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By R. R. Hawkins

PEoperly designed tubing strings make it possible to continue the flowing life of wells beyond the stage where ordinarily they would be put to pumping. Wells no longer able to flow through 2-in. tubing can be made to produce through smaller tubing if conditions within the well are carefully studied and correctly designed strings are installed. In this way, pumping expense may be postponed and in some pools it is within reason that the entire recovery may be obtained by natural flow if maintenance of pressure is practiced. Infrequent tubing changes would be necessary but their cost would be much less than that of installing and maintaining pumping equipment. If small wells are to be made to flow naturally, careful consideration must be given the actual lifting mechanics within the string, so that fairly accurate knowledge of reservoir conditions, especially pressure, is essential. Wells producing between 5 and 25 bbl. daily are classified here as "small wells." Exponential Flow A maximum of the energy contained in the expanding gas must be employed to do useful work if natural flow is to be continued. It is evident that adiabatic expansion would defeat this purpose, therefore the velocity of the gas must be held down to a minimum in order that isothermal expansion may be approached. Of course, true isothermal expansion would not be obtainable in an oil well, hence the use of the term "exponential." 1 Obviously the closer the approach to isothermal expansion, the more efficient the lift. Experiments by the U. 8. Bureau of Mines² have shown that for isothermal expansion to take place in a gas well where water is being produced, a definite relationship exists between the depth of the well and the minimum operating pressure. The latter must be such that the tubing fill-up, if static conditions prevailed, would be equivalent to 14 per cent of the distance between the top of the fluid inside the tubing and the tubing head. It has been observed that variations in this essential ratio

Jan 1, 1932

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 G. L. Oldright

THE metallurgist is familiar with the rapid development of concentration -by flotation and smelting in the reverberatory in recent years, brought 'about chiefly by the exhaustion of' bodies of .rich, coarse, direct smelting ore. Geologically speaking, in many porphyry-copper districts, the richer contact or replace let deposits surrounding 'the main ore-forming igneous intrusion have been exhausted, and it is necessary to beneficiate the copper minerals disseminated throughout the mass of the intrusion itself. The organization of great companies to treat such low- grade ores on a large scale and the practices resulting from the necessity for an economic method of treatment 'are among the most prominent metallurgical developments of the past decade. It is interesting to note the effect of the present trend of practice on the inter-relationship of the concentrator and smelter, on the constituents of the smelter charge, and on smelting in general.

Jan 1, 1925

By C. P. PERIN, DONALD BELCHER

T HE production of pure iron by electrolyzing solutions of its salts has been the object of scientific curiosity and research for about 80 years; and in the last two decades a realization of the unusual physical and chemical qualities of electrolytic iron has turned the attention of chemists and metallurgists toward a commercial application of this accumulated knowledge. Thus Burgess and Hambuechen in America, . Cowper-Coles in England, and Fischer in Germany- devised methods, more or less successful, for the electrolytic refining of iron, but none of these processes has yet attained large-scale operation. During the war some interesting ,work was done in France and England on building up worn or defective machine parts by electrodeposition of iron. It remained for the Société "Le Fern in France to carry on the process commercially. For six years Les Fonderies et Forges. de Sainte-Maire et Gravigny and the works of Bouchayer & Viallet at Grenoble have manufactured pure-iron boiler tubes in competition with established practice. The French process originated in the researches of Anthelme Boucher in 1910, and was, not put into operation until several years of experimentation had passed.

