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By J. W. Downey, M. V. Nevitt

MUELLER and Knott' have reported that Ti2Cu has the Si2Mo-type (Cllb) structure. The lattice parameters of Ti2Cu and the positions of the titanium and copper atoms are given by them as follows: ao = 2.944A; co = 10.786A 6 atoms per unit cell: 2 Cu (a) 000; 1/2: 1/2, 1/2 4 Ti (e) 002; 1/2, 1/2, 1/2 + z 00 -2 ; 1/2. 1/2. 1/2- z where z = 0.341 We have found eight other binary compounds which appear to be isostructural with Ti2Cu. All of them involve the combination of a titanium group element with a copper group element or a titanium group element with palladium. The compounds and their lattice parameters are given in Table I. The alloy samples were prepared by arc melting metals having a purity of 99.9 pct or better. They were homogenized for 72 hr at 900°C in evacuated capsules and quenched in tap water. Filings were prepared, and these were reannealed for 4 hr at 700°C, also in evacuated tubes. The lattice parameters were determined by a least squares Bnalysis of the back reflection lines of patterns made with cobalt radiation. It was not possible to make a precise determination of the lattice parameters of Zr2Au because the filings underwent rapid oxidation at room temperature. The evidence supporting the large tetragonal cell containing 6 atoms involves the presence of the reflections 002, 101, 004, 112, 114, 202, and other reflections with higher indices for which I = 3n. Three or more reflections corresponding to these indices, which cannot be indexed on the basis of a small body-centered tetragonal cell containing 2 atoms, are observed in the patterns of all of the compounds listed in Table I. They are strongest and most numerous when the components have large differences in their atomic scattering factors, as is the case in Ti2Pd, Zr2Cu, and Hf2Cu. The values of the z parameter should be regarded as approximate They were selected on the basis of the best agreement between the observed intensities of two pairs of closely spaced powder pattern lines (004): (112) and (114): (202) and the corresponding intensities calculated for several values of z. An ordering scheme was assumed in which titanium, zirconium, or hafnium atoms occupy the titanium positions of Ti2Cu, and copper, silver, palladium, or gold atoms occupy the copper positions. Calculated and observed intensities of the aforementioned lines and the other lines of the patterns are in satisfactory agreement, but a refinement of the z parameters and a final confirmation of the ordering arrangement must await a more detailed study. It is interesting to note that in transition metal systems at A2B stoichiometry the Si2Mo-type structure competes for stability with two other fre-

Jan 1, 1962

By Arne Paus-Jenssen

Some aspects of the policies developed by Saskatchewan with respect to the provincial potash industry are discussed. The provincial potash policy was developed initially to deal with problems associated with an excess supply and consisted of output restrictions and floor prices. Changing market conditions led to a situation of rapidly increasing prices and revenues for the potash producers, and the nature of the policy problem switched from one of stabilizing the industry to one of levying increased taxes to enable the government to capture a portion of the revenues. The first part of the paper explains why a provincial potash policy was developed, the problems it attempted to deal with and how. The second part is an attempt to examine, from a public policy point of view, the impact of these policies on the potash industry.

Jan 1, 1977

By Dennis V. D’Andrea, Robert C. Steckley, William C. Larson, Richard A. Dick

A fragmentation experiment was performed in cooperation with Duval Corporation in a porphyry copper molybdenum deposit near the Sierrita pit south of Tucson, Ariz. A 10-hole test blast was detonated to establish relationships between blasthole spacing and the resulting fragmentation. Blastholes were 9 in. in diameter and 110 ft deep. The 10 blastholes contained a total of 17,400 lb of aluminized slurry blasting agent in 50-ft columns with 60 ft of stemming. Blasthole spacings of 25, 20, and 15 ft were tested. Diamond drill core examination was the primary method used to determine the condition of the rock before and after blasting. Topographic surveys were used to measure the rock swell produced by the blast and a fragment size distribution was obtained for the rubblized material on the surface. The rubble zone at the surface was ideal for in situ leaching. Fragmentation to depths of 110 ft was excellent from the 15- to 20-ft blasthole spacing patterns. Good breakage was also produced by the 25-ft pattern although the effects of the blast were not as obvious. In situ leaching tests were not conducted. However, based on size consideration only, all three blasting patterns produced adequate breakage for successful leaching.

