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By F. W. Rols-Hausen, F. W. Jessen

It is the purpose of this paper to present data on brines occurring in the Frio formation of the Texas Gulf Coast, and to show how their composition varies, (1) with depth below the surface, (2) with depth below the top of the formation, and (3) along the approximate strike. The brines vary in chloride content from 3,180 to 73,000 p.p.m., though the average salinity of the salt waters is shown to vary with total depth; the concentration being 35,000 to 40,000 p.p.m. at 3500 to 5500 ft., slightly less than 50,000 p.p.m. chloride at 5500 to 6500 ft. and average 38,000 to 40,000 below 6500 feet. From the analyses available, it appears that the highest concentration of salts occurs in the upper 300 ft. of the formation, while lower salinity is found with increasing depth below this point. The salt waters from wells in Starr County show less concentration of dissolved salts than in any other group of wells farther north along the strike. In all, 116 analyses from 63 fields and 14 wildcats, from depths ranging from 1300 to 11,400 ft. below the surface and from z to 3240 ft. below the top of the Frio, are recorded. Introduction Brines have been studied for many Years in an attempt to solve some of the geologic and production problems associated with the production of oil and gas. One practical application of study of . water analyses is the correlation of waters occurring above, in, or below the producing sand in the same field or throughout the same formation. The Frio formation, the series of sands and shales occurring below the Marginulina zone and above the Vicksburg, is one of the major oil and gas-producing formations in the Texas Gulf Coast. Fossils are rare or absent in the upper Frio throughout most of the area. When available, cuttings and cores, and electric logs were used to determine the top of the Frio. A change in lithology was used to determine this point in most of the wells, and fossils were used in some of the deep wells. It is realized that a change in lithology is not perfect for correlation purposes over long distances and some of the trends may be influenced by the inability to differentiate between the nonfossiliferous Marginulina zone and the Frio. It underlies virtually all the area shown on the accompanying map (Fig. I). Although it is not productive in the updip facies, it has been explored to a limited degree below I2,000 ft. Further more, toward the coast line future drilling to deeper depths should encounter this formation. Although thousands of wells have penetrated or drilled entirely through the formation, very few water samples have been secured from the many sands occurring in this formation and analyzed. Previous Investigation No previous published study has been made of the chemical composition and concentration of waters from the Frio formation. However, one water analysis

Jan 1, 1944

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to I700°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid,i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By F. W. Jessen, F. W. Rols-Hausen

It is the purpose of this paper to present data on brines occurring in the Frio formation of the Texas Gulf Coast, and to show how their composition varies, (1) with depth below the surface, (2) with depth below the top of the formation, and (3) along the approximate strike. The brines vary in chloride content from 3,180 to 73,000 p.p.m., though the average salinity of the salt waters is shown to vary with total depth; the concentration being 35,000 to 40,000 p.p.m. at 3500 to 5500 ft., slightly less than 50,000 p.p.m. chloride at 5500 to 6500 ft. and average 38,000 to 40,000 below 6500 feet. From the analyses available, it appears that the highest concentration of salts occurs in the upper 300 ft. of the formation, while lower salinity is found with increasing depth below this point. The salt waters from wells in Starr County show less concentration of dissolved salts than in any other group of wells farther north along the strike. In all, 116 analyses from 63 fields and 14 wildcats, from depths ranging from 1300 to 11,400 ft. below the surface and from z to 3240 ft. below the top of the Frio, are recorded. Introduction Brines have been studied for many Years in an attempt to solve some of the geologic and production problems associated with the production of oil and gas. One practical application of study of . water analyses is the correlation of waters occurring above, in, or below the producing sand in the same field or throughout the same formation. The Frio formation, the series of sands and shales occurring below the Marginulina zone and above the Vicksburg, is one of the major oil and gas-producing formations in the Texas Gulf Coast. Fossils are rare or absent in the upper Frio throughout most of the area. When available, cuttings and cores, and electric logs were used to determine the top of the Frio. A change in lithology was used to determine this point in most of the wells, and fossils were used in some of the deep wells. It is realized that a change in lithology is not perfect for correlation purposes over long distances and some of the trends may be influenced by the inability to differentiate between the nonfossiliferous Marginulina zone and the Frio. It underlies virtually all the area shown on the accompanying map (Fig. I). Although it is not productive in the updip facies, it has been explored to a limited degree below I2,000 ft. Further more, toward the coast line future drilling to deeper depths should encounter this formation. Although thousands of wells have penetrated or drilled entirely through the formation, very few water samples have been secured from the many sands occurring in this formation and analyzed. Previous Investigation No previous published study has been made of the chemical composition and concentration of waters from the Frio formation. However, one water analysis