Jan 1, 1921

By L. W. Emery

Undergrorlnd combustion operations were initiated in a 60-acre Bartlesville sand "shoe-string" reservoir in Allen Connty, Kans., in 1956. Tests in separate patterns were conducted using various co~nbinations of air and recycle gas to propagate combustion fronts from the injection toward the producing wells. These patterns were made up of 6 injection and 20 prodrrcing wells Gas and liquid prorluctiorz from each pattern was measured on an individual-well basis, and comparisons were made between the three patterns to ascertain the relative effects of injected gas composition on production behavior. Breakthrough of the combustion front at a well was characterized by an increase in water production from the well followed by an increase in bottomhole temperatrrre to approximately 250" F. After burning fronts had broken through at five producing wells, operations were terminated in 1960. From the total project approximately 79,000 bbl of oil were produced during thermal operations at a cumulative produced GOR of 23 Mcf/bbl. No appreciable change in the character of the produced crude was observed. Combustion in the reservoir was maintained with injected gas compositions ranging fronz 6 per cent oxygen in recycle gas to 100 per cent air. lnjectiotz of large quantities of recycle gas resulted in higher producing GOR's from offset wells than were measured from a pattern into ~vhich straight air ~vas injected. The air required to move the combustion front through I acre-ft of reservoir was computed to be 20 MMscf. This valrre was found to be relatively independent of the quantities of recycle gas injected. The recovery efficiency from the swept area was esti~izated to be about 59 per cent. Areas swept were similar in shape to tlzose obtained with a laboratory potentiometric model. Samples of sund taken from behind the burning front by coring indicated almost total oil removal from the sand. Petrographic analysis of the core samples indicated that the sand had been heated to peuk temperature of rlbout 1,200" F. No rignificant difference in peak temperature was forrnd in two areas where compositions of injected gas were quite different. Compression costs for thermal recovery were estimated to be $1,20/bhl of produced oil. INTRODUCTION The use of the "forward combustion" process as an oil recovery method has received a great deal of attention. This method involves ignition of the formation in an injection well, followed by propagation of a combustion front through the reservoir. Combustion is maintained by the injection of an oxygen-containing gas to react with reservoir hydrocarbons. As the flame front progresses through the reservoir, oil and formation water are vaporized, driven forward in the gaseous phase and recondensed in the cooler part of the formation. In turn, the condensed fluids push oil into the producing wellbores. Completed field tests of the process were first reported by Kuhn and Koch,' and by Grant and Szasz.' Results from other tests have since been reported by Walter,3 by Moss, White and McNeil,' and by Gates and Ramey." ach of these tests essentially utilized a single injection well surrounded by four or more producing wells. Sinclair Research, Inc., elected to do field experimental work using a number of test patterns in a single field in order that comparisons between various operating schemes could be made. The site selected and purchased in 1955 for this experimental work was a 60-acre Bartlesville sand reservoir located in Allen County, Kans. Combustion operations were initiated in mid-1956. Between that time and termination of the project in mid-1960, combustion fronts were propagated from injection wells to producers in three separate well patterns, using different mixtures of air and recycle gas. The test was terminated before sweep of the three patterns was complete so that information about the effect of combustion on the swept areas could be obtained by coring. Results from the test in the form of injection and producing well performance have been carefully recorded, and these form the general basis for this paper. DESCRIPTION OF RESERVOIR The reservoir in which the combustion tests were conducted is a Bartlesville sand "shoe-string", typical of a number of small reservoirs in Southeastern Kansas. Average reservoir characteristics are shown in Table 1. Fig. 1 is an isopachous map of the producing sand showing the reservoir to be approximately 400-ft wide and 2,500-ft long. Maximum net productive sand thickness is 21 ft. Fig. 2 shows a typical core analysis obtained by coring with water-base mud. The reservoir has no appreciable dip and is closed on the sides by degradation of sand into shale. The main body of sand is heavily laminated with shale stringers, which are not continuous between wells. The main reservoir is overlain by 30 to 40 ft of laminated low-permeability sand and shale streaks. No information is available on the original properties of

By D. J. Carney, J. Chipman, N. J. Grant

An absolute calibration has been achieved for sampling and analyzing liquid steel for hydrogen based on Sieverts' values of hydrogen solubility in iron. Further checks were made in nickel, iron-nickel, and 18-8 stainless melts. The sampling method was successfully applied to a large number of commercial steel melts in various types of furnaces. The concurrent problem of sample storage was also solved. THE problem of sampling of liquid steel for hydrogen is more difficult than the problem of analysis. Hydrogen has a greater mobility than any other element; it is the only element that will diffuse out of steel at room temperature. In accordance with the known relation between temperature and diffusivity, the diffusion of hydrogen is extremely rapid at the temperature of liquid steel. Consequently, in the past, attempts to quench molten steel to retain the dissolved hydrogen have not been as successful as similar attempts with nitrogen or oxygen. The retention of hydrogen is especially difficult since it will continue to escape at room temperature even if the molten metal has been rapidly quenched. The hydrogen sampling methods may be classified broadly as (1) the rapid quenching techniques which attempt to preserve super saturation and (2) those methods which attempt to collect the gases evolved as the metal freezes and cools to room temperature. With all methods of sampling but especially with the rapid quenching methods, there is also a concurrent problem of storing the sample until analysis is undertaken. The two problems are interrelated and must be considered together when discussing liquid steel sampling techniques. The major obstacle in liquid steel sampling has been that there was no way of evaluating properly the various sampling and storage techniques which have been developed. It has not been possible to compare the accuracy of the various methods. For evaluation of sampling methods some known standard is required; this may be found in the published work on the equilibrium solubility of hydrogen in liquid iron which has been determined in three separate investigations.1,2,3 The data are shown in table I. Sieverts' original method of obtaining gas solubilities involved measurement of the volume of gas required to saturate the liquid metal contained in an evacuated bulb of known volume. This procedure, improved by introduction of high frequency induction heating, has yielded reproducible results which appear to be entirely dependable. Using Sieverts' method, it has been proved for iron and other metals and alloys that the hydrogen solubility is proportional to the square root of the pressure of the hydrogen gas above the liquid, so that one may work with various partial pressures of hydrogen to put different amounts of hydrogen in solution. From Sieverts' law it is possible to know accurately what amount of hydrogen is dissolved in the liquid metal at the time of sampling. The accuracy of a sampling method may be gauged by reference to this known solubility. It was the purpose of this investigation to develop a method for sampling liquid steel and for storing the sample so that the analytical result would represent the actual hydrogen content of the metal bath. For this purpose an induction furnace was