Jan 1, 1974

By H. O. Jahns, R. A. Greenkorn, R. E. Haring, L. K. Shallenbarger

This paper is a study of the effects of heterogeneity on flow in an analog of porous media, the Hele-Shaw model. l-3 A set of experiments in heterogeneous Hele-Shaw models showed streamlines through and around heterogeneities of various sizes, shapes and levels. (A level, we define as the ratio between the transmissibility of the heterogeneity and that of the rest of the model.) The heterogeneities were restrictions or expansions of the flow stream analogous to variations in the transmissibility of porous media. The experimental data agreed well with numerical results and with an analytical solution, which we derived for a circular heterogeneity in an infinite field. This study considers the flow-stream distortion due to the shape, size and level of heterogeneities. Size and level are much more important than shape provided the heterogeneity is not long and narrow. Our analytical solution shows that a circular heterogeneity in a large field can be replaced by an equivalent circle of either zero or infinite permeability. The radius of the. equivalent circle is a simple function of size and level of the actual circle. INTRODUCTION With the availability of high-speed computers and numerical procedures to predict reservoir behavior, we are faced with an important question. How much information about the reservoir do we need to justify the cost of the computer in any given case? To answer this question, we have to know how various reservoir parameters affect flow behavior. Reservoir heterogeneity is one of these parameters. In this study, we used a simple, two-dimensional model of porous media, the hele-shaw model, to investigate the effect of heterogeneity on flow behavior. We restricted ourselves to linear, single-phase, steady-state flow in a rectangular field with a single heterogeneity at its center. The analogy between flow in Hele-Shaw models and in porous media is easily verified. Let us first consider a homogeneous Hele-Shaw model with constant plate separation h. (The Hele-Shaw model is constructed by placing two plates, usually glass, very close together and allowing liquid to flow between them. Streamlines are made visible by introducing colored fluid into the space between the plates at a number of points across the model.) We assume a cartesian coordinate system with its origin in the middle between the plates and the z axis directed perpendicular to the glass plates (Fig. 1). The fluid flow is always in a direction parallel to the glass plates and varies from a maximum value to zero in the very small distance from the middle (z = 0) to either plate (z = h/2). For slow motion of an incompressible fluid, neglecting inertia and body forces, we have the viscous flow equation: where p is the fluid pressure, p the viscosity, and v the velocity vector with components u, v and w in the x, y and z directions, respectively. In our rase. and the derivatives of 3 with respect to x and y are small as compared with the derivative in the z direction. Therefore, approximately, with Vp and v being two-dimensional vectors in the x-y plane. Two integrations with respect to z give

Jan 1, 1965

By E. D. Hummer, J. A. Younkins. J. P. Proctor

Comparatively little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission Of any effluent Of high ''lid 'content to be rep1aced by 'lean water in Order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the Purpose of this Paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settlillg and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." General Arrangement of Water System So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers,1,2 The washer, which handles o to 4-in, raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. I) consists of twin 48.in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By J. A. Younkins. J. P. Proctor, E. D. Hummer

Comparatively little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission Of any effluent Of high ''lid 'content to be rep1aced by 'lean water in Order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the Purpose of this Paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settlillg and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." General Arrangement of Water System So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers,1,2 The washer, which handles o to 4-in, raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. I) consists of twin 48.in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By W. M. Rust, W. D, D. W. Mounce

