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By J. J. McKetta, O. L. Culberson

INTRODUCTION The equilibrium constants for methane and for water, and for ethane and water have been calculated from experimental data for the two binary systems.2,3,11,12 These constants are for the two-phase systems for the temperature range of 100" to 340°F and the pressure range of 200 to 10,000 psia. The constants for ethane are greater than those for methane. Equilibrium constants for a natural gas from a natural gas-water system6 are about the same as those for methane. Equilibrium constants for water in all three systems are very nearly the same over the greater part of the range of temperatures and pressures studied. In ideal solutions, the vapor-liquid equilibrium constants for a component should be the same in all such solutions at a given temperature and pressure.5 Few solutions are ideal, and consequently the use of generalized constants often leads to error in situations where they do not actually apply. In decidedly non-ideal systems, it is desirable to have equilibrium constant data for the specific system. Vaporization equilibrium constants may be calculated either by thermodynamic methods or from experimental vapor-liquid equilibrium data. In the thermodynamic calculation. the equilibrium constant K may be shown to be" K = fP,/fl'..........(1) where fPi is the fugacity of the pure component i at the given temperature and at the vapor pressure of the pure component, and fp is the fugacity of pure i in the gaseous state at the temperature and total pressure of the system. At best the thermodynamic calculation results in a K applicable to ideal solutions. Equilibrium constants calculated from Equation (1) have been found to have only limited agreement with experimental values, even though the solutions for which they were calculated approached ideality."'" If the more volatile component is at a temperature above its critical, the accuracy of the equilibrium constant for the component is made more doubtful by the use of the vapor pressure term under such conditions. In order to make the thermodynamic calculation on a component above its critical temperature, one must resort to one of the empirical methods of extrapolation of the vapor pressure to conditions above its critical point.13 Application of the thermodynamic equilibrium constant then to the methane-water or the ethane-water systems would be risky since the systems are non-ideal, and the methane and ethane are above their critical in most petroleum operations. ETHANE-WATER SYSTEM In the temperature range of from 100° to 340°F and for pressures up to 10,000 psia, the vapor-liquid equilibrium data 'References given at end of paper. Manuscript received in the office of the Petroleum Branch March 16, 1951.

Jan 1, 1951

By Forest Mintz

Many oil and gas producers find it advantageous to borrow against the value of their hydrocarbon re- serves. This paper considers the requirements for a reserve based loan and the calculations that a bank would perform to arrive at a loan amount. Three of the most common loan structures, i.e. a term loan, a production payment, and a revolving credit/term loan will be discussed. A typical outline for each type of loan is presented. Finally, a comparison of major considerations in the three financing techniques is shown.

Jan 1, 1982

J. E. Johnson, Jr., Glen Wilton, Va. (communication to the Secretary*):—Mr. Meissner announces early in his paper that one of its purposes is the discussion of my paper entitled, Notes on the Physical Action of the Blast-Furnace,' with which he disagrees in part; and as the second stage of the discussion of this important subject has centered around his paper, some reply by me may not be amiss. Unfortunately, Mr. Meissner has not indicated a single statement or conclusion in my paper that he wishes to controvert; but as there is evidently a difference of opinion between us I will disregard this fact, and will discuss those conclusions of his that seem to me not to be justified by the facts of general practice, or even by the data which he produces to support them. Let me say, however, that I am a believer in the dry-air

Jan 1, 1908

By H. L. Marcus, P. W. Palmberg

As can be seen from the phase diagram A1-W1 the equilibrium solubility of tungsten in aluminum is practically nil at room temperature. By quenching from the liquid state (50,000°C per sec), Varic, Burov, and Kolesnicenko2 obtained A1-W solid solutions up to 0.15 at. pct W. The quenched alloys were in the form of foils, 0.2 to 0.3 mm thick. Considering the results of Duwez and Willens,3 it is obvious that this thickness, which makes impossible a sufficiently rapid quenching, was the main reason for the relatively low content of tungsten dissolved in aluminum found by Varic.2 he present note shows that the metastable solubility of tungsten in aluminum can be appreciably extended in aluminum-rich A1-W alloys. The quenching technique and the procedure employed for the preparation of the alloys have been described previously.475 The resulting quenched flakes varied in thickness from 1 to 20 µm from experiment to experiment. However, the measurements of the lattice parameters were carried out only with flakes thinner than 5 µm. The areas of quenched flakes were between 0.1 and 15 mm2. The quenched flakes were placed into a 0.3-mm glass capillary tube which was then mounted in a 114.6-mm-diam Debye-Scherrer camera. Straumanis asymmetric film position and nickel-filtered CuKa radiation were used. The lattice spacings were computed taking X(CuKa1) = 1.54050A for resolved and ?(CuKa) = 1.54178A for unresolved doublets. All specimens were rotated at room temperature, 26" +2°C. The lattice parameters were estimated from extrapolation against the Nelson-Riley function. It was estimated that the error in the lattice parameter of the measurements on a single film lies within +0.0004A for lower and about +0.001A for higher concentrations of tungsten. The lattice parameters of the metastable solid solutions A1-W are plotted vs the concentration of tungsten in Fig. 1 together with the parameters measured by previous investigators.' Each point of the present measurements represents a determination of the lattice spacing on different quenched flakes, for a given concentration of tungsten. With experimental accuracy, the lattice parameters of the metastable solid solutions fall on the straight line passing through the already known data.' As estimated from the uncertainties in the lattice spacings of the solid solutions, the alloys were homogeneous within 0.1 at. pct W. The solubility of tungsten in aluminum-rich A1-W solid solutions obtained by a very rapid quenching technique is increased to about 0.95 at. pct W. This value is 6 times greater than the amount known up to now. -he lattice parameters of the resultant aluminum solid solutions with higher concentrations of tungsten than 0.95 at. pct W did not remain constant AUGER electron spectroscopy has been used to clarify the role of impurities in the embrittlement of AISI 3340 steel. Analysis of fracture surfaces has shown that the embrittled condition is correlated with appreciable antimony segregation at grain boundaries. The low temperature (400" to 600°C) temper embrittlement of low alloy steels containing various combinations of Cr, Ni, Sb, Mn, P, Sn, and As has been examined extensively for many years. General reviews of the area have been made by McMahon1 in 1968, LOW' in 1959, woodfine3 in 1953, and Holloman4 in 1946. Recent work by Low, Stein, Turkalo, and LaForce5 has done much in separating the alloy and