Jan 1, 1951

By K. K. Clark

Excessive injection pressures in water injection wells may create deeply penetrating fractures, or may open up existing reservoir fractures. If these fractures are oriented toward offset producing wells, oil recovery at injected water breakthrough and ultimate recovery will be impaired. A method of calculating fracture lengths from pressure fall-off test data is presented. The method is based on a linear flow model that simulates conditions present during the early-time period after shutting in an injection well. Fracture lengths can be calculated directly if formation permeability is known. A graphical technique is presented that provides fracture lengths based on permeabilities calculated from normal fall-off tests, where those permeabilities are adjusted for flow geometry. Test data from four injection wells and results obtained from applying the method to these wells are discussed. Introduction Rates of water injection into nonstimulated wells in low permeability reservoirs frequently fall below economically desirable levels. Therefore, some form of stimulation such as hydraulic fracturing often is performed on these wells. Usually these fractures penetrate a short distance from the well — short as compared with interwell spacing — and therefore should not create problems of water channeling to offset producing wells. In the past, some operators have been tempted to increase injection pressures continually to maintain a specified injection rate. But pressures cannot be increased indefinitely. Field data indicate that continued injection above fracture opening pressure can cause excessively long fractures to approach between well distances. If these long fractures intersect or closely approach offset producing wells, premature water breakthrough can result. It is difficult to seal effectively these fractures by various workover procedures after premature water breakthrough has occurred. This paper describes testing procedures that are potentially capable of detecting premature water breakthrough before it occurs. Knowledge of fracture lengths and fracture opening pressures can assist field engineers in selecting optimum operating conditions for water injection wells. Fracture lengths should be calculated from pressure fall-off tests on injection wells, and maximum permissible iniection pressures should be determined from step-rate injectivity tests. Equipped with this information, the field engineer is in a better position to recommend for a particular injection well the optimum operating conditions that will lessen the chances of channeling to offset producers. Historically, pressure transient tests have been conducted primarily on producing wells and analysis procedures have been based on radial flow concepts. Several authors have suggested that these same procedures be applied to tests conducted on water injection wells. This application is justified for wells that are not connected to extensive fracture systems. However, if the formation is severely fractured, the interpretation methods must be modified. Several authors have presented the pressure response of various systems that are intended to simulate reservoir conditions. A paper by Russell and Truitt* on vertically fractured svstems is probablv the most useful from the standpoint bf the fieid engineer. Russell and Truitt presented the pressure-vs-time behavior of a well connected to vertical fractures with various fixed lengths. Their permeability adjustment technique is used in this paper to refine methods of calculating fracture length and interwell permeability. Theory and Definitions Three flow-system geometries are considered in analyzing injection well test data. These various geometries are applicable during specific time intervals of transient pressure tests. Schematic drawings of the flow models, and the time intervals over which they are applicable, are shown in Fig. 1 in the chronological order that they are applied to the pressure response of water injection wells in fractured formations. The very early response is simulated by an infinite linear system as shown in Fig. 1A. This representation permits the calculation of matrix surface area exposed to the fracture. The model shown in Fig. 1B is identical with the one studied by Russell and Truitt. They evaluated the transient pressure response of this vertically fractured system by finite difference techniques. The results were presented as tabulations of dimensionless pressure drop functions for a range of fracture lengths. A semilog plot of these data shows that the apparent matrix permeability can be related to the true matrix permeability by a simple exponential function. Their adjustment factor is used in this paper to improve the accuracy of matrix-permeability and fracture-length calculations.