The almost universal acceptance of electrical logging by the petroleum industry calls for a critical examination of the physical bases of the common methods. This is particularly needed for the natural potential log. The conventional explanations are based on the phenomena of electrofiltration and electro-osmosis. However, experimental data show that they fail to give a basis that is quantitatively sound. Moreover, they lead to interpretations of details of electrical logs that are erroneous. It was found experimentally that when a plug of shale is placed in a chain of dissimilar electrolytes, a current flow results. Experiments on oil-well cores and fluids similar to those existing in wells show that potentials are set up which are in reasonable agreement with those encountered in electrical logging. Doubtless other sources of potential are important but this explanation not only accounts for much of the potential but also clarifies some fairly familiar examples of misinterpretations. Introduction The extraordinary value of electrical well logging as a tool for petroleum engineers and geologists is now so uni- versally recognized that it is not necessary to point out the ways in which it can be useful. It is sufficient to mention only the saving that has resulted from the elimination of much coring that would have been necessary under former practices and the considerable additions to reserves resulting from the discovery of sands missed in coring. Paradoxically, the very remarkable success that has resulted from the application of electrical logging to correlation and completion problems has cost some of its most consistent users dearly.' The fact that some operators have placed unwarranted faith in erroneous interpretations of electrical logs does not reduce the value of the logs. It should, however, make one pause long enough to ask why experienced users should be misled. The answer to this question is not hard to find. In nearly every case, the fault has been oversimplification. This is illustrated very aptly by the familiar interpretation and theory of the natural potential log. Recording and Interpreting Logs The natural potential log is extremely simple to record precisely enough for all present-day uses. One needs only an electrode, a cable to lower the electrode through the drilling mud, a recording meter and a surface ground connection. The electrode can be elaborate but need not be. A simple brass rod 2 in, in diameter and 2 or 3 in. long is quite satisfactory. The cable need not be particularly well insulated, nor need it have a very low resistance. The recorder can be a vacuum-tube 1 References are at the end of the paper.

Jan 1, 1944

By W. D, D. W. Mounce, W. M. Rust

The almost universal acceptance of electrical logging by the petroleum industry calls for a critical examination of the physical bases of the common methods. This is particularly needed for the natural potential log. The conventional explanations are based on the phenomena of electrofiltration and electro-osmosis. However, experimental data show that they fail to give a basis that is quantitatively sound. Moreover, they lead to interpretations of details of electrical logs that are erroneous. It was found experimentally that when a plug of shale is placed in a chain of dissimilar electrolytes, a current flow results. Experiments on oil-well cores and fluids similar to those existing in wells show that potentials are set up which are in reasonable agreement with those encountered in electrical logging. Doubtless other sources of potential are important but this explanation not only accounts for much of the potential but also clarifies some fairly familiar examples of misinterpretations. Introduction The extraordinary value of electrical well logging as a tool for petroleum engineers and geologists is now so uni- versally recognized that it is not necessary to point out the ways in which it can be useful. It is sufficient to mention only the saving that has resulted from the elimination of much coring that would have been necessary under former practices and the considerable additions to reserves resulting from the discovery of sands missed in coring. Paradoxically, the very remarkable success that has resulted from the application of electrical logging to correlation and completion problems has cost some of its most consistent users dearly.' The fact that some operators have placed unwarranted faith in erroneous interpretations of electrical logs does not reduce the value of the logs. It should, however, make one pause long enough to ask why experienced users should be misled. The answer to this question is not hard to find. In nearly every case, the fault has been oversimplification. This is illustrated very aptly by the familiar interpretation and theory of the natural potential log. Recording and Interpreting Logs The natural potential log is extremely simple to record precisely enough for all present-day uses. One needs only an electrode, a cable to lower the electrode through the drilling mud, a recording meter and a surface ground connection. The electrode can be elaborate but need not be. A simple brass rod 2 in, in diameter and 2 or 3 in. long is quite satisfactory. The cable need not be particularly well insulated, nor need it have a very low resistance. The recorder can be a vacuum-tube 1 References are at the end of the paper.