Jan 1, 1970

By R. Priestner, R. F. Krause

Solid, cylindrical crystals of a iron have been fractured at 10°K by the simultaneous application of tension and torsion stresses. Thus, a complex distribution of normal (sN) and shear (ss) stresses existed in a cleavage plane at fracture. In every crystal the clearage-plane normal was inclined to the specimen axis, so that a unique point, M*, in the operative cleavage plane was defined where the quantities sn and s2 N + s2 S) were maximized. It is shown that the maxirrzum resolved normal stress on the cleavage plane at fracture decreased as the resolved shear stress in the cleavage plane at M* increased. Thus, a normal stress la?*! for fracture was not satisfied. A fracture law which takes shear stress into account. and which predicts that (s2 N +s2S) should be constant, is to be preferred. However, the data is best represented by a linear dependence of sN on sS, sS which 110 physical significance can be attached. It is suggested that the fracture-nucleating -mechanism is a short-range one. A critical stress law has not yet been unequivocally established for the propagation of cracks in metals. Measurements of the tensile fracture stresses of variously oriented zinc single crystals1 failed to establish the normal stress law expressed by In Eq. [1], sN is the fracture stress, P, resolved normal to the fracture plane, and 0 is the angle between the fracture -plane normal and the stress axis. Similarly, a comprehensive investigation failed to verify the normal stress law for the tensile fracture of a-iron single crystals.' However, a subsequent investigation,3 using iron from the same ingot, presented fracture data which obeyed the normal stress law. It has been shown previously4,5 that the Griffith criterion for fracture6 does not predict such a normal stress law. This result is of particular significance in considering the fracture of metals, such as zinc and iron, which may fail by cleavage. In these metals fracture propagates in a well-defined "cleavage" plane, whether or not an applied stress is normal to it. When the cleavage-plane normal deviates from the direction of application of a uniaxial stress, for example, the crack propagates under the combined action of normal (sN) and shear (ss) stresses. When the presence of a resolved shear stress in the crack plane is taken into account, the Griffith criterion is expressed by4

Jan 1, 1967

By A. Lubinski, J. L. Logan, W. S. Althouse

A4ost gas twells and flowing oil wells are completed and treated through a string of tubing and a packer. Changes in temperature and in pressure inside or outside the tubing will: (I) if free motion of the tubing inside the packer is permitted, increase or decrease the length of the rubing; or (2) if free motion is prevented, induce forces in the tubing and on the packer. If pressure inside the tubing is greater than outside, the tubing may buckle helically even in the presence of a packer-to-tubing tension. The tubing will always buckle, and much more severely, if free motion is permitted. The buckling may be prevented by pulling the tubing in sufficient tension. The prediction of these forces and tubing movement has here to fore been based upon calculations that did not inciude helical buckling. This paper preseitts means with which these length or force changes can be calculated while taking into account the effect of helical buckling. To avoid damaging formations, failure of remedial operations, or damage to the tubing or packer, application is made to practical problems involving calculations of the required length of seals, amount of sluckoff or tension, and prevention of permanent corkscrewing. INTRODUCTION Leakage of a packer may result in costly failures of such operations as squeeze cementing, hydraulic fracturing, etc. To avoid such failures, the authors are often asked questions pertaining to the length of necessary seals, the amount of necessary slackoff, etc. Published work' does not take into account helical buckling of tubing. Investigation of helical buckling was prompted by the fact that allowance must be made for this phenomenon in order to provide relevant answers. In the past, theoretical work on helical buckling was confined to conditions for which such buckling does not The mathematical treatment of behavior in a buckled condition, given in the Appendix, is novel. Assumptions upon which this investigation is based are listed and discussed in a special section. The following are a few of the many kinds of problems which may be solved with this paper. 1. Consider a packer in which tubing may move. Such movement will occur after pressures and temperature are changed. The paper provides means for: (a) calculating the amount of such movement and, therefore. the required length of seals; and (b) calculating the necessary amount of initial slackoff, for which there is no danger of unsealing the packer, if the length of seals is given. Such calculations, as well as those which follow, tully take into account the fact that part of the movement ib due to elastic helical buckling of the lower part of the string. This buckling may occur even in tubing under tension. Insufficient initial slackoff for a given length of seals, or insufficient length of seals for a given slackoff, may result in costly failures. A field case of such a failure will be given further in this paper. 2. In the case in which tubing cannot move in the packer, changes of pressure and temperature result in tubing-to-packer forces and forces in the tubing above the packer, both of which may be calculated. This knowledge is important because, if these forces are too large, the) could damage the packer or the tubing. 3. For wells in which wireline tools are to be run through the tubing, the paper provides means to keep the tubing from buckling, thereby permitting free passage of tools. 4. In deep wells, mainly in the presence of large casing, tubing may become "corkscrewed", i.e., take a permanent helical set. A field case is described further in the text. Using this paper, one may calculate in advance conditions under which permanent corkscrewing would occur, and then take preventive steps. HELICAL BUCKLING Consider a string of tubing, freely suspended in the absence of any fluid inside casing, as shown in Fig. I(a). Now consider an upward force F applied at the lower end of this tubing. This force compresses the string; and if the compression is large enough (which is always the case in actual problems), the lower portion of the string will buckle into a helix, as shown in Fig. 1 (b). The lower end of the tubing is subjected to a compression F. This compression decreases with the distance from the bottom and becomes nil (neither compression nor ten-