Jan 1, 1969

By R. F. Yap, N. Arbiter, C. C. Harris

A fully-instrumented driving mechanism has been constructed to study the power, aerating and solid suspension characteristics of several laboratory flotation machines. Machines operating over normal flotation speed ranges give substantially constant power numbers in liquid systems indicating that they operate close to fully baffled turbulent flow conditions. Owing to lack of geometrical scaling, power numbers for different sizes of cells of the same make are different. Even larger differences occur between cells of different manufacturers. For a given impeller, varying the tank size did not significantly affect the power consumption. Tank geometry and baffling has a slight effect on power consumption with shrouded impellers. For a given impeller speed, suspension height decreases while power increases with increasing mass of solids in suspension. While power consumption is hardly affected by particle size and clearance between the impeller and tank bottom, the suspension height significantly increases as clearance increases and as particle size decreases. Aeration was found to affect not only power but also the suspension characteristics of the machine. For closely sized particles, drastic sedimentation occurred when a critical value of the air flow number was exceeded. The critical air flow number decreased with increasing particle size. This effect was less marked with a wide particle size range. The self-aerating capacity of flotation machines increases with cell size at a given speed for the same impeller-shroud system, but decreases in the presence of frother and solids. Equations have been established for correlating all of the studied variables. Data taken from the literature were also correlated with these equations. The modern mechanical flotation machine has, over a period of 60 years, displaced other designs to become the dominant type. Once the correct chemical environmental conditions have been established, the major requirement, selective mineral-air adherence, is essentially a function of two operating variables — impeller speed and air rate. The special nature of this dependence is such that in the same apparatus, but under different operating conditions, adherence can be either prevented or destroyed. Another aspect of this observation is that flotation machines though differing in detail to a considerable extent can produce similar metallurgical results. It must be concluded that having determined the correct reagent levels, establishing the correct operating conditions are at least as important as machine design. Since about 1960, after 30 years of fairly stable circumstances, manufacturers have been developing new types of machines whose major feature is emphasis on pulp flow characteristics by virtue of new im-peller-stator designs. As far as can be ascertained, these new designs necessitate radical departures from accepted impeller speed-air rate values. Performance data are still awaited. Flotation machine development has been empirical, as is selection of operating conditions. The purpose of the work at Columbia University has been to elucidate the fundamentals of the subject so that the purely mechanical aspects of the flotation process can be understood in hydrodynamic terms.1-6 Hopefully, this might lead to intelligent selection of a particular machine and its operating conditions for a specific ore based on a minimum of testing, or even to new types of flotation machines. The present investigation is the most comprehensive to date.7,8 Earlier work, which was largely exploratory, has been repeated and extended and employes the most accurate measuring techniques available. Additionally, sufficient hydrodynamic data were obtained under flotation conditions to delineate the relevant operating ranges. Attention has been given to scaling in that several geometrically scaled tanks and impellers have been constructed and tested; it has been pointed out elsewhere that undistorted geometrical scaling rarely pertains in flotation machine design.5 This paper is divided into sections dealing with relevant combinations of the three phases: liquid, air and solid. Summaries of the literature have been given in previous publications2-4 and will not be repeated here. Recently, several reviews of mixing have appeared, which can be usefully referenced.9-11 It is of interest to note that flotation is not included