Jan 1, 1944

By Donald W. Scott

Generally speaking, there is nothing very difficult about taking good microgrztphs of photogenic thin sections or grains with a petrographic microscope-camera setup. However, sometimes it is desired to show some detail that cannot be illustrated satisfactorily by the usual micrographs taken with parallel polarized light, with crossed nicols, or even with two micrographs. A simple procedure giving good results has been used at Battelle Memorial Institute for subjects falling into this classification, and it is believed to be of interest, especially to research people who must sell a point to executives through the medium of well-illustrated reports. The following problem illustrates a typical application: It is desired to photograph a thin section of an iron ore to illustrate the character and association of the iron oxides and the individual quartz crystals. A magnification of 75 dia. is acceptable. A micrograph of the field in question (Fig. Ia) was taken with parallel polarized light. Due precaution was taken to provide critical illumination, correct exposure, a sharp focus, a good darkroom technique, and other essential conditions. It illustrates correctly the iron oxides, but it fails to show the individual quartz crystals. A micrograph of the identical field (Fig. Ib) was taken under the same precise conditions, but with crossed nicols. It gives a better idea of the character of the individual quartz crystals but is likely to be misinterpreted unless accompanied by a lengthy descriptive note. This micrograph suggests that the centrally located, large black area is composed entirely of iron oxides. That this' is an incorrect interpretation is evident by reexamining the micrograph of Fig. Ia. The correct interpretation is that the dark area contains quartz crystals oriented with their optical directions parallel to, or nearly parallel to, the vibration directions of the polarizer and analyzer of the microscope. Thus, the executive, or anyone who had not done the work personally, would get no more than a fair interpretation, even if two micrographs were included; and in the interests of both brevity and clarity, one micrograph usually is more desirable. Exactly how many quartz crystals occur in this region cannot be told from the two micrographs, and a printing of the two negatives in register would likewise not show the detail desired. Thus, it is evident that some subjects cannot be satisfactorily illustrated by the usual procedures. In photographing Fig. Ic the light was subdued and, during the entire exposure of 75 sec., the analyzer nicol was rotated uniformly in its mounting from a crossed position to 45° uncrossed position to introduce the desired amount of contrast in the various individual quartz crystals. The true reproduction of the character and association of the iron oxides, and the additional structure and detail in the quartz areas, is apparent. It might be

Jan 1, 1949

By Donald W. Scott

Generally speaking, there is nothing very difficult about taking good microgrztphs of photogenic thin sections or grains with a petrographic microscope-camera setup. However, sometimes it is desired to show some detail that cannot be illustrated satisfactorily by the usual micrographs taken with parallel polarized light, with crossed nicols, or even with two micrographs. A simple procedure giving good results has been used at Battelle Memorial Institute for subjects falling into this classification, and it is believed to be of interest, especially to research people who must sell a point to executives through the medium of well-illustrated reports. The following problem illustrates a typical application: It is desired to photograph a thin section of an iron ore to illustrate the character and association of the iron oxides and the individual quartz crystals. A magnification of 75 dia. is acceptable. A micrograph of the field in question (Fig. Ia) was taken with parallel polarized light. Due precaution was taken to provide critical illumination, correct exposure, a sharp focus, a good darkroom technique, and other essential conditions. It illustrates correctly the iron oxides, but it fails to show the individual quartz crystals. A micrograph of the identical field (Fig. Ib) was taken under the same precise conditions, but with crossed nicols. It gives a better idea of the character of the individual quartz crystals but is likely to be misinterpreted unless accompanied by a lengthy descriptive note. This micrograph suggests that the centrally located, large black area is composed entirely of iron oxides. That this' is an incorrect interpretation is evident by reexamining the micrograph of Fig. Ia. The correct interpretation is that the dark area contains quartz crystals oriented with their optical directions parallel to, or nearly parallel to, the vibration directions of the polarizer and analyzer of the microscope. Thus, the executive, or anyone who had not done the work personally, would get no more than a fair interpretation, even if two micrographs were included; and in the interests of both brevity and clarity, one micrograph usually is more desirable. Exactly how many quartz crystals occur in this region cannot be told from the two micrographs, and a printing of the two negatives in register would likewise not show the detail desired. Thus, it is evident that some subjects cannot be satisfactorily illustrated by the usual procedures. In photographing Fig. Ic the light was subdued and, during the entire exposure of 75 sec., the analyzer nicol was rotated uniformly in its mounting from a crossed position to 45° uncrossed position to introduce the desired amount of contrast in the various individual quartz crystals. The true reproduction of the character and association of the iron oxides, and the additional structure and detail in the quartz areas, is apparent. It might be