By K. Leutwyler, H. L. Bigelow

Jan 1, 1966

By B. S. Butler

AN understanding of mineralizing solutions and how they carry and deposit metals is of prime importance to students of ore deposits. Lindgren states: "The whole problem surely is very complicated. One difficulty is that we know so little about the stability field of ore minerals."1 Lindgren further states: It is believed that they [the solutions] were in small part oxidized to sulphates, for instance, but in large part they were composed of hydrogen sulphide, alkaline sulphides and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of the double sulphides as important constituents of the solutions probably holds good. In the fourth edition of Mineral Deposits2 Lindgren had changed his views somewhat: From the work of Day, Allen, Shepard, and others, it would seem probable that many of the volcanic gases are acid when given off but are in unstable equilibrium, and could not have preserved this acid character after having been long in contact with the surrounding rocks. It is believed that they were in small part oxidized to sulphates, for instance, but in larger part they were composed of hydrogen sulphides, alkaline sulphide, and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of double alkaline sulphides as important constituents of the solution probably holds good. The writer wonders if progress would not result from an attack on the problem in steps, the steps to contribute to the attack on the whole. The initial step would deal with the simpler bodies of supposed magmatic (hydrothermal) origin, that is, those composed essentially of silicates, oxides, sulfates, and sulfides. The following discussion attempts to develop one step of a method that was proposed on a more comprehensive scale in 1929 by the writer and W. S. Burbank.3 The accompanying partial table (Table I) of the electromotive series is from a table distributed by Merck & Co. Inc., manufacturing chemists, prepared in turn from Fundamental Chemistry.& The electromotive arrangement brings together elements that in hypogene ore deposits occur: 1) in oxygen combination only; 2) in combination with sulfur as well as with oxygen; and 3) as sulfides, arsenides etc., and as native metals, see Table 11. The writer clearly recognizes that he is not qualified to discuss the formation of ore deposits as a chemical problem, but he feel that some of the relations that are met by the geologist can well be stated with the hope that the chemical explanation will be forthcoming. By consideration of a group including mainly the elements oxygen, hydrogen, sulfur and iron, complications are avoided, especially with elements of the lower electromotive group. The results can only contribute to the solution of the problem, not to the completion of it. The pH and Eh of the solutions and also temperature probably determine what minerals form. The mineral groups that contain elements high in the electromotive series are alumino-silicates, titanites, simple silicates, spinels, oxides, carbonates and sulfates, in all of which the elements are combined with oxygen. These groups are also recognized as the general order of temperature at which the minerals start to form, see Table 11. At low temperature are sulfides, arsenides, antimonides, sulfo-salts, and native metals, in all of which the elements are characteristically not combined with oxygen. The intermediate temperature group contains elements that form both oxygen compounds and sulfur compounds.

Jan 1, 1957

By R. A. Greenkorn, R. C. Smith

Hele-Shaw cells are used to model creeping flow through porous media (where Darcy&apos;s law is valid). The effects of inertia on flow about obstructions in a Hele-Shaw cell can be calculated by a perturbation method if one can determine a solution to Laplace&apos;s equation. Results of a computer solution for flow about circular, square and elliptical obstructions are presented. These results show that or a modified Reynolds number of less than I, the inertia terms are small; and for values of less than 3, the average streamline predicts the ideal flow. Therefore, the analogy might be used for studying flow in porous media up to a modified Reynolds number of at least 3. INTRODUCTION The nature of fluid flow in porous media is of interest in the fields of soil mechanics, ground water flow, petroleum production, filtration and flow in packed beds. Because it is very difficult to study the phenomenological behavior of flow in porous media, homologs and analogs are used to study flow characteristics. A Hele-Shaw model, made of two closely spaced plates - usually glass — is often used as an analogy to two-dimensional flow in porous media. Hele-Shaw2 showed experimentally that the streamline configuration for creeping flow around an obstacle located between two closely spaced parallel plates is the same as for two-dimensional, ideal flow about the same obstacle. Stokes7 verified these observations mathematically. The usual equation of motion for flow in porous media is Darcy&apos;s law. The form of the mathematical statement of Darcy&apos;s law is identical, within a multiplicative constant, to the expression for the average velocity over the plate gap in the plane of a Hele-Shaw model. These models may be used to describe flow in both homogeneous and heterogeneous porous media. In the mathematical proof of the Hele-Shaw analogy it is assumed that the convective terms in the Navier-Stokes equations are negligible and that the equations of motion degenerate to Laplace&apos;s equation, with pressure the dependent variable. Whenever a Hele-Shaw model is used as an analogy to flow in porous media, .the validity of this assumption is in question. Riegels5 showed that if convection is not neglected, the velocity distribution around a cylindrical obstruction in the flow field depends on a Reynolds number, the plate spacing, and a dimension characteristic of the obstacle. Riegels&apos; solution, a perturbation solution, uses the boundary condition that the flow rate into the obstacle averaged over the plate gap at any point on the obstacle is zero. The method requires that a solution to Poisson&apos;s equation for the perturbation pressure be found. Riegels evaluated this solution for the case of the cylindrical obstruction. His method may be simplified by eliminating the need for solving Poisson&apos;s equation for the perturbation pressure. Instead, an analytic expression for the perturbation pressure gradient is obtained (valid for arbitrary shapes) and used to eliminate pressure from the equations for the perturbation velocities. The results show, for symmetrical shapes, that if NRe < 1, the convective acceleration terms are small, and that the average velocities represent ideal flow up to at least NRe = 3, where: L is a characteristic dimension of the obstacle perpendicular to flow, b is the plate spacing, u is viscosity, v, is velocity of approach and p is density. THEORY* Incompressible fluid flow through a Hele-Shaw model and a porous medium are analogous because the equations for the average velocity components in two-dimensional flow are identical if:

Jan 1, 1970

By George F. Learning

TOTAL DIRECT IMPACT The uranium mining industry&apos;s principal economic impacts on the Texas economy are the result of three flows of money from the industry into the remainder of the state&apos;s economy. These three are: (1) money paid to individuals (personal income) ; (2) money paid to other businesses (business income); and (3) money paid to state and local governments (government revenues). As these direct payments from the uranium industry to various other sectors of the Texas economy subsequently circulate and recirculate within the state, the indirect effects of uranium mining&apos;s direct impacts multiply to reach amounts significantly higher than the direct income flows alone. Over the past decade, the uranium mining industry has substantially increased its role as a provider of jobs, personal income, business income, and government revenues in Texas. The growth has come almost exclusively in a largely rural, seven-county area that lies within the triangle formed by the Laredo, San Antonio, and Corpus Christi metropolitan areas. The uranium mining industry, in fact, has been the major dynamic element in this rural area despite relative stagnation in most of the region&apos;s other basic economic sectors. Over the three years from 1976 to 1978, the South Texas uranium mining industry directly contributed a total of $115 million to the economy of the seven- county region in which it operated and $164 million to the economy of the entire state of Texas. In 1979 alone, the total direct contribution of the industry to the Texas economy had climbed to $124 million in personal, business, and government income. PERSONAL INCOME IMPACT In the period from 1976 through 1978, the South Texas uranium mining industry provided an average of $12.5 million in personal income each year directly to residents of Atascosa, Bee, Duval , Karnes, Live Oak, McMullen, and Webb counties -- the seven Texas&apos; counties that make up the South Texas Uranium Belt. A1 though 84 percent of this resulted from the employment of area residents in uranium industry jobs, some amounts were also provided by the payment of rents and royalties to land owners for the use of their land and mineral rights in uranium mining operations. In 1979, the uranium industry provided approximately $38 million to residents of the Uranium Belt and the rest of Texas. This was more than double the average of $16.1 million provided to Texas residents during the 1976 to 1978 period. The full importance of the uranium industry as a source of personal income, however, should not be reckoned merely by the amount of wages and salaries that it pays directly to its own employees, nor by its rent and royalty payments paid directly to land and mineral rights owners living in Texas. The added payments that the industry makes directly to other Texas businesses and state and local governments in Texas are themselves converted into personal income as those business firms and government units in turn pay their employees. All of the direct income payments made by the uranium industry circulate and recirculate within the state&apos;s economy, multiplying their impact as they go, until they eventually all leak out of the state as federal taxes or as payments to individuals or businesses located outside of Texas. The combined circulation and recirculation of the direct personal, business, and government income that was provided by the-uranium industry in Texas during 1976, 1977, and 1978 resulted in an average annual amount of indirect personal income of more than $83 mill ion. This alone was $20 mill ion more than the industry&apos;s average annual sales during the same years. The total of combined direct and indirect personal income contributed to the Texas economy by the uranium mining industry in that same three-year period thus averaged almost $100 million annually. In 1979, the amount of indirect personal income contributed to the Texas economy by the circulation of uranium mining&apos;s direct contributions had risen to about $196 million, more than double the average of the previous three years. The combined direct and in- direct personal income impact in 1979 thus amounted to $234 million. BUSINESS INCOME IMPACT The income provided directly to other Texas business firms through the purchase of needed goods and services by the uranium industry has been twice as big as the industry&apos;s payrolls. In 1976, 1977, and 1978, the South Texas uranium industry spent an average of almost $36 million each year to buy both goods and services from other Texas businesses. By 1979, this direct contribution to the Texas economy had swollen to $76 million. The biggest share of the uranium industry&apos;s payments to other businesses have gone to contracting firms, including both construction firms and those providing specialized mining services. In the past four years, about 40 percent of the direct payments made by Texas uranium producers to other Texas firms have been to contractors. Texas wholesale and retail firms have also shared in the business sales provided by the South Texas uranium mining industry. Over the past four years, Texas wholesale and retail trade businesses have accounted for about 34 percent of the uranium mining industry&apos;s purchases from other Texas businesses. Public utilities firms have received another six per- cent, while Texas manufacturers and transportation firms have accounted for about five percent each. The other sectors of the state&apos;s economy, including other mineral industries, agriculture, finance, insurance, real estate, and services, have accounted

