngstomn, Ohio. For a time he was inspector of munitions for the British Government and stationed at the Railway Steel and Spring Co. at Latrobe, Pa. For a short time, in 1917, he was Inspector of Ordnance for the U. S. Government, and the following year, having entered the U. S. Naval Reserve Force, he was ordered in a similar capacity to the Midvale Steel Co. In September, he removed to the Navy Yard, League Island, Philadelphia, to train for the obligatory minimum of six months' sea duty. There he contracted influenza, which was followed by pneumonia, from which he died, September 27, at the Navy Yard Hospital. Captain Braxton Bigelow* Captain Braxton Bigelow was the son of Major John B. Bigelow, U. S. A., retired, and grandson of the late John Bigelow, author, and Minister to France under President Grant. Captain Bigelow graduated

Jan 1, 1920

By J. D. Mooney, D. L. Darnell

The accompanying chart has been drawn for the convenicncc of engineers as' a means of quickly determining the correct number of plies of conveyor belts operating under specific conditions. The calculations are based on the average safe strength (factor of safety, 15) of the various standard rubber conveyor belts. The calculations assume maximum loading conditions; that is, the belt is considered as carrying the greatest load that it will handle without spillage at ordinary belt speeds. This not only produces the most economical operating conditions, but also the maximum tension in the belt. The chart is a graphical representation of the formula: Where, p = kg W(L + 10H) p = the correct number of plies k = a constant, depending on the type of drive g = the weight 'in pounds per cubic foot of material handled W = the width of the belt in inches L = the length of the belt in feet (approximately twice the center distance). H = the difference in elevation between the head and tail pulleys, in feet. For a simple drive, with a bare pulley, k = ----1 For a simple drive, with a rubber-lagged pulley, k = --- 1 For a, tandem drivej with bare pulleys, k = 1/375.000 For a tandem drive, with rubber-lagged pulleys, k = ---1 The chart is drawn for a simple drive, with a bare pulley (k — =e)1 ; therefore, the number of plies obtained from the chart should be multi- ' plied by the factor 0.83 or 5/6 for simple, lagged drive; the factor 0.67 or 2/3 for tandem, bare; and the factor 0.55 or 11/20, for tandem, lagged. The formula p = kgW(L + 10H) has been developed mathematically

Jan 1, 1916

By R. G. Grieves, G. Thodos

A method is presented for the accurate calculation of the cricondentherm and cricondenbar pressures of multicomponent hydrocarbon mixtures of known composition. The mixtures may contain six and quite possibly any number of components including paraffins, isoparaffins, olefins, acetylenes, naphthenes and aromatics. The approach is similur to that used for calculating critical pressures and cricondentherm and cricondenbar temperatures. The critical pressure, the normal boiling point and the approximate vapor pressure behavior of each component are all that art required. A stepwise culculation procedure is necessary for mixtures containing more than two components. From an analysis of 22 binary systems and 118 mixtures, the average deviation of calculated cricondentherm pressures from reported values is 2.4 per cent. For nine multicomponent mixtures the average deviation is 1 per cent. Considering 19 binary systems and 108 mixtures, the average deviation of calculated cricondenbar pressures from reported values is 1.7 per cent. For 15 multi-component mixtures, the average deviation is 2.2 per cent. INTRODUCTION A knowledge of the phase behavior in the critical region of multicomponent hydrocarbon mixtures is of value both in industrial processing operations and for the optimum operation of gas condensate reservoirs. Accurate methods of calculating the critical temperatures and critical pressures4,6,7,8,9,23 and cricondentherm and cricondenbar temperatures6p10 of multicomponent hydrocarbon mixtures are available in the literature. If the cricondentherm and cricondenbar pressures could be calculated with equal accuracy, the entire phase diagram of a multicomponent hydrocarbon mixture could be well approximated. The work of Etter and Kay6 is limited to systems containing the normal paraffins and has not been tested on systems containing a heavier component than heptane. In addition, the development of their multicomponent equations is based upon a limited number of mixtures containing from three to six components. Silverman and Thodos have considered systems containing both paraffinic and non-paraffinic hydrocarbons, but their correlation is limited to binary systems and is highly inaccurate for methane systems. Eilerts has done extensive work on the cricondenbar pressure; he has produced an excellent correlation for binary systems. However, his procedure for multicomponent mixtures is chiefly useful for highly complex mixtures requiring a knowledge of the vapor-liquid equilibrium behavior of the mixtures; he has not considered the cricondentherm pressure. The objective of this study was the development of an accurate and rapid method for the calculation of the cricondentherm and cricondenbar pressures of multicomponent mixtures containing all types of hydrocarbons and having a wide volatility range. The approach that was adopted is similar to that used by Grieves and Thodos for cricondentherm and cricondenbar temperaturesl0 and for critical pressures.9 However, methane systems had to be considered separately and a modified stepwise calculation procedure was utilized for the cricondertherm pressure. The correlations were developed in a manner similar to those for critical pressures and cricondentherm and cricondenbar temperatures. Based upon binary data reported in the literature it was observed that the ratios of cricondentherm and cricondenbar pressure to the pseudocritical pressure (molar average), pt/ppc and pp/ppc, respectively, in two-component systems depended upon the mole fraction of the low-boiling component and upon the diversity in properties of the two components. A dimensionless boiling-point parameter Tb,/Tb was chosen to represent the diversity in properties of the components. For a binary system, Ti,'is the molar average of the normal boiling points of the two components involved. For a multicomponent system it is either the molar average of the normal boiling points of all of the components involved or the molar average of the normal boiling point of the pure low-boiling component and of the atmospheric boiling point of the low-boiling-free mixture of