Jan 1, 1949

By V. B. Tare, H. Schmalzried

The use of solid electrolytes for determining kinetic paraneters at elevated tevnperatures is pointed out. The reaction rate constant k1 of the phase-boundary reaction during oxidution of iron to wiistite by CO2-CO gas mixtures has been deternined between 850 nnd 975C, using ZrOz(+CaO) as an electrolyte. Values are between 1.4 x 10-a and 5.2 x 10 ole per sq ctn atm. The tzain difficulty is due to mixed potentials arising from side reactions at the electrolyte inteyface. In a number of papers the calcium-doped zirconia electrolyte has been used for the determination of thermodynamic data from measured differences in oxygen activities (or potentials) between two electrodes. The purpose of this note is to suggest the use of this solid electrolyte for kinetic measurements as well. The principle can be seen from Fig. 1. A thin and compact phase II (electron conductor) is fixed on a plate of gas-tight, polished ZrO2(+CaO) (I), which separates two compartments with different oxygen potential. p, is a constant reference pressure of oxygen (1 atm). The electromotive force of this galvanic cell is given by E = RT5 In pep, and pe is the oxygen partial pressure at the interface electrolytephase 11. If phase I1 is in equilibrium with the surrounding gas phase, p, = DR. If pg changes sud- denly to a value pi, p, and therefore the electromotive force, E, change as a function of time according to the phase-boundary reaction rate at the gas phase I1 interface and the transport processes inside phase 11. It is assumed that local equilibrium is established at the boundary electrolytephase 11, that the gas phase shows no concentration gradients, and that the con-

Jan 1, 1967

By L. S. Darken

It has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernstl in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and FuossZ with results which have recently been confirmed experimentally by Harned and Nuttall. This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author,4,5 who pointed out4 that "for a system of more than two components it.is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepti- cism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley" in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion of acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 10500 C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1949

By C. R. Dodson, D. Goodwill, E. H. Mayer

The paper summarizes the historical background of the pressure-volume-temperature analyses of reservoir fluids, the errors involved in both the sampling and testing of reservoir fluids, the type of information required of a PVT determination, and the field conditions that limit the application of any one analysis. Particular emphasis is placed on the necessity for approximating as closely as possible the liberation sequence occurring in the producing formation, flow string, and surface separators. A combined differential and flash or "composite" liberation is suggested as the best means of approximating this liberation sequence. HISTORICAL BACKGROUND Petroleum reservoir engineering commonly is considered to be one of the newest fields of petroleum science, yet much work of a theoretical and intuitive nature was done many years before the modern techniques of reservoir analyses were developed. The period 1910-1924 saw considerable work in the field of reservoir behavior done by the U. S. Bureau of Mines. This work:.' although entirely theoretical, pointed out the importance of gas in the recovery of oil from the reservoir. The statement by J. 0. Lewis that 20 per cent or less of the oil originally in place in a pool was recovered from the ground under uncurtailed production conditions caused some operators to re-examine and modify their production methods. However, though these works showed methods of production that have subsequently resulted in greater oil recoveries, they in general went unnoticed, even though there was a fear that the nation's petroleum resources were being exhausted. The period 1924-1933 saw the industry take considerably more interest in reservoir behavior because of an unfounded fear of its inability to replace oil reserves, the possibility of government regulation, and the energy of one man, Henry L. Doherty. Doherty aroused heated discussions in the industry concerning conservation. To prove or disprove his theories the first experimental work on the reservoir behavior of petroleum was undertaken. The papers of Dow and Calkin,' Beecher and Parkhurst," and Mills and Heitheckere are classics although their experimental procedures were crude. These papers proved that the properties of petroleum in the reservoir are quite dissimilar to the properties measured at the well head. Gas dissolved in the oil phase was recognized as having considerable importance as had been predicted by the earlier theorists. Slightly later Miller and his co-workers assembled the first text correlating all the known data on the reservoir behavior of petroleum and used, these data to show the economic value of conservation. Quantitative application of pressure-volume-temperature analyses of reservoir fluids was given in the paper of Coleman, Wilde, and Moore"; this work showed that with sufficient laboratory and production data prediction of reservoir behavior was possible. The refined sampling and labora-