Jan 1, 1980

By B. M. Larsen

AN increasing amount of attention is being paid to the possible influence of oxygen, in its several modes of occurrence in steel, upon some of the properties of the metal; but clearly investigations along this line are unlikely to yield significant results until reliable analytical methods for the determination of oxygen have been established. This paper presents some results of a study of an improved Ledebur method which aims to determine a definite portion of the oxygen; namely; that which presumably is present in diffusible form in the. solid steel. These more or less preliminary results lead us to believe that the oxygen so determined has some significance; their presentation at this time will, we hope, stimulate discussion of, and focus attention upon, certain rather neglected aspects of the problem. Considerable work has been done recently on methods of estimating inclusions and on the vacuum-fusion method for oxygen; with results which, however, are of somewhat questionable significance. It is commonly presumed that the oxygen in a bath of molten steel in a furnace is present partly as a separate phase consisting of suspended particles of oxides or silicates, partly in solution, the latter being probably the more important. Upon addition of a deoxidizer, it reacts with some portion of the dissolved oxygen and precipitates it as additional suspended particles; the oxygen not eliminated in this way, which remains in solution in the liquid steel, may be regarded indifferently either as dissolved oxygen or as dissolved FeO. When the steel is poured, some of the suspended particles rise towards the surface, others remain trapped in the finished steel, appearing as nonmetallic inclusions in amounts corresponding usually to about 0.01 to 0.03 per cent 02 in the steel. The dissolved oxygen may be partly eliminated as CO during freezing of the ingot, but some remains either in solution or in part precipitated as FeO. Finished steels may thus contain oxygen in several forms: (1) In non-metallic inclusions which are probably quite insoluble in the solid metal at all temperatures; (2) in solid solution which at lower temperatures may be supersaturated; (3) in FeO particles produced by relief of this

Jan 1, 1932

By John C. Gifford, Charles L. Thomas

A unique and reproducible method is presented for the determination of water vapor in tough pitch wire bar copper. The procedure involves reduction of the water vapor with molten aluminum to form hydrogen, which is subsequently measured by mass spectroscopy. Average water vapor pressures within the porosities of the wire bar samples are calculated. Correlation is to exist between the specific gravities of the samples and their measured water vapor contents. The method should find application as a very sensitive means of detecting hydrogen embrittlement in copper. The nature and quantity of gases evolved and retained during the horizontal casting of tough pitch wire bar copper have long been of interest to the metallurgist. Considerable work has been done at this laboratory on the determination of these gases. The work has involved not only qualitative but also quantitative analysis, so as to provide a basis for a total accounting of the porosity which is associated with the cast product. From a knowledge of the gas-forming elements within the copper, and the practice of melting and protecting it with a reducing flame followed by contact with a charcoal cover in the casting ladle, the gases which one might expect to find in the pores of the cast product are sulfur dioxide, carbon monoxide, carbon dioxide, hydrogen, and water vapor. Hydrogen sulfide, nitrogen, and hydrocarbons would be other possibilities; however vacuum fusion-mass spectroscopy techniques employed at this laboratory have shown that no hydrogen sulfide and only traces of nitrogen and methane are present. It is highly improbable according to phillipsl that any sulfur dioxide could be evolved in wire bar copper with 10 ppm or less sulfur under normal freezing conditions. Mackay and smith2 have noted that porosity due to sulfur dioxide only becomes noticeable at concentrations above 20 ppm S. Investigation of carbon monoxide and carbon dioxide by a variation in the method of Bever and Floe showed that these two gases could only account, at 760 mm and 1064°C (Cu-Cua eutectic temperature), for a maximum of about 25 pct of the total porosity in a wire bar having a specific gravity of 8.40 g per cu cm. phillips&apos; has noted that no normal furnace atmosphere is ever sufficiently rich in hydrogen to cause porosity in copper from hydrogen alone. In addition, using a hot vacuum extraction technique for hydrogen,4 values have never been observed in excess of 10 ppb in tough pitch wire bar. On the basis of the preceding considerations of gases in tough pitch wire bar, only water vapor is left to account for the major portion of the porosity. Direct determinations of water vapor are virtually impossible at low concentrations by any presently known technique, due to adsorption and desorption within the walls of the apparatus used.5 The present investigation deals with a method for the determination of water vapor by an indirect procedure, using molten aluminum as a reducing agent to form hydrogen according to the reaction: 2A1 + 3H2O — A12O3 + 3H2 The evolved hydrogen can then be measured quantitatively by mass spectroscopy. EXPERIMENTAL A 10-g piece of 99.9+ pct A1 was charged into a porous alumina crucible (Laboratory Equipment Co., No. 528-30). Fig. 1 shows the crucible in place at the bottom of an 8-in.-long quartz thimble. A funnel tube with two l1/8-in.-OD sidearms extending at a 90-deg angle from each other was attached to the top of the thimble. One of the sidearms was joined to the inlet system of the mass spectrometer (Consolidated Electrodynamics Corp. Model 21-620A) via a mercury diffusion pump situated between two dry-ice traps. The copper samples were placed in the other sidearm, followed by a glass-enclosed magnetic stirring bar for pushing the samples into the crucible. All ground joints were sealed with vacuum-grade wax. The entire system was evacuated and the aluminum was heated with a T-2.5 Lepel High Frequency Induction Furnace for 21/2 hr at a temperature visually estimated to be 900°C. The temperature was then lowered and the hydrogen was monitored on the mass spectrometer until it was given off at a constant rate of about 4 to 5 1 per hr. This rate corresponded to a slope of 2 to 3 divisions per min on the X3 attenuation of a 10-mv recorder at a hydrogen sensitivity of approximately 100 divisions per 1. A micromanometer (Consolidated Electrodynamics Corp. Model 23-105)