Jan 1, 1944

By David B. Burrows, Rlkl Kobayashi, Norman L. Carr

The viscosity of hydrocarbon mixtures, whether in the gas or liquid phase, is a function of pressure, temperature, and phase composition. This paper presents methods for the prediction of the viscosity of the gas or less dense fluid phase over the practical range of pressure, temperature, and phase compositions encountered in surface and subsurface petroleum production operations. The correlation necessary to predict the effect of pressure on viscosities is presented in Part I. Serious discrepancies in high pressure gas viscosity data in the literature are discussed. The application of the correlation to predict absolute viscosities is discussed in Part 11. Auxiliary correlations are presented to enable calculations of viscosities from a knowledge of the pressure, temperature, and gravity of the gas phase. INTRODUCTION A knowledge of the viscosity of hydrocarbon fluids is needed to study the dynamical or flow behavior of these mixtures through pipes, porous media, or more generally wherever transport of momentum occurs in fluid motion. Since flow is predominantly in the laminar region in petroleum reservoirs, the influence of fluid viscosity on this flow is especially important. As early as 1894, Onnes1 and Onnes and de Haas' noted that the viscosities of homologs under corresponding states could be correlated. The theorem of corresponding states has been further developed and applied to the viscosity of pure, nonpolar gases under pressure by Comings, Mayland, and Egly.3 It was demonstrated that the viscosity ratio could be expressed rather closely as a function of reduced pressures and temperatures, 1.e.: µ/µ1 = f( TR2 PR) ........(1) temperature, absolute units where: TR =------------------------------ ------ critical temperature. absolute units _pressure, absolute units critical pressure, absolute units µ = viscosity of gas at reduced temperature TR and reduced pressure PR µ1 =. viscosity of gas at atmospheric pressure and at temperature TR Serious discrepancies in the viscosity of pure hydrocarbon gases at high pressures have been called to Our attention by Comings, and and Egly. They made a careful analysis of the following methods commonly used to measure gas viscosities: 1. Oscillating disc viscometer4,5 2. Rolling ball viscometer6,7 3. Capillary tube viscometer12 On the basis of their analysis of the problem and their experimental data on the viscosities of methane, ethylene, carbon dioxide, and propane, they preferentially selected data obtained by the capillary tube viscometer to develop their viscosity correlation. Since then a need has existed to verify the experimental technique of Comings, Mayland, and Egly for the determination of viscosities at high pressure; to extend the data to mixtures of hydrocarbons; and to extend the range of their correlation to include higher pressures. Using the correlation procedure of Comings, May-land, and Egly, the prediction of gas viscosities is resolved into the correlation of the effect of pressure, temperature, and composition on the viscosity of hydrocarbons and their mixtures and the prediction of viscosities of mixtures of hydrocarbons and other natural gas components at one atmosphere pressure.