Jan 1, 1953

By C. R. Kyle, R. L. Perrine

A transparent model of a reservoir has been used to study some characteristics of instability in miscible displacement. The linear model dimensions are 1/4 in. x 91/2 in. x 10 ft. The model is packed with spherical glass beads. Thee groups of experiments have been performed. The objectives were to measure, respectively, the rate of growth of the transition zone, flow velocity variations in the transition zone, and the effect of a graded viscosity zone on stability. All experiments were compared, where possible, with theory. The transition zone grew almost linearly with distance traveled, regardless of flow rate, where adverse viscosity ratios were used. At very adverse viscosity ratios and large distances traveled, some reduction below linear growth was noted. This could be attributed to the effects of mixing. General similarity in flow pattern was commonly shown in different tests, although exceptions occurred at the higher viscosity ratios. Injection of tracer spots permitted direct experimental measurement of velocity variations. Statistical methods were used to compare observed velocity variations with recently published theories. Surprisingly good agreement with some theoretical predictions was obtained. In the experiments using an initially graded viscosity zone, macroscopic stability was reached before predicted by theory. Under conditions theoretically considered to be slightly unstable, any fingering tendency was too slight to become observable within a 10-ft long system. The general correlation of all experiments with published theory was good, and suggests that theoretical predictions can be extended to reservoir problems. INTRODUCTION Early laboratory studies of miscible displacement demonstrated the high recovery efficiency possible with this method. Linear laboratory models showed that, under some circumstances, all in-place hydrocarbons could be recovered using as little solvent as 5 per cent of the pore volume. These results led to a series of pilot field projects. Under realistic conditions, however, other laboratory studies showed that a small solvent bank may not recover much more oil than a conventional gas drive. The cause of this lack of efficiency is unstable viscous fingering. The size of the solvent bank required to give optimum recovery is, therefore, a question of great economic significance. The object of the experiments described in this paper was the quantitative measurement of unstable flow parameters, the verification of present theories on the miscible displacement process, and correlation of these theories with ex peri mental observation. Of the theories which have been advanced, those by Dougherty, Koval and Perrine show promise of predicting reservoir performance with reasonable accuracy.l-7 The present experiments were correlated, where possible, with the theories of Koval and Perrine. Dougherty's theory was not used because of the additional computational difficulty it presented and the belief that no further information would result. EXPERIMENTAL EQUIPMENT A transparent reservoir model, consisting of a vertical reinforced plexiglass column, was used for the experiments. The column was packed with glass beads, which served as the porous medium. To induce a known velocity disturbance in the flow, a double cosine wave restriction in the transverse cross-section was placed at the top of the column. To mark the flow field and provide a means of measuring the local fluid velocity, a dye-spot injection system was provided. The column was 10 ft high by 1/2 in. wide by 1/4 in. deep. The cosine restriction was placed 16 in. from the top of the column. The glass beads were smooth and spherical and had a mean diameter of 0.0102 cm. Liquids entered the top of the column through a manifold allowing three points of entry (left, center, and right, or any combination of these). A positive-displacement pump with variable-speed drive was used to control liquid flow rates. The pump transferred viscous oil from a reservoir to an accumulator, which displaced the test liquid into

Jan 1, 1966

By John J. Reed

This paper was prepared as a supplement to the general review by Dr. N. G. W. Cook. His analysis of the problem in terms of the strain energy involved in making the excavation is excellent. It will contribute much towards a clearer understanding of rock behavior and control. Several of the practical applications described herein can be directly related to Dr. Cook's theories and conclusions, and are based on the very same principles. CONTROLLED BLASTING IN ROCK EXCAVATION Generally speaking, the natural rock is a relatively strong and competent structural material, if we conserve its inherent good properties and perhaps reinforce its weak spots. The difficulty often lies in blasting out the tunnel or chamber without damaging the walls and roof we wish to have remain afterwards. Much progress has been made in the last five years in better understanding the controlled excavation of rock. The specialized techniques known as smooth wall blasting and presplit blasting have now developed from the status of curiosities of rock excavation to the point where these techniques are specified in contracts drawn up for such rock excavation projects as tunnels, underground pourer houses, etc. These techniques have been well described and discussed in previous publications; there is no need to reiterate here. It might be well to point out that recent research has demonstrated the effect that inherent rock stress may have on presplitting in certain directions. Material can be presplit most readily parallel to the direction of maximum compressive stress, and this may not always be in the direction desired. Inherent rock stress measurements by stress relief over coring, etc., may have important value in deciding how to best presplit proposed excavations. In addition, recent work at the Colorado School of Mines has demonstrated the feasibility of con-