Jan 1, 1965

By S. Pearson, L. Rotherham

Measurements have been made of the variation of internal friction with temperature for OFHC copper, and for a series of binary solid solutions of high purity copper with zinc, gallium, germanium, arsenic, and silicon, to investigate the effect of alloying elements in substitutional solid solution on grain boundary viscosity. The apparatus used was of the torsional pendulum type developed by KeI1 modified so that the specimen and vibrating system could be maintained in a high vacuum. The activation energy for grain boundary relaxation in copper is 33,000 cal per mol. This is considerably less than the activation energy for self-diffusion, in disagreement with Ke's theory2 that the two activation energies should be the same. All the alloying elements increase the activation energy for grain boundary relaxation to approximately 44,000 cal per mol, increasing the grain boundary viscosity at a given temperature. The results are discussed in terms of theories of grain boundary slip put forward by MottQ and by Ke.+ Experiments have also been made to investigate the effect of small amounts of oxygen on the variation of internal friction with temperature for copper. EXPERIMENTS described in this paper were designed to investigate the effect of alloying elements in substitutional solid solution on grain boundary viscosity, using the internal friction method developed by Kel for measuring grain boundary viscosity. It was considered desirable to make the system under investigation as simple as possible by making experiments on a comprehensive series of binary alloys of copper with the elements immediately following it in the periodic table, i.e., zinc, gallium, germanium, and arsenic. These elements are within the range of favorable size factor for solution in copper, and the systems have been extensively investigated by Hume-Rothery and his co-workers." Later, in order to study the effect of the relative size of the solvent and solute atoms, experiments were made on a series of Cu-Si alloys, since the apparent atomic diameter of silicon when in solution in copper—the diameter necessary to assign to the solute atoms to account for the lattice constant of the solid solutiona—is almost the same as that of the solvent atoms. Preliminary experiments were made to measure the variation of internal friction with temperature for pure copper. Ke made some experiments on copper," but found that the curves obtained were not reproducible in consecutive experiments. The copper was maintained in an argon atmosphere during the experiments but, although he took precautions to exclude oxygen, Ke came to the conclusion that the precautions were not entirely satisfactory, and that the lack of reproducibility must be due to absorption of oxygen by the copper. Experiments have therefore been made to investigate the effect of small amounts of oxygen on the variation of internal friction with temperature for copper. Previous Work Ke made extensive experiments on high purity aluminum and was able to show that the grain boundaries behave viscously at high temperatures. He found that the relative rate of movement of the grains could be expressed as Where v is the velocity of slip, A is the constant, u is the shear stress, H is the activation energy, R is the gas constant, and T is the absolute temperature. By assuming that the boundary layer was one atom thick, he obtained a value for the viscosity which, when extrapolated to the melting point, gave good agreement with the viscosity of the liquid metal at the melting point. Ke also made experiments on other high purity and commercial purity metals:, and on some alloys." " He came to the conclusion2 that the activation energy for grain boundary slip was the same as for self or volume diffusion and for steady state creep in single crystals. Rotherham, Smith, and Greenough" have shown recently that the activation energy for grain boundary slip is not the same as for self-diffusion in tin,