Jan 1, 1970

By H. M. Otte, A. L. Esquivel

A new leasl-squares method is Presented for determining lattice parameters of hexagonal or tetragonul structures. The method is adapted for use on electronic computers and involves a reiterative procedure. The correction factor employed raries linearly with the lattice parameter, a (determined from the Brag, angle). In contrast, Cohen's method and recent modifications of it use a correction factor that varies incersely as the squure of the lattice paramneter, a. While the recent modifications attempt to improve the precision of the extrapolated lattice parameter, a, (or-cu). by stressing the importance of the weighting factor. the present approach emphasizes the need for choosing the correct extrapolation function. A comparison between the present method (the Linear method) and Cohen's method indicates that the Linear method may be more appropriale in certain cases. through a priori no critertion appears to he available for making a chorce between the methods. The size of hexagonal and tetragonal crystal lattices is determined by two parameters, a, and c,. Although in principle the two lattice parameters can be determined independently from reflections for which h - k = 0 and 1 = 0, respectively, in practice this may be inconvenient (because of the angular positions at which these reflections may occur) or not easily possible (because of low intensity). Furthermore, if a high precision or accuracy is required, the limited number of reflections of this type available, particularly in the high-angle region, is not sufficient for the necessary corrections (mainly due to absorption) to be determined with accuracy. Several methods1-7,11-13 have been proposed employing all reflections, to obtain the optimum values, a. and co, either by a trial and error procedure or a least-squares fit. Of the latter method, cohen's5 is the best known one since it provides explicit expressions for the optimum a. and c,. However, Cohen's method is only strictly valid if an extrapolation function is used that varies linearly with l/a2 or lie2 (see Section 3), a requirement that does not appear to be generally appreciated. On the other hand, all the better known and more widely used A recent trial and error method was proposed by Massalski and King8,7 who computed extensive auxiliary tables of axial ratios vs the functions A = [(4/3)(h2 + hk +k2) + l2+(a/c)2] and C = A(c/a)2 used in computing a and c values from the observed Bragg angles. These values of a and c were then plotted against a function which permitted linear extrapolation. As a criteria; for the "optimum" values, Massalski and King rely upon a visual fitting of the line through points representing reflections of low 1-index points to compute the extrapolated value of ao and high 1-index reflections to obtain CO. The successive computations and graphical plotting required to reach the "optimum" value are quite lengthy and tedious even on a desk calculator and no quantitative assurance is obtained of having in fact selected the optimum value.* If the method of Massalski and King is used on an electronic computer, then their published tables become redundant and a least-squares fit becomes a natural selection for the choice of optimum values. Such an approach will be called the Linear method. For work now in progress on the effect of certain physical variables on the lattice parameters of hexagonal crystals, it has become essential to determine the confidence limits of small changes in the lattice parameters. Since extrapolation functions that varied linearly with a and c actually also appeared to vary linearly with l/a2 or l/c2 when tested against published as well as our data, a comparison of Cohen's method and the Linear method was considered desirable (Sections 3 and 4). For the latter method an electronic computer was required since a reiterative procedure to obtain the optimum ao and co values had to be employed. The purpose of this paper is to describe the principles of the Linear method, illustrate its application, and compare it with Cohen's method. 1) THE LINEAR METHOD The standard practice in obtaining the lattice parameters in the Debye-Scherrer method is to