Jan 1, 1967

By J. W. Evans

ONE possible method for the separation of hafnium from zirconium is by the vapor phase oxidation of the purified mixed chlorides. An important factor for success depends on the difference in free energies of the following reactions: ZrCl(g) + O2 = ZrO2(s) + 2C12 [1] HfCl4(g) + O2 = HfO2(s) + 2C12. [2] Prakash and Sundaram1 have calculated these values from certain data and carried out experimental work with partial success. However, their free energy values for reaction 2 diverge rather widely from other data which are presented here. The possibility of successful separation is briefly considered in the light of these alternative values. Table I shows the free energy values (?F°) for reactions 1 and 2 derived from the recent compilation of data on oxides and chlorides by Glassner.2 The corresponding values of Prakash and Sundaram for the same temperatures are also shown. The alternative values to those of Prakash and Sundaram for reaction 2 are substantially confirmed by the data of Kubaschewski and Evans" and Cough-lin' on heats of formation, entropies, and heats of vaporization. In spite of the considerable uncertainty in the hafnium data it is reasonable to suppose that the oxide-chloride free energy difference for two such chemically similar elements would not be very far apart. These figures indicate clearly that the oxidation of hafnium chloride is appreciable at all temperatures. Nevertheless, there is a significant difference between the values for reactions 1 and 2

Jan 1, 1959

By E. E. Carpenter

(San Francisco Meeting, September, 1915) BELIEVING that the results accomplished in the mill of the Churchill Milling Co., Wonder, Nev., during the fiscal year ended Sept. 30, 1914, will be of interest, I am presenting the more prominent facts and figures showing the progress made in treating this ore with especial reference to tonnage, supplies, costs, and extractions. The mill is situated at Wonder, Nev., in the Wonder mining district, 55 miles east from Fallon, Nev., the nearest railroad point. All supplies are hauled this distance by freight teams, this method of transportation having been found more reliable for continuous service than trucks, the price paid for hauling being slightly under one cent per pound. In this mill are treated the ores of the Nevada Wonder Mining Co. ,

Jan 6, 1915

By Charles Legrand

The power plant of the Burro Mountain Copper Co. is located near Tyrone, N. M., at 5,950 ft, elevation. It is interesting because it uses the largest stationary Diesel engines in the United States. The general layout of the plant is shown in Figs. 1 and 2. The building is of steel-frame construction with hollow-tile walls and corrugated-iron roof; the floor is concrete and all windows have steel frames, making a fireproof building. The building is made to accommodate one more electric generator unit, which is being installed; also two 4,000-cu. ft. air compressors direct-connected to three-cylinder engines with the same size cylinders as the electric units. The power plant consists of two 815-kva., 60-cycle, three-phase, 6,600-volt, 180-r.p.m. generators, direct-connected to five-cylinder, two-cycle Diesel engines; the necessary circulating pumps for cooling water, cooling towers and oil storage tanks. A portion of the power is used in the same building as the generating units to run one of two 200-kw. rotary converters delivering 260-volt direct current, and a 2,500-cu. ft. air compressor, delivering air at 95 1b.-pressure, direct-connected to a 400-hp., 6,600-volt, three-phase synchronous motor. The remainder of the power is used to run a 1,500-ton concentrating mill 3 1/2 miles from the power house, various hoists, pumps and motors about the mines and the lighting and water-works of the town of Tyrone. The direct current is used for electric traction in the mine, also to run hoists and motors that were installed before the new power plant was built. Due to the large hoists that take starting peaks of 250 kw. and the 10-ton electric locomotive that takes at times 150 kw., the load is extremely variable, as shown in Fig. 3. The two five-cylinder vertical Diesel engines, which are rated at 1,250 b.hp. at sea level, have cylinders of 525-mm. diameter (20.6 in.) and