Jan 1, 1969

By D. M. Beeson, G. D. Ortloff

Water-propelled banks of carbon dioxide recovered both high- and low-viscosity crude oil substantially in excess of that recovered by water flood in linear flow model experiments. The increase in oil recovery is explained by oil swelling and viscosity reduction. Additional oil was recovered by solution gas drive at the end of the carbon dioxide floods when the model systems were depres-sured. This study was an investigation of the use of a water-driven carbon dioxide bank to recover crude oil. Techniques involving the injection of carbon dioxide have aroused con-siderable interest in recent years among methods considered for increasing oil recoveries. A number of investigators have studied the process in the laboratory1-&apos; and in the field.7,5 Laboratory studies referenced indicate that carbon dioxide in conjunction with water flooding recovers more oil than does water flooding alone. These re- ports diverge widely, however, in stating magnitude of improvement. We believed that a water-driven carbon dioxide bank would increase recovery of crude oils by two mechanisms: viscosity reduction and oil swelling. Due to reduction in the oil viscosity caused by solution of carbon dioxide, displacement efficiency should be improved. In addition, the residual oil should be highly swollen by the carbon dioxide held in solution. Thus, the final residual oil saturation, in terms of stock-tank oil, would be lower than in the absence of carbon dioxide. To test this hypothesis, experi-

By E. P. Mathewson

DURING the past 35 years it has been my privilege to deal with hundreds of recent graduates from engineering schools all over the world. In consequence, I, feel that I have learned something about the training of, engineering students. In the first place, I believe that too great specializa-tion is a mistake. A student should receive general training in engineering for at least three out of the four years of the course, and any specializing that may be required should come in the fourth year. Too great emphasis can not be laid upon the fact that the four years&apos; training does not make an engineer; on the contrary, the graduate is only fitted to enter the pro-fession. He becomes an engineer in the true sense of the word only after years of practice; the college train-ing merely shows him where to look for information and develops his intellectual powers. Some of our engineering schools have lengthened the term of study to five years and talk of increasing it still further. This, in my opinion, is a mistake. A young man who spends more than four years in college is apt to become too academic and theoretical. It is better to stiffen the matriculation examinations than to prolong the years of study in college. No matter how good the faculty may be and how carefully selected the course of study, the graduate can never become an engineer unless he has some natural qualifications for the vocation. There are one or two subjects in which most recent graduates seem to be weak; these are accounting, the command of English, and training in the writing of reports. A short course in general accounting should always be included in the curriculum. To this should be added instruction in the preparation of estimates and cost statements. In making reports it should be borne in mind that these reports are to be submitted to busy men,-and not to technical men. The busy man wants the gist of the report summarized on the front page of the report. He wants to know that if he expends a certain sum of money in a certain way, he will get certain results and make so much profit. This should be put clearly before him in short statements, free from technical terms. The details of the report can follow .at greater length; it should be remembered that the employer is not going to read these details, but will confine his attention to the summary.

Jan 1, 1923

By N. J. Olson, G. W. Toop

A series of equations previously derived for calculating ternary thermodynamic properties using binary data has been applied to the problem of predicting ternary phase diagrams and quaternary excess free energy. The methods are considered to be rigorous for regular ternary and quaternary systerns and empirical for nonregular systems. The equations have been used to predict ternary phase boundaries in the Pb-Sn-Zn system at 926°K and the Ag-Pd-Cu system at 1000ºK. Calculated quaternary excess free-energy values are presented for the Pb-Sn-Cd-Bi system at 773°K. A method for predicting the location of ternary phase boundaries would be a useful supplement to experimental measurements in ternary systems. This has been recognized with the considerable work that has been done to find models to predict or extend thermodynamic properties and phase diagrams in binary and ternary systems1-18 for which direct experimental measurements are limited. With the access to highspeed digital computers and mechanical plotting devices, it is currently rather easy to compare mathematical models with experimental data. The regular-solution model is consistent with systems which exhibit negative heats of mixing, positive heats of mixing, and miscibility gaps, and therefore it is applicable to simple phase diagrams. The purpose of this paper is to illustrate the use of regular-solution equations to predict, empirically, phase equilibria in some types of nonregular ternary systems. Corresponding equations for regular quaternary systems are given and used to calculate empirical quaternary excess free-energy data. METHOD FOR PREDICTING THE LOCATION OF TERNARY PHASE BOUNDARIES USING BINARY DATA Meijerin1,6 has used the regular-solution model to calculate common tangent points to ternary free energy of mixing surfaces and hence to determine phase boundaries in ternary systems involving miscibility gaps. He used the following equation to calculate ternary excess free energy of mixing values: stants characteristic of the binary solutions, and Ni is the mole fraction of component i. An alternate expression which gives for regular solutions as a function of binary values of along composition paths with constant N1/N2, N2lN3, and N1/N3 may also be derived:15 ternary r xs 1 ?c-*n.Ti*.U*. This expression for is more useful for the empirical calculation of ternary excess free-energy values for nonregular systems because actual binary AFXS data may be used in the expression rather than attempting to find suitable constants for Eq. [I]. The results of this feature of Eq. [2] are illustrated in Table I where calculated excess free-energy values for the Ni-Mn-Fe system at 1232°K are compared with experimental data of Smith, Paxton, and McCabe.19 Although regular-solution equations have been shown to give calculated thermodynamic quantities which agree quite well with experiment for single-phase nonregular ternary systems,14,15 care should be exercised in the use of the equations to predict thermo-dynamic properties of multiphase ternary systems in which strong compound formation is suspected. This precaution is consistent with the simple regular-solution model which for negative values of ai_j will indicate a tendency toward compound formation but even for very large negative values of ai-jwill not give multiphase binary or ternary systems involving a distinct stable compound. Hence, calculated ternary free-energy data using Eq. [2] might be expected to vary between being rigorous and poor, in the following order, for ternary systems which are: a) regular solutions, b) nonregular single-phase liquids in which random mixing is nearly realized, c) nonregular single-phase solids, d) nonregular multiphase systems exhibiting miscibility gaps, e) nonregular multiphase systems with binary compounds but no ternary compounds, f) nonregular multiphase systems with highly stable binary and ternary compounds. The calculated data will be expected to be least accurate for the last two cases. The general method adopted in this paper involves two-dimensional plots of ternary activity curves. The principle used is that tie lines indicating two-phase equilibria join conjugate phases a and B for example, for which a1(a) = a1(B), a2(a) = a2(B), and a3(a) = a3(B). Tie lines may be determined by plotting the ternary activities of two components along an isoactivity line for the third component and the unique points where the above equalities hold may be found graphically.