Jan 1, 1955

By Richard Conkling

A SHALE layer, buried beneath two or three thousand feet of strata, in some instances, will upon folding become thicker in the synclines and thinner on top of the anticlines. This can be accounted for, in part, by the stretching on the crests of the fold and the compressing in the troughs; but this will by no, means account for all of it, as is shown in the example herein set forth. It is my firm belief that the rest of the thickness is due to flow. What causes the movement, however, does not concern us here, so long as there is movement, for this article purposes to show its effect upon the producing area of different sands. It is the author's hope, in this way, to drop a hint or two that may be valuable to the oil geologist, in making estimates of future productions and values of oil properties. An example will be given from property in the famous Cushing Pool in northeastern Oklahoma, where the author has had occasion to make a detailed study before recommending some property to his company, and has then been able to watch the results of this work. The author never mapped the surface structure in this pool, as this had been done by Frank Buttram when he was with the Oklahoma Geological Survey. We are using, therefore, a section of his map in this article for our surface contours. The main east clip comes farther east than this section shows.

Jan 10, 1916

By Keith Leonard Sutherland, Ian William Wark

Mercaptobenzthiazole and its sodium salt are marketed under the trade names Flotagen and Flotagen S respectively, for use as collectors for cerussite and other minerals. The structural formulas for sodium rnercaptobenzthiazole and for sodium ethyl xanthate are: Chemically there is a resemblance between the two compounds, though the free acid (mercaptobenzthiazole itself) is much more stable than xanthic acid. Both are readily oxidized, e.g., by iodine to disulphides, and can be estimated by iodometric titration. Qualitatively they are similar as collectors in flotation, although there are quantitative differences between them that may be important in practice. It is deduced that the influence of the nitrogen atom is subordinated to that of the sulphur atoms, and that the dominant group of these compounds is the mercapto group —SH or —5Na. The general method of investigation has been based on contact tests. Two temperatures, 10" and 35" C., have been chosen, and with a standard concentration of 20 mg. per liter of mercaptobenzthiazole (i.e., of the free acid) the influence of alkali, cyanide and copper sulphate on contact at sulphide mineral surfaces has been studied. This standard concentration corresponds to about 19 mg. per liter potassium ethyl xanthate; it brings out the differences between the minerals better than a higher concentra-

Jan 1, 1939

By Ian William Wark, Keith Leonard Sutherland

MERCAPTOBENZTHIAZOLE and its sodium salt are marketed under the trade names Flotagen and Flotagen S respectively, for use as collectors for cerussite and other minerals. The structural formulas for sodium mercaptobenzthiazole and for sodium ethyl xanthate are: [ ] Chemically there is a resemblance between the two compounds, though the free acid (mercaptobenzthiazole itself) is much more stable than xanthic acid. Both are readily oxidized, e.g., by iodine to disulphides, and can be estimated by iodometric titration. Qualitatively they are similar as collectors in flotation, although there are quantitative differences between them that may be important in practice. It is deduced that the influence of the nitrogen atom is subordinated to that of the sulphur atoms, and that the dominant group of these compounds is the mercapto group -SH or -SNa. The general method of investigation has been based on contact tests. Two temperatures, 10º and 35º C., have been chosen, and with a standard concentration of 20 mg. per liter of mercaptobenzthiazole (i.e., of the free acid) the influence of alkali, cyanide and copper sulphate on contact at sulphide mineral surfaces has been studied. This standard concentration corresponds to about 19 mg. per liter potassium ethyl xanthate; it brings out the differences between the minerals better than a higher concentra-