Jan 1, 1917

By Luther W. Bahney

(San Francisco Meeting, October, 1911.) LIME is the alkali that is almost universally added to the solutions in the cyanide process of gold- and silver-extraction for maintaining the so-called, protective" alkalinity. It is produced by the burning of limestone. The value of lime for this purpose depends upon the percentage of calcium oxide contained, which is determined by three factors : 1, purity of the limestone used; 2, degree of the burning-temperature and the period of burning; and 3, length of time of storage of burned material and the condition stored, and whether it has been damp or wet during the storage. These three factors render uncertain the quality of lime bought in the open market. In the United States, lime bought from reliable manufacturers, who thoroughly burn a pure limestone and deliver at once to the consumer from the kilns, may be of a fairly-high and uniform composition ; but in Mexico and Central America, where it is purchased from many small producers, who often start with a poor grade of limestone and burn it in small crude kilns with as little fuel as possible, the quality of the product is quite variable. In consideration of the foregoing, it is apparent at once that there is a great need for a rapid technical method for the valuation of the lime to be used in a cyanide-plant. The determination of calcium by the gravimetric method, with the necessity of determining also the proportion of carbon dioxide, silica, and iron, requires too much time, and is usually out of the question for an isolated plant unequipped with a skilled chemist and, the necessary apparatus. The calculating of all the calcium so found to calcium oxide, although sometimes done, is manifestly very inaccurate.

Nov 1, 1911

By J. Offeringa, C. van der Poel

The report describes scaled model experiments on the recovery of oil from porous sands by the injection of miscible liquids [solvents] and the subsequent recovery of the solvents by water flooding. Special attention has been paid to the scaling problem. Scaling rules are deduced and their correctness is checked by carrying out experiments in tubes of various sizes. Data are submitted on the effect of the viscosity ratio oil-solvent on the efficiency of the displacement process, the viscosity ratio varying from 1.5 to 5,000. Breakthrough recoveries obtained when flooding with kerosene as a solvent, are equal to those obtained in water flooding at the same viscosity ratio, indicating that he phenomenon of viscous fingering is decisive. After breakthrough, however, flooding with a miscible liquid becomes much more efficient than a water flood and this is more pronounced as the viscosity ratio oil-solvent is higher. Although high oil recoveries are obtained and most of the solvent in the sand can be recovered by a subsequent waterdrive, a straight flood with miscible liquids does not appear economically attractive because of the large quantities of solvent required. Therefore, a circulation process is introduced, the features of which are described in this paper. Though by means of this circulation process the amount of solvent required can be drastically reduced, the process is not yet economic. SCOPE OF THE INVESTIGATION The recovery efficiency by water flood of oils of viscosities exceeding 50 cp is low. As interest in production of these highly viscous oils is growing at the moment, it was considered worthwhile to gain basic information on the feasibility of first flooding such oils with a low viscous miscible liquid [solvent] and subsequently producing the latter in a conventional way, e.g. by water flooding. The method has the obvious drawbacks that return on the investment is delayed until water flooding has begun and that it requires the investment of a more valuable product to produce a less valuable one. On the other hand, it may be expected that the displacement of one liquid by another is more efficient when the two liquids are miscible than when they are immiscible. As laboratory data on this point are scanty, the present investigation seemed justified. Another argument for carrying out these experiments is that they present a valuable contribution to our concepts of the scaling problem in reservoir engineering studies. Some major difficulties which are encountered in the scaling of the waterflooding process such as the scaling of the capillary forces and the difficulty of obtaining the same permeability characteristics in the model do not present themselves in this case. As the fluids are miscible capillary forces do not play a role and as there is only one fluid phase, Darcy's law is valid in its original form. Consequently it is felt that the scaling rules can be deduced with a greater amount of certainty. An essential feature of the experiments is that they are scaled model ones, which are, however, somewhat

Jan 1, 1955