Jan 1, 1965

By K. M. Myles

The vapor pressure of palladium over a series of Rlz-Pd alloys has been measured by the torsion-effusion method. The thermodynamic properties of the alloy system at 1575=K have been calculated from the vapor pressure data. The activities and the free energies of formation exhibit large positive deviations from ideal behavior. The enthalpies of formation are endother-mic. The entropies of formation are positive and larger than the ideal entropy of mixing. All of the thermodynamic properties suggest that a strong tendency toward phase separation exists in the solid solutions. The possible origin of the phase instability and the various factors that influence the thermodynamic properties are discussed. RECENT studies of the thermodynamic properties of alloys of palladium with nontransition elements have indicated that a significant contribution to the enthalpy of formation is related to the redistribution of the conduction electrons upon alloy formation.'-' The present work was undertaken to ascertain the importance of this contribution in Pd/transition-metal alloys. The Rh-Pd system was chosen for this investigation for several reasons: 1) The thermodynamics of the system were unknown. 2) Rhodium and palladium are completely soluble at high temperatures; below 1118OK the solid solution becomes immiscible.', 3) The difference in magnitude between the vapor pressures of rhodium and palladium permitted the use of an existing effusion apparatus. 4) Additional information was known about the alloy system that would facilitate the interpretation of the thermodynamic results. EXPERIMENTAL PROCEDURE The thermodynamic properties of the Rh-Pd alloy system were calculated from the vapor pressure of palladium over solid palladium and over several solid Rh-Pd alloys. The vapor pressure was measured by means of the torsion-effusion apparatus that has been described previously. In this method, an effusion cell is suspended from a tungsten filament inside a high-temperature furnace. Two orifices are located eccentrically such that the effusion of the vapor creates a rotational torque in the filament. The angle of rotation is directly related to the total vapor pressure within the cell. As the vapor pressures of rhodium and palladium are approximately five orders of magnitude apart," the total vapor pressure was considered to be effectively equal to the equilibrium vapor pressure of palladium. The effusion cells were made from high-purity alumina since auxiliary experiments indicated that essentially no reaction occurs between alumina and solid Rh-Pd alloys. Unfortunately, because the orifices were irregular, an accurate calculation of the Free- man-Searcy correction factors" could not be made. The constants were determined in an independent experiment where the vapor pressure of copper, as measured in the alumina cell, was compared with an accurate value of the vapor pressure, which had been determined previously.4 Depletion of palladium from the surfaces of the specimens was minimal as the deflection of the cell remained constant, for at least 15 minutes, at each of the experimental temperatures. Lattice parameter measurements of the postrun alloys also indicated that no changes in the composition of the surfaces had occurred. The alloys were prepared by arc melting the requisite amounts of the 99.99 pct pure elements. The four most palladium-rich alloys were remelted in a levita-tion furnace since complete melting of the components had not occurred in the arc furnace. All of the alloys were subsequently homogenized at elevated temperatures in sealed alumina thimbles. After heat treatment, the alloys were analyzed chemically and were in essential agreement with the nominal compositions. The thermal histories and nominal compositions of the alloys are given in Table I. Lattice parameters of the heat-treated alloys were computed, by means of the method described by Mueller et a1. ,I2 from X-ray diffraction powder patterns obtained with filtered copper radiation in a 114.6-mm-diam Straumanis-type Debye-Scherrer camera. The results, which are tabulated in Table I, exhibit a slightly greater negative deviation from Vegards' law than the values reported by Raub et al.13 The diffraction lines were sharp and well-resolved and thus indicated that the alloys were homogenous. RESULTS The logarithms of the individual values of the vapor pressure of palladium were fit, by the least-squares method, as a linear function of the reciprocal of the absolute temperatures. The constants of the equations are given in Table I along with the temperature range over which the data was accumulated. The latent heat of vaporization at 298.15"K for pure palladium, calculated by the third-law method,14 showed no systematic temperature dependence. The average value of 88,920 * 20 cal per g-atom agrees favorably with the average of the results obtained in the most reliable previous investigations.15"19 The activities of palladium were computed from the vapor pressure data at 1525', 1575", and 1625OK. Consistent with the mass spectrometric study of the atomicity of palladium vapor,lg the vapor was assumed to be monoatomic. The activities of rhodium were determined by integrating the Gibbs-Duhem equation with the aid of the a function.20 In the calculations, the activities of the pure solid metals were assigned the value of unity. From the activities, the partial and integral free energies, entropies, and enthalpies of formation at 1575° K were computed; they are assembled in Table 11.

Jan 1, 1969

By R. K. Waring, E. C. Truesdale

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By E. C. Truesdale, R. K. Waring

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By Nico Van Wingen

Experiments performed with distilled water, unconsolidated sand and dead oil for the purpose of determining the influence of oil flow on the water content of sands were described. While results found are not necessarily, therefore, identical with those that would be obtained under natural petroleum reservoir conditions, the following conclusions were drawn. 1. When oil under constant head is flowed through an unconsolidated sand, the amount of water retained in the core is inversely proportional to the specific permeability of the core. This corroborates the view that the degree to which oil displaces water out of the pore space is limited by the size of the pores. 2. For the range investigated, the displacing action of a more viscous oil of higher specific gravity was found to be the same as a less viscous oil, or lower specific gravity. 3. The amount of interstitial water retained in the sand bears an inverse relationship to the pressure head of the displacing liquid. 4. The degree of retained water saturation of the sand appears to approach 100 per cent as the specific permeability approaches zero. 5. For the higher values of specific permeability and for the pressure range investigated the remaining amount of water in the sand occupies approximately 10 per cent of the pore space. This, together with the fact that the limiting oil velocity curve approaches approximately 10 per cent water saturation as an asymptote, indicates that beyond this point removal of water is achieved only by a stripping of the grains requiring considerable pressure drops across the sands; or by a balancing of the molecular forces. 6. As the water saturation of the sand exceeds approximately 15 per cent of the pore volume, the permeability of the sand to oil decreases rapidly. 7. Sands with water saturations as high as 40 per cent were found to produce 100 per cent oil.