Jan 1, 1939

By Ian William Wark, Keith Leonard Sutherland

Mercaptobenzthiazole and its sodium salt are marketed under the trade names Flotagen and Flotagen S respectively, for use as collectors for cerussite and other minerals. The structural formulas for sodium rnercaptobenzthiazole and for sodium ethyl xanthate are: Chemically there is a resemblance between the two compounds, though the free acid (mercaptobenzthiazole itself) is much more stable than xanthic acid. Both are readily oxidized, e.g., by iodine to disulphides, and can be estimated by iodometric titration. Qualitatively they are similar as collectors in flotation, although there are quantitative differences between them that may be important in practice. It is deduced that the influence of the nitrogen atom is subordinated to that of the sulphur atoms, and that the dominant group of these compounds is the mercapto group —SH or —5Na. The general method of investigation has been based on contact tests. Two temperatures, 10" and 35" C., have been chosen, and with a standard concentration of 20 mg. per liter of mercaptobenzthiazole (i.e., of the free acid) the influence of alkali, cyanide and copper sulphate on contact at sulphide mineral surfaces has been studied. This standard concentration corresponds to about 19 mg. per liter potassium ethyl xanthate; it brings out the differences between the minerals better than a higher concentra-

Jan 1, 1939

By C.H. Lorig, M.C. Udy

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By M. C. Udy, C. H. Lorig

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By H. M. Chance

The great outspread of the coal measures over portions of thirtyone of the sixty-seven counties of Pennsylvania, and the large number of workable seamy comprising the coal series,—together with some workable seams lately shown to belong to the (so-called) barren measures,—-create the impression that these fields contain a practically inexhaustible supply of fucl, and those who have estimated or attempted to estimate their available tonnage have generally promulgated this view. But the actual total contents of this coal-field is of no importance to us at present; calculations including all seams, whether thick enough to mine or not, whether pure enough to furnish a marketable fuel or not, whether accessible at reasonable depth or not, are of no practical value. As coal producers, we are interested not in the total contents, but in the total amount of easily accessible coal of good quality contained in beds thick enough for remunerative mining. The estimates contained in this payer refer exclusively to workable and accessible coal of commercial value,—we may call it available" coal. I am not aware that any one has as yet attempted to estimate in

Jan 1, 1882

By H. M. Chance

THE great outspread of the coal measures over portions of thirty-one of the sixty-seven counties Of Pennsylvania, and the large number of workable seams comprising the coal series, together with some workable seams lately shown to belong to the (so-called) barren measures, create the impression that these fields contain a practically inexhaustible supply of fuel, and those who have estimated or attempted to estimate their available tonnage have generally promulgated this view. But the actual total contents of this coal-field is of no importance to us at present; calculations including all seams, whether thick enough to mine or not, whether pure enough to furnish a marketable fuel or not, whether accessible at reasonable depth or not, are of no practical value. As coal producers, we are interested not in the total contents, but in the total amount of easily accessible coal of good quality con-tained in beds thick enough for remunerative mining. The estimates contained in this paper refer exclusively to workable and accessible coal of commercial value, we may call it "available" coral. I am not aware, that any one has as yet attempted to estimate in

Jan 1, 1882

By William Garrett

I have heard it said that the late Mr. Holley made use of this remark: " There is an inherent, cussedness about rolls which, so far, no man has been able to find out." I think this can be safely claimed in reference to steel, as there are certain peculiarities about it that are pretty hard to account for. Previous to the introduction of the Bessemer process there was, as it were, a great chasm between iron and crucible steel; and, outside of what futile attempts had been made in puddling steel, nothing had been done to fill this gap. The Bessemer steel struck a medium between the two, the softest of it not being able to take the place of good iron, while the hardest was not suitable to encroach very far upon the crucible-steel trade. The open-hearth process made quite an inroad into the latter, but only for the lower and cheaper grades; and, beyond a doubt, for the finest grades of tool-steel, the cruciblesteel business has a long life before it. On the other side of the line comes the " basic " process, which brings us a step nearer iron ; but to fill up the gap completely, comes the Clapp-Griffiths process, which makes a grade of material—call it what you will—that is as soft as iron, welds as readily, and is in a fair way to supersede iron altogether. For fifteen years, I was in the employment of the Cleveland