Jan 1, 1957

By J. E. Flinn, S. A. Duran

The steady-state creep behavior of poly crystalline cad mi inn was studied over a temperature range of (1.56 to 0.94 Tm. Two distinct mechanisms were found to occur over this temperature range. They were described by: where and represerqt the minimum strain rates corresponding to the low- and high-temperature regions, respectirely. The two regions of constant acti11ation energy were connected by a transition region where the strain rate was controlled by both mechanisms acting in parallel. At temperatures below a transition temperature of about 0.7 Tm the agreement between the activation energy value for creep and that for self-diffiision suggests a rate-controlling mechanism of dislocation climb. For cadwzium, steady-state creep at temperatures above 0. 7 Tm appears to be controlled by another mechanism, perhaps involving the behavior of dislocation jogs. FRENKEL et al.1 studied the high-temperature creep of polycrystalline cadmium and reported an activation energy of 21 kcal per mole for the 0.5 Tm < T < 0.8 Tm range. Based on observations of creep rate at only two temperatures, a value of 22.1 kcal per mole was determined by Medbury. These two investigations were for the purpose of showing agreement between the activation energy for creep and that for self-diffusion, reported3 as 18.2 and 19.1 kcal per mole, respectively, for diffusion parallel and perpendicular to the hexagonal axis. Gilman4 investigated prismatic glide in single crystals of cadmium over a higher-temperature range of 0.72 to 0.93 Tm, and found an activation energy of 29 kcal per mole. He also reported5 an activation energy higher than that of self-diffusion for prismatic glide in zinc single crystals deformed at temperatures near the melting point. This value was in good agreement with those found for an equivalent temperature range by Flinn and Munson6 and by Tegart and sherby7 for polycrystalline zinc. These two independent studies also disclosed at lower temperatures another value of activation energy near that for self-diffusion. It would be expected from the creep results on zinc and single-crystal cadmium that creep studies on polycrystalline cadmium, extended to temperatures near the melting point, might yield an activation-energy value higher than the 22 kcal per mole value found in earlier studies. The purpose of this paper is to report the steady-creep behavior of polycrystalline cadmium over a temperature range of approximately 0.5 to 0.9 Tm EXPERIMENTAL METHOD The cadmium used in this study was obtained in the form of as-cast rods, 0.5 in. diam, through the courtesy of the Bunker Hill Mining Co. The material was of 99.995 pct purity, as determined by spectro-chemical analysis. The creep specimens, which were 0.250 in. diam by 0.400 in. long and annealed at 300°C for 45 min to produce a stable average grain diameter 0.25 mm, were tested in compression using an apparatus similar to that described by Sherby.8 The specimen temperature was controlled to within ±0.5°C with the help of appropriate constant-temperature baths. The applied stress was maintained within 1.0 pct of the desired value by the additions of lead shot at fixed strain increments. No barreling was observed over the strains encountered during testing. Isothermal creep tests9 were used in the study with only a few differential temperature tests10 run for comparison purposes. Steady-state creep data were obtained over a temperature range of 60 to 287°C (0.56 to 0.94 Tm) at five stress levels ranging from 28.1 to 140.6 kg per sq cm. RESULTS The minimum or steady-state creep rate may be described by an equation of the following form:" where i is the minimum strain rate, S is the structure factor, F is a stress function, Qc is the energy of activation, T is the absolute temperature, and R is the gas constant. The minimum strain rates obtained in this study for cadmium were recorded on a semilogarithm plot as a function of the reciprocal absolute temperatures for the various stress levels, as shown in Fig. 1. This figure shows a characteristic transitional behavior" with a parallel interaction of two mechanisms. It is obvious that the activation energies corresponding to the individual processes are insensitive to stress because the curves are parallel. The discrete activation-energies values for the low- and high-temperature regions for the various stress levels are reported in Table I, and were determined by the least-mean-square method. For the low-temperature region, an activation energy of 20.7 ± 0.6 kcal per mole was obtained, and for the

Jan 1, 1967

By William H. Callahan

"For his exceptionally successful career as a geological mentor, for his ore-finding skills, and particularly the discovery of the Central Tennessee Zinc District and for his lecture, &apos;Prospecting in the USA-Promise and Problems.&apos; " Recipient of the 1982 D.C. Jackling Award

Jan 1, 1983

DEPENDENCY on foreign sources for many mineral raw materials is a characteristic of our economy which is becoming painfully evident. Although investment in foreign mining projects has increased, it has not kept up with the growing demand for foreign minerals. The sphere of American investment capital in mining ventures abroad has been severely limited by the rise of nationalism in many underdeveloped countries. Consequently, we can look back over half a century in which mining investment, exclusive of petroleum, has increased by 50 pct whereas other American investments abroad have multiplied by better than 300 pct. Investment in foreign mining or petroleum encounters different problems than capital investment for other industries. It is rarely invested in industrialized nations. Most of it goes to countries with expanding frontiers, like Canada, or to underdeveloped nations like Liberia. It must be used for building communities, recruiting and training labor, and establishing lines of communication and transportation. These complications are an accepted part of the mining game. However, the most complex problem is in those countries which consider mineral exploitation a usurpation of the people&apos;s natural heritage. This is a characteristic of the young government existing by a tenuous balance of power in an underdeveloped nation. American mining capital understandably has shunned these nations as being poor investment risks. However, they possess minerals which are needed by industry. Our government has attempted to stimulate mineral supplies beyond those provided from abroad by private capital. ECA, now under DMPA, makes loans to foreign mining companies. Since the ECA program cannot be expected to continue indefinitely, Point IV seems to be the logical next step to encourage foreign countries to fill our shortages. However, only 1 pct of the $35 million budget provided in the first year for Point IV was alloted for mining programs. Considering the need for minerals and the difficulties of procuring them by private investment, a larger share is needed and justifiable. Those who have been engaged in foreign mining can vouch for the fact that it takes many decades to teach the complex technology and economics of mining to the natives of under-developed countries. For this reason Point IV must be considered a long range program. Mineral requirements for the present must be met by more direct measures. Encouragement of private investment in foreign mining by such incentives as tax relief on profits from foreign sources, international bank-borrowing facilities for private capital, and diplomatic assistance in encouraging foreign countries to cooperate are imperative for our future mineral security.

Jan 1, 1952