Jan 1, 1939

By Nico Van Wingen

Experiments performed with distilled water, unconsolidated sand and dead oil for the purpose of determining the influence of oil flow on the water content of sands were described. While results found are not necessarily, therefore, identical with those that would be obtained under natural petroleum reservoir conditions, the following conclusions were drawn. 1. When oil under constant head is flowed through an unconsolidated sand, the amount of water retained in the core is inversely proportional to the specific permeability of the core. This corroborates the view that the degree to which oil displaces water out of the pore space is limited by the size of the pores. 2. For the range investigated, the displacing action of a more viscous oil of higher specific gravity was found to be the same as a less viscous oil, or lower specific gravity. 3. The amount of interstitial water retained in the sand bears an inverse relationship to the pressure head of the displacing liquid. 4. The degree of retained water saturation of the sand appears to approach 100 per cent as the specific permeability approaches zero. 5. For the higher values of specific permeability and for the pressure range investigated the remaining amount of water in the sand occupies approximately 10 per cent of the pore space. This, together with the fact that the limiting oil velocity curve approaches approximately 10 per cent water saturation as an asymptote, indicates that beyond this point removal of water is achieved only by a stripping of the grains requiring considerable pressure drops across the sands; or by a balancing of the molecular forces. 6. As the water saturation of the sand exceeds approximately 15 per cent of the pore volume, the permeability of the sand to oil decreases rapidly. 7. Sands with water saturations as high as 40 per cent were found to produce 100 per cent oil.

Jan 1, 1939

Swedish mining companies are noted for their excellence in underground mining practice, and this classification certainly has to be applied to their design of crushing plants also. All these mines are highly mechanized with either rail or truck haulage, and typical examples of underground crushing plants designed for each of these haulage practices are presented here. Almost all the primary breakers are of the overhead eccentric, single- toggle jaw crusher type with units as large as 55 by 71 in. (1400 by 1800 mm) being used. In contrast to North America, where jaw crushers are almost always preceded by apron or vibrating feeders, many of the. Swedish crushers are choke fed with the dump pocket being located directly above the crusher. This practice results both from excellent knowledge of the ore characteristics and the ability of the overhead eccentric crusher to also act as a feeder. An excellent example of a crushing plant of this design is shown by the sketch of the LKAB Alliansen Crusher No. 64 at Malmberget, Sweden. Forty-six st (42 mt) trucks dump magnetite ore into a 91.6 cu yd (70 m3) dump pocket mounted over a 55 by 71 in (1400 by 1800 mm) Morgards- hammar overhead eccentric crusher using a 180 hp (132 kw) motor and belt drive. Crushed ore at 10 in. (250 mm) size drops onto an air- operated tipping chute which diverts the ore to either of two 1962 cu yd (1500 m3) pockets equipped with 3 ft 11 in. by 7 ft 11 in. (1200 by 2000 mm) Schenk vibrating feeders. Dust is drawn into a wet scrubber and exhaust air is combined with mine exhaust air. Because the crusher must be assembled underground, a 45/5 ton crane is installed over the crushing installation. A crusher above ground such as at Sacaton can easily utilize a smaller crane. Capacity of this 'most interesting crushing installation is 1653 st (1500 mtph) .

Jan 1, 1978

By H. B. Pulsifer

THIS paper outlines a method for rapid production of flat, granular surfaces on many of the medium hard- alloys. Grinding wheels and fabrics on wheels are not used; the purpose is accomplished by rubbing on emery papers and on fine abrasives heaped on hand boards. The advantages of chromic acid in the solutions for etching nickel and copper alloys are explained. Steels may require an additional step in the mechanical smoothing owing to the lack of an ideal etchant. Chloric acid is a. rapid etchant for steel. Thirty-six photomicrographs illustrate the steps in smoothing and the clearness with which structures can be rapidly exposed. New structures in low-carbon steels are announced. After a little practice, many materials can be finished within two or three minutes. CUPRONICKELS In the previous papers on the metallography of copper and magnesium which the author has presented to this Institute there has been an attempt to demonstrate the advantages of minimizing the mechanical work of surfacing and depending more on chemical means; the present paper continues the research into a still wider field. It is obvious that the success of a chemical method for smoothing and etching depends almost entirely on the use of a suitable reagent. The etchant must remove the surface granulations and outline the structures. A very special type of reaction between reagent and metal must be displayed. Promiscuous corrosion or the intensification of the attack about local couples -formed by impurities or components must not be in evidence. There are several reagents that etch highly polished nickel and copper alloys very well. Acidified ferric chloride solutions, concentrated and dilute nitric acid solutions, and nitric and acetic acids in acetone have -been used to good advantage for the purpose. However, if they are expected to etch rather deeply-that is, smooth as well as characterize-the results may be far from satisfactory.