Jan 1, 1886

By D. R. Conlon, E. R. Brownscombe

Errors in measurement of reservoir pressure include: (I) gauge errors, and (a) interpretation errors. Gauge errors may be reduced by: (a) reading charts with a comparator microscope, (b) use of hard metal stylus points to give clear lines, (6) insuring temperature equilibrium, and (d) making multiple tests. Check calibrations are equally as important as check well tests. A statistical analysis of such check runs shows quantitatively the advantages of a standardized "zero pressure line'' and of the use of field calibrations made at bottom-hole temperature on the same chart run in the well. Interpretation errors include: (a) fluid heads, which should be corrected to the top of the perforations on the basis of well-fluid gravity and from the top of the perforation to the datum level on the basis of reservoir-fluid gravity, and (b) gradients around the well. Conventional shut-in periods may be entirely inadequate to overcome these, necessitating a reservoir study based on build-up curve data, reservoir history, core analysis and any other available information. Interest in engineering studies of the pressure changes in oil and gas reservoirs is increasing. This type of work yields important information and doubtless will be greatly extended in the future. One of the factors limiting the work, however, is the accuracy with which the reservoir pressures can be determined; for if the inaccuracies in the pressure measurements represent an appreciable percentage of the pressure changes, the engineer is seriously handicapped, and must delay the reservoir study until the reservoir pressure has changed a relatively large amount. This delay can greatly reduce the benefits of such studies, at least from the point of view of aiding the leasing, drilling and completion programs. Thus, from the point of view of reservoir analysis, it is frequently important to obtain the most accurate pressure data possible early in the history of any field—particularly for the gas-distillate fields now being developed. This paper deals with improvements in the measurement of bottom-hole pressures that permit pressures even as high as 4000 or 5000 lb. per sq. in. to be determined with gauge errors of only+ ±I to 2 lb. per sq. in. Since pressures out in the reservoir rather than in the bottom of the hole concern the reservoir analyst, differences between bottom-hole pressures and actual reservoir pressures are also considered. In general, errors in pressure measurement may be divided into: 1. Gauge errors: a. Errors due to inaccuracies in reading the pressure charts. b. Errors due to irreproducibility of the pressure element and recording system. c. Errors caused by failure to allow the gauge to reach temperature equilibrium. 2. Internretation errors: a. Errors caused by a fluid head between the gauge position in tubing and the pressure at the datum level in the reservoir. b. Pressure gradients in the reservoir.

Jan 1, 1946

By D. R. Conlon, E. R. Brownscombe

Errors in measurement of reservoir pressure include: (I) gauge errors, and (a) interpretation errors. Gauge errors may be reduced by: (a) reading charts with a comparator microscope, (b) use of hard metal stylus points to give clear lines, (6) insuring temperature equilibrium, and (d) making multiple tests. Check calibrations are equally as important as check well tests. A statistical analysis of such check runs shows quantitatively the advantages of a standardized "zero pressure line'' and of the use of field calibrations made at bottom-hole temperature on the same chart run in the well. Interpretation errors include: (a) fluid heads, which should be corrected to the top of the perforations on the basis of well-fluid gravity and from the top of the perforation to the datum level on the basis of reservoir-fluid gravity, and (b) gradients around the well. Conventional shut-in periods may be entirely inadequate to overcome these, necessitating a reservoir study based on build-up curve data, reservoir history, core analysis and any other available information. Interest in engineering studies of the pressure changes in oil and gas reservoirs is increasing. This type of work yields important information and doubtless will be greatly extended in the future. One of the factors limiting the work, however, is the accuracy with which the reservoir pressures can be determined; for if the inaccuracies in the pressure measurements represent an appreciable percentage of the pressure changes, the engineer is seriously handicapped, and must delay the reservoir study until the reservoir pressure has changed a relatively large amount. This delay can greatly reduce the benefits of such studies, at least from the point of view of aiding the leasing, drilling and completion programs. Thus, from the point of view of reservoir analysis, it is frequently important to obtain the most accurate pressure data possible early in the history of any field—particularly for the gas-distillate fields now being developed. This paper deals with improvements in the measurement of bottom-hole pressures that permit pressures even as high as 4000 or 5000 lb. per sq. in. to be determined with gauge errors of only+ ±I to 2 lb. per sq. in. Since pressures out in the reservoir rather than in the bottom of the hole concern the reservoir analyst, differences between bottom-hole pressures and actual reservoir pressures are also considered. In general, errors in pressure measurement may be divided into: 1. Gauge errors: a. Errors due to inaccuracies in reading the pressure charts. b. Errors due to irreproducibility of the pressure element and recording system. c. Errors caused by failure to allow the gauge to reach temperature equilibrium. 2. Internretation errors: a. Errors caused by a fluid head between the gauge position in tubing and the pressure at the datum level in the reservoir. b. Pressure gradients in the reservoir.