Jan 1, 1970

By K. E. Brown, A. R. Hagedorn

Continuous, two phase flow tests have been conducted during which four liquids of widely differing viscosities were produced by means of air-lift through 1%-in. tubing in a 1,500-ft. experimental well. The purpose of these tests was to determine the effect of liquid viscosity on two-phase flowing pressure gradients. The experimental test well was equipped with two gas-lift valves and four Maihak electronic pressure transmitters as well as instruments to accurately measure the liquid production, air injection rate, temperatures, and surface pressures. The tests were conducted for liquid flow rates ranging from 30 to 1,680 BID at gas-liquid ratios from 0 to 3,-270 scf/bbl. From these data, accurate pressure-depth traverses have been constructed for a wide range of test conditions. As a result of these tests, it is concluded that viscous effects are negligible for liquid viscosities less than 12 cp, but must be taken into account when the liquid viscosity is greater than this value. A correlation based on the method proposed by Poettmann and Carpenter and extended by Fan-cher and Brown has been developed for 1¼-in. tubing, which accounts for the effects of liquid viscosity where these effects are important. INTRODUCTION Numerous attempts have been made to determine the effect of viscosity in two-phase vertical flow. Previous attempts have all utilized laboratory experimeneal models of relatively short length. One of the initial investigators of viscous effects was Uren1 with later work being done by Moore et al.2,3 and more recently by Ros.4 However, the present investigation represents the fist attempt to study the influence of liquid viscosity on the pressure gradients occurring in two-phase vertical flow through a 1¼-in., 1,500 ft vertical tube. The approach of some authors has been to assume that all vertical two-phase flow occurs in a highly turbulent manner with the result that viscous effects are negligible. This has been a logical approach since most practical oil-well flow problems have liquid flow rates and gas-liquid ratios of such magnitudes that both phases will be in turbulent flow. It has also been noted, however, that in cases where this assumption has been made, serious discrepancies occur when the resulting correlation is applied to low production wells or wells producing very viscous crudes. Both conditions suggest that perhaps viscous effects may be the cause of these discrepancies. In the first case, the increased energy losses may be due to increased slippage between the gas and liquid phases as the liquid viscosity increases. This is contrary to what one might expect from Stokes law of friction,&apos; but the same observations were made by ROS4 who attributed this behavior to the velocity distribution in the liquid as affected by the presence of the pipe wall. In the second case, the increased energy losses may be due to increased friction within the liquid itself as a result of the higher viscosities. The problem of determining the li- quid viscosity at which viscous effects becomes significant is a difficult one. Ros4 has indicated that liquid viscosity has no noticeable effect on the pressure gradient so long as it remains less than 6 cstk. Our tests have shown that viscous effects are practically negligible for liquid viscosities less than approximately 12 cp. Actually there is no single viscosity at which these effects become important. These effects are not only a function of the viscosities of the liquids and of the gas but are also a function of the velocities of the two phases. The velocities in turn are a function of the in situ gas-liquid ratio and liquid flow rate. Furthermore, the role of fluid viscosities in either slippage or friction losses will depend on the mechanism of flow of the gas and liquid, i.e., whether the flow is annular. as a mist, or as bubbles of gas through the liquid. These mechanisms are also a function of the in situ gas-liquid ratios and the flow rates. It would thus seem that the best one could hope for is to determine a transition region wherein the viscous effects may become significant for gas-liquid ratios and liquid production rates normally encountered in the field. The viscous effects might then be neglected for liquid viscosities less than those in the transition region but would have to be taken into account when higher viscosities are encountered. There are numerous instances where crude oils of high viscosity must be produced. The purpose of this study has been to evaluate the effects of liquid viscosities on twephase vertical flow by producing four liquids of widely differing viscosities through a 1 % -in. tube by means of air-lift. The approach used in this study was as follows:

Jan 1, 1965

By B. M. Larsen, T. E. Brower

An increasing amount of attention is being paid to the possible influence of oxygen, in its several modes of occurrence in steel, upon some of the properties of the metal; but clearly investigations along this line are unlikely to yield significant results until reliable analytical methods for the determination of oxygen have been established. This paper presents some results of a study of an improved Ledebur method which aims to determine a definite portion of the oxygen; namely, that which presumably is present in diffusible form in the solid steel. These more or less preliminary results lead us to believe that the oxygen so determined has some significance; their presentation at this time will, we hope, stimulate discussion of, and focus attention upon, certain rather neglected aspects of the problem. Considerable work has been done recently on methods of estimating inclusions and on the vacuum-fusion method for oxygen; with results which, however, are of somewhat questionable significance. It is commonly presumed that the oxygen in a bath of molten steel in a furnace is present partly as a separate phase consisting of suspended particles of oxides or silicates, partly in solution, the latter being probably the more important. Upon addition of a deoxidizer, it reacts with some portion of the dissolved oxygen and precipitates it as additional suspended particles; the oxygen not eliminated in this way, which remains in solution in the liquid steel, may be regarded indifferently either as dissolved oxygen or as dissolved FeO. When the steel is poured, some of the suspended particles rise towards the surface, others remain trapped in the finished steel, appearing as nonmetallic inclusions in amounts corresponding usually to about 0.01 to 0.03 per cent Oz in the steel. The dissolved oxygen may be partly eliminated as CO during freezing of the ingot, but some remains either in solution or in part precipitated as FeO. Finished steels may thus contain oxygen in several forms: (1) In non-metallic inclusions which are probably quite insoluble in the solid metal at all temperatures; (2) in solid solution which at lower temperatures may be supersaturated; (3) in FeO particles produced by relief of this

Jan 1, 1932

By George W. Friesen

This paper presents the historical trend and de- fines the causes of drilling cost escalation in the Gulf of Mexico during the 1970&apos;s. The three major components of escalation are: 1) inflation, 2) supply-demand imbalance (demand pull) and 3) decreases in drilling efficiency. The decade was divided into three periods. During each period one component of escalation was responsible for most of the rise in costs. From 1970 through 1973 only inflation pushed costs upward. During 1974 and 1975 a supply- demand imbalance caused most of the escalation. Since 1975, decreases in drilling efficiency have produced the major component of escalation. During any one year or period of years, the sum of the three components will give the total escalation rate. The reasons why different components contribute more toward escalation during certain years than others are shown by following the timing of oil and gas price increases, the overall quality of the acreage offered each year in offshore lease sales and the resulting drilling activity.

Jan 1, 1982

By W. R. Ingalls

WHAT proportion of the national wealth is represented by&apos; the producing mines of the country?&apos; Or by the- mining and metallurgical industry-as a whole, for it is impossible to make-an economic distinction between the mines that produce the ore and the plant that is used to get the metals from it. The total national wealth in fixed property is about $270,000,000,000. How much for the mines? I do not know that any one &apos;else has ever tried to furnish answers to these questions. In making such an attempt I am conscious that the result can be nothing more than a rough approximation. Yet even that will give an idea of relative values. No separate valuation for the mines of the country has appeared in any inventory of the national wealth previous to that which I compiled and published for 1916. -In earlier census estimates mines were supposed to be included under the head of real estate. However, an examination of the laws and practices of the several states with respect to mine taxation will make it evident that no good idea of the value of the mines of the coun¬try is obtainable from the assessment rolls. In my previous estimate for 1916, I computed the value of the mines at $8,000,000,000, which was approxi¬mately 10 times their net income as reported to the Bureau of Internal Revenue. In making that estimate I fell grossly into error, for several reasons that it is unnecessary to explain, but chiefly because the net income of the mines of the country in that year was exceptionally large. The whole subject of valuing the mines of the country en bloc is extraordinarily difficult At the best, no one can hope to arrive at, anything more than a rough idea about it. However, elements of reason may be introduced and may be made to serve as chief bases.

Jan 1, 1921

With only one certain exception coal was never used by the Indians, before white men came to America, for any purpose except as an ornament or for paint. Within the past few years it has been discovered that the Hopi Indians in Navajo County, Arizona, used lignite for burning pottery, about 1000 A. D., as dated by tree rings. They were able to obtain a clear color in their ware that could not be obtained with brushwood fires. The coal was mined by hammers from outcrop openings, some of which can still be seen, and the tools used have been found in them.1 (See also p. 376.) Small figurines made of splint or cannel coal have been found at various localities in western New York, in Ohio and possibly other places, evidently made for ornaments. There is no reason to think they are of any greater age, if as old, as that mentioned above. Some crushed coal was used by the Indians as a black pigment in painting themselves, but apparently the eastern Indians never used coal for any other purposes. Some think that several tribes of Indians in the Northwest, along the Missouri, used coal as fuel, the basis being a statement attributed to Radisson about 1660. In the Jesuit Relations of 1659-1660 it was stated that Radisson anti Groseilliers had just returned from a visit to Lake Superior and beyond. "In the country of the Poualak, which means &apos;warriors&apos; they say `as wood is scanty in supply and small in size in their country, nature has taught them to make fire with coal from the earth (charbon de terre) and to cover their cabins with skins.&apos;"2 This statement was only hearsay with the good fathers, and the reputation for veracity of the two explorers is not of the best, and it is extremely probable that instead of coal they used turf, dry grass or buffalo chips. In fact in Radisson&apos;s Voyages&apos; he does not mention coal at all in his account of the third voyage, when he was supposed to have seen it used. His accounts of his travels are badly mixed, and he and his companions were much better travellers than narrators. None of the early travellers up the Missouri River saw any evidence even then that the Indians were familiar with the use of coal. In the writer&apos;s opinion it is unlikely that coal was used as stated by the Jesuits.

Jan 1, 1942