Jan 1, 1928

By John Chipman, Karl L. Fetters

Tax relationship between the composition of the slag and that of the underlying metal during the refining of a heat of liquid steel may best be studied in the light of the two broad physicochemical concepts of equilibrium and reaction rate. Actual steelmaking processes, typified by basic open-hearth practice, involve such complexities of operating variables that it is impossible to distinguish with any degree of certainty between the general limiting conditions imposed by chemical equilibrium and the effects associated with rates of diffusion or of chemical reaction. Further advances in the physical chemistry of steelmaking will depend upon our ability to distinguish clearly between these two kinds of effects, and the experimental work that must be done falls naturally into two classifications. The first is the study of chemical equilibrium that cannot be carried out with assurance under operating conditions but must be done in the laboratory. The second is the subject of rates of reaction and diffusion and the mechanism of the process as a whole, which can best be studied under operating conditions. The latter is not entirely independent of the former, since its interpretation often requires a knowledge of the equilibrium state. It is the purpose of this and of several papers that will follow to present the results of laboratory investigations of equilibria involving liquid steel and slag. Open-hearth slag is a complex mixture containing at least eight major components and perhaps twice as many whose influence may be classified as probably minor. It is not surprising that progress toward a complete understanding of such a material at high temperatures has been slow. Attempts to apply the established principles of physical chemistry to the behavior of the individual components of this mixture have been beset by an almost complete lack of data on its chemical properties in the liquid state. This has necessitated the adoption of various methods of approximation based upon such assumptions as, for example, that for a given component the ratio of its mol fraction in the slag to that in the metal is a constant, or that the molecular composition of the liquid slag is the same as its crystalline constitution after solidification. From the thermodynamic viewpoint, such assumptions are merely useful dodges, which enable one to hazard a guess as to the magnitude of the more fundamental quantities, the chemical potentials and activities of the components of slag. The problem of determining the activity of each substance in an eight-component system seems too complex to be undertaken without the aid of generalizations derived from experimental data on similar systems containing a smaller number of components. Accordingly, it was planned in the present investigation to study the equilibrium of molten iron with the simplest

Jan 1, 1941

By Charles A. Ashburner

THE appliances which have been proposed, and the modifications in the construction of boiler-furnaces which have been made for the prevention of smoke, and the utilization of what are ordinarily called the waste products of combustion, have been innumerable.

Jan 1, 1882

By E. M. Chance

HERBERT M. WILSON, Pittsburgh, Pa. (written discussion).-Permit me to endorse the author's conclusions and their form of presentation as ,being, in my judgment, the last word 'on the subject of lights for the illumination of coal mines. I also feel that the open-flame oil lamp has outlived its usefulness, and that it should go, in the interests not only of safety but of efficiency. Where an open-flame lamp can be used with safety in non-gaseous mines, the acetylene light adds materially to efficiency by its better illumination, and to safety for the numerous reasons given by Mr. Chance. The latter, however, lays chief stress on the value of the acetylene because of its non-fouling and non-obscuring effect on the atmosphere. Another important advantage over any other form of illumination is the clear, bright light projected at the point where the workman may look for danger. The better illumination materially safeguards the worker against obstacles over which he may stumble when traveling, and against dangers from falls of roof or of coal, weakness in timbering, and similar conditions. The acetylene lamp, where it may be used with safety, has advantages even over the present electric cap lamp, in that it gives a higher luminosity; and when the miner comes to learn its signals, as he will in time, just as he learns those given by the open-flame or the safety lamp, he will find that the acetylene lamp is a fair detector not only of methane but of carbon dioxide, as clearly shown by Mr. Chance. The only, serious objection, raised against the use of carbide lamps. has been recently in Pennsylvania, due to the belief of the State Mine Inspection Department that it endangered miners working on pillar work, or other places where carbon dioxide might accumulate, or where there is lack of sufficient ventilation, and because it was believed that the indications of the carbide lamp would not give the miner sufficient warning. On this point Mr. Chance has clearly shown the fallacies of the objections. I may add that for those unable to detect carbon dioxide with the acetylene lamp, the maximum of protection would be afforded by using an open oil lamp or a flame safety lamp in such places; or, because the miner might not watch his oil light, a better, protection still would be offered by a sufficient number of daily inspections of such working places by a fire boss or other official, with flame safety lamp.

Jan 4, 1917