Jan 1, 1946

By Henry Eyring, Jay W. Fredrickson

MANY theories have been advanced to explain the phenomena of elastic and plastic deformation. The object of this report is to present a mechanism for deformation, not radically differing from existing theories, but embodying certain principles and concepts of these theories. This proposed theory cannot be the complete answer to the age-old problem of deformation but it is believed that it will be a step further in the proper direction. The plastic properties of solids have recently been reviewed by Seitz and Read.1 Zener2 has reviewed and correlated the existing work on the anelasticity of metals. With these and othersa3,4,5 present theories of deformation are well-known. Of the many theories now extant, those receiving most attention have been proffered by Griffith,6 Becker,7 Smekal,8 Polanyi,9 Orowan10 and Taylor.11Although differing quite widely in details, these theories are based more or less on a common principle of flaws or dislocations that exist in the crystal lattice. The effect of stress concentrations surrounding a flaw or crack has been treated most recently by Fisher and Hollomon.12 The various authors differ as to the exact nature of the flaws or dislocations, the causes of their appearance, or the manner in which they initiate slip. All of the theories agree that the number of dislocations increases with progressing deformation. It is universally agreed that the shearing process is not a simple gliding of ideally perfect atomic lattice planes. It is also agreed that the "macroscopic process of gliding, or slip, is brought about by the spreading of a large number of locally initiated "glide steps" through the whole crystal. The occurrence of these "glide steps" is closely related to the presence of some kind of deviations from the "ideal" lattice structure, even in the undeformed crystal. These deviations are overcome "one at a time," in a manner of speaking, due to some stress-concentrating effect." PROPOSED THEORY Many solids show a continuously increasing deformation if subjected to a constant load of suitable magnitude in an extended range of temperature for a sufficient time. This deformation, or flow, may be said to be due, in general, to the tendency of the atoms or molecules in an elastically stressed body to readjust themselves in such a way that if the deformation were kept constant, a release of stress would take place. If rupture does not occur, this process of relaxation causes the rate of flow to obtain a final constant value, as shown in the curve (Fig I) obtained by Taylor and Quinney.14 In. this state the release of stress by relaxation exactly counterbalances the increase due to the elastic strain on the test pieces. .

Jan 1, 1948

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

In two previous paperslJ dealing with the carbon-oxygcn reaction, and the simultaneous content of each, in liquid steel in the furnace, we have made use of the quantity A[O], defined as the excess oxygen beyond what would be in equilibrium with carbon then present if the pressure of carbon monoxide were I atm.; that is, if [C] X [O] is taken as 0.00222, A[O] = [O] - 0.0022[C] where [O] is the percentage of oxygen by weight as measured by the method described earlier.3 This quantity ?[O] proves to be substantially independent of carbon content over the range 0.08 to I,z per cent, as well as of the basicity of the slag, and is nearly always within the limits o.o15 to o.oz5 per cent when the bath is boiling normally and is in what we have termed a steady state, Apparently it must be at least about 0.014 per cent before boiling occurs; but this threshold value seems to depend upon the ease of bubble formation at the metal-hearth interface, hence upon the condition of the surface of the hearth. In any case, ~(01, on the average, changes considerably following any disturbance of the bath, as by addition of ore. The present paper deals with the average changes in A[O] level following addition of spiegel or crop ends, or after procedures to promote stirring, or by tapping of the steel from the furnace. The observations were made on a large number of commercial heats, and consequently are subject to the influence of various disturbing factors; the results have the compensating merit of showing the consistency obtainable under the limitations imposed by practical operation. Variability of Excess Oxygen in Normal Open-hearth Operation The preceding genera' statements refer to the average value of A[0] particularly in heats that are boiling actively; on individual heats, which are less active, there may be a variable time lag between the disturbance and its effect, which complicates the interpretation of what is going on. For instance, if in the normal refining process boiling is sluggish, the slag usually is gaining Oxygen from the gas phase above it, Or from added Ore$ faster than it is losing oxygen to the metal; Yet when the bath starts to boil vigorously, the opposite condition may prevail for Some time. The consequence of this lag is a variation of A[o], the interpretation of which in a sing1e heat may not be immediately obvious. This condition is illustrated in Figs. I and 2. In Fig. 1, A[0] at the beginning of the test period was near the lower limit of its usual range (dashed lines) in the steady state as a consequence of the lime boil, which had ended about as indicated. The bath is now cold, carbon drop is slow, and the first small orc feed causes only a small rise in A[O]; as the temperature rises and as lime dissolves in the slag, and the bath becomes more active, the

Jan 1, 1948

By A. B. Dyes, P. H. Braun, B. E. Cole

This paper presents a reservoir engineering analysis of the performance data for a waterflooding project in the Johnson Lease, South Ward field. This type of engineering analysis adds to the knowledge of the mechanics of water flooding. This study reveals that in general (a) high ultimate areal sweep-out efficiencies (95 to 100 per cent) can be expected, and (b) cross-flow among strata of different permeabilities during the fill-up phase can have an important influence on the behavior and should be dealt with in studying reservoirs for water flooding. The analysis further showed that the recovery predictions based on what was considered a consistent interpretation of core data and logs were low because little contribution was assumed from the low permeability, oil-bearing sand sections which have apparently yielded considerable waterflood oil. This project has yielded in excess of 2 1/2 times as much oil by water flooding as by primary depletion. These very favorable results were achieved without the use of any special injection well completion techniques. However, all of the low permeability material war included in the section open to injection despite its poor estimated primary yield. LEASE PERFORMANCE HISTORY The South Ward field lies in the southeast corner of Ward County near the southern tip of the tremendous Yates trend. Deposition of sand bodies along the seashore reefs during the latter part of the Permian period established what have turned out to be ideal conditions to form a great number of independent productive sands. Probably, these reservoirs in Ward and Winkler counties are providing operators with some of the nation's richest sources of secondary oil reserves through the use of waterflooding techniques. In South Ward field water has been very successfully used to flood oil from the Bennett sand occurring at a depth of about 2,300 to 2,400 ft. About 150 ft above the Bennett sand reservoir, the Grand Falls sand produced gas from a large cap extending over most of the field. The Atlantic Refining Co.'s 320-acre W. D. Johnson lease (Fig. 1) is on the northwest edge of the structure with only gas cap apparently present in the Grand Falls sand. The Bennett sand under this lease is oil productive, however, having a gross sand thickness averaging about 80 ft with a net of 18 ft of fairly clean, highly permeable sand, and about 36 ft of oil-bearing sand with low permeability and high water saturation. The lower permeability sand is interbedded with numerous layers of lime, shale, and anhydrite. Radioactivity logs from 12 wells and cores from two, examples of which are shown in Fig. 2, reveal that the total Bennett sand pore volume is about 71,000 bbl/acre. The estimated initial water saturation averages 41 per cent in the 54 ft of sand considered to contain oil; thus, also considering an estimated 18 per cent oil shrinkage, the lease originally contained about 34,000 bbl of oil per acre. Original pressure was probably about 1,400 psig. PVT correlations indicate that the reservoir fluid was originally saturated with gas. After discovery of the field in 1930, Atlantic completed the first well on the Johnson lease in March,

Jan 1, 1958

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

In two previous paperslJ dealing with the carbon-oxygcn reaction, and the simultaneous content of each, in liquid steel in the furnace, we have made use of the quantity A[O], defined as the excess oxygen beyond what would be in equilibrium with carbon then present if the pressure of carbon monoxide were I atm.; that is, if [C] X [O] is taken as 0.00222, A[O] = [O] - 0.0022[C] where [O] is the percentage of oxygen by weight as measured by the method described earlier.3 This quantity ?[O] proves to be substantially independent of carbon content over the range 0.08 to I,z per cent, as well as of the basicity of the slag, and is nearly always within the limits o.o15 to o.oz5 per cent when the bath is boiling normally and is in what we have termed a steady state, Apparently it must be at least about 0.014 per cent before boiling occurs; but this threshold value seems to depend upon the ease of bubble formation at the metal-hearth interface, hence upon the condition of the surface of the hearth. In any case, ~(01, on the average, changes considerably following any disturbance of the bath, as by addition of ore. The present paper deals with the average changes in A[O] level following addition of spiegel or crop ends, or after procedures to promote stirring, or by tapping of the steel from the furnace. The observations were made on a large number of commercial heats, and consequently are subject to the influence of various disturbing factors; the results have the compensating merit of showing the consistency obtainable under the limitations imposed by practical operation. Variability of Excess Oxygen in Normal Open-hearth Operation The preceding genera' statements refer to the average value of A[0] particularly in heats that are boiling actively; on individual heats, which are less active, there may be a variable time lag between the disturbance and its effect, which complicates the interpretation of what is going on. For instance, if in the normal refining process boiling is sluggish, the slag usually is gaining Oxygen from the gas phase above it, Or from added Ore$ faster than it is losing oxygen to the metal; Yet when the bath starts to boil vigorously, the opposite condition may prevail for Some time. The consequence of this lag is a variation of A[o], the interpretation of which in a sing1e heat may not be immediately obvious. This condition is illustrated in Figs. I and 2. In Fig. 1, A[0] at the beginning of the test period was near the lower limit of its usual range (dashed lines) in the steady state as a consequence of the lime boil, which had ended about as indicated. The bath is now cold, carbon drop is slow, and the first small orc feed causes only a small rise in A[O]; as the temperature rises and as lime dissolves in the slag, and the bath becomes more active, the

Jan 1, 1948

By D. L. Harris, A. M. Gaudin

THE following results, presented here in condensed form,1 were obtained in a preliminary study of the adsorption of n-hexane thiol, hexyl mercaptan, on sphalerite, zincite, willemite, and quartz, from aqueous solution and from a gas. Interest in this subject was aroused by a Belgian report2 of effective use of hexyl mercaptan for flotation collection of oxidized zinc minerals. The relatively low boiling point, 149°C, of the mercaptan3 suggested the desirability of extending the usual measurements of partition of collector between aqueous solution and gas and between gas and mineral. It is believed that this paper presents the first measurements of this type on a flotation system. Attempts were made to carry out the measurements at equilibrium, but as the work progressed it became increasingly doubtful that this desirable condition had been achieved. To control composition and extent of the gas phase, the apparatus was a wholly-enclosed thermally-controlled glass system. Because of these constraints and the desirability of dealing with pure minerals, a scale of operations was chosen in which a few grams of deslimed mineral were used in each test. It was also necessary to choose a particularly sensitive method for mercaptan analysis, and in fact a method that would permit the experimenters to follow the approach to equilibrium. For these reasons mercaptan marked by radiosulphur 35 was used. An analysis was made for the radiosulphur by a modification of the method of Gaudin and Carr.4

Jan 9, 1954