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By W. E. Bergman, P. G. Carpenter, H. B. Fisher

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By John C. Calhoun, Raymond G. Loper

Theoretical calculations for the decline of pressure and the variation of instantaneous producing gas-oil ratio with increased cumulative production have been made for reservoir systems under various producing drawdown values and for various spacings. These variables have been included by a modification of previously Published techniques. This consists essentially of utilizing a radial system flowing gas and oil in a succession of steady state calculations. The results of the calculations do not show any variation in the predicted behavior of the internal gas drive reservoir when either the drawdown or the spacing are changed. The prediction of performance on an internal gas drive reservoir has been presented by various authors. ',"' These predictions are in the form of a pressure decline and an instantaneous producing gas-oil ratio as a function of cumulative oil withdrawal. In making these predictions a basic assumption has been that the saturation of the reservoir is uniform throughout at any time, or that the pressure differential imposed on the reservoir system is zero. Because of these assumptions the validity of such predictions has been questioned. Their application to actual systems, where saturations are not uniform and where producing differentials exist, has been a hazardous procedure. The authors cited have used different methods of approach to the derivation of equations for making their predictions and for arriving at a solution of both equations, but basically the same relationships are utilized in each case. In all instances the instantaneous producing gas-oil ratio is calculated from the equation: In utilizing this equation an average reservoir pressure and an average reservoir saturation must be known, the former to define ß, v, s, and uo/ug and the latter to define kg/ko. Predictions can be made, therefore, only for the conditions of a uniform reservoir saturation and a uniform reservoir pressure. This restriction of requiring a uniform oil saturation can be resolved by applying two-phase steady state flow for the radial system to the reservoir's history. Radial steady state flow is defined when the ratio of phases flowing,

Jan 1, 1949

By W. F. Kieschnick, C. C. Miller, E. R. Brownscombe

The possibility has been mentioned that large pressure gradients in a solution gas driven field caused by high production rates might lead to a reduction in the ultimate recovery obtainable compared to that which would be obtained by a very slow rate of production. In the present study the reservoir conditions accompanying a high rate of production and the corresponding ultimate recovery were compared with those obtained if the reservoir were produced at some marginal rate throughout its entire life. The method of calculation involved the application of fluid flow - material balance analysis to a series of successive steady state conditions in the reservoir. In the case studied very little difference in recovery was obtained at the abandonment pressure. An analysis of the basic factors involved indicates that the sane results would hold for considerable variation in properties of reservoir fluids, permeability of the formation or well spacing. Even if the reservoir has a water drive it appears that no harm will be done by- open flow production if the rate is cut back before any appreciable free gas is produced. However, any condition which leads to disproportionate withdrawal rates and which causes large pressure differences over large areas might result in substantial loss in ultimate recovery. INTRODUCTION When the pressure declines in a reservoir, gas is evolved from solution causing a shrinkage in the reservoir oil so that a stock tank barrel of oil with its residual dissolved gas occupies a smaller volume than originally. For a given reservoir oil saturation, therefore. stock tank oil content will be higher at the lower pressure. At the same time the evolved gas which remains in the reservoir reduces the reservoir oil saturation, and this would be expected perhaps to cause a reduction in stock tank oil content. However, around the well the shrinkage occurs so rapidly that stock tank oil may actually accumulate in this region in spite of the simultaneous reduction in reservoir oil saturation. If this accumulation should continue, spreading into a larger zone, the loss might be appreciable and because larger pressure gradients accompany higher rates the accumulation might possibly be large if wells are produced at too high a rate. It is the purpose of this paper to determine the effect of rate of flow on ultimate recovery by solution gas drive. The problem under consideration involves the unsteady state flow of oil in a closed radial system from which oil is produced by the evolution of gas as a finite drawdown is estalllished and the reservoir pressure declines. A somewhat similar unsteady state production problem dealing, however, with a linear system has been considered by Muskat and Meres, but these authors do not discuss the effects which rate may have on recovery. Other methods have been reported for estimaling recovery as a function of pressure decline when producing at an infinitesimal rate, and Muskat and Taylor' have shown the effect of fluid and reservoir characteristics on recovery under these conditions. Assuming steady state to exist, Babson has given a procedure for computing the decline in well productivity as the field is depleted, and Moyer has combined these methods to estimate abandonment conditions and the resulting ultimate recovery. These latter approaches to the problem either do not consider the effect of rate or assume steady state can be established. In detail this paper presents the behavior of the reservoir producing under unsteady state conditions and considers the effect of production rate during this unsteady state flow on the recovery attained. The analysis also shows that there will exist at abandonment a type of steady state, and on this basis a method has been clevelopetl for rapid calculation of abandonment conditions.

Jan 1, 1949

By H. L. Bilhartz, H. F. Dunlap, C. R. Bailey, Ellis Shuler

Data are presented which indicate that the saturation exponent, n, in the equation, R. = R100S-11, relating core resistivity, I:,. to the resistivity at 100 per cent saturation. R100. and to the saturation, S. may vary appreciably from the value of two which is usually assumed for this exponent when interpret ing well logs. Values ranging from one to two and one-half have been found on (.ore sample investigated to date. Attempts to correlate this saturation exponent with porosity or permeability of the core have not been successful. The saturation exponent is apparently not a function of the interfacial tension between the brine and the displacing fluid. Some evidence is given indicating that the resistance of the core is not a unique function of the saturation but depends upon the manner in which this saturation was achieved. Equipment and technique are discussed for measurement of resistivities in core plugs in which water saturation can be varied. lNTRODUCTION A number of investigations of the resistivity-saturation relationship for un-c~~nsolidated sands and consolidated (.ore samples have been reported in the literature. According to most of these: R. = R¹ººS², where R² = the resistivity of a formation at saturation S, and R¹ºº= the resistivity of the formation at 100 per cent water saturation. Much of this work was (lone on unconsolidated sands desaturated by gas or oil. Hen-clerson and Ynster worked exclusively with dynamic systems, flowing oil or gas through consolidated cores. There is some doubt as to how well this reproduces static reservoir conditions. Jakosky and Hopper³ onsidered also the case of consolidated core plugs, but the oil-water distribution in the emulsions which they used to saturate their cores is almost certainly different from that occurring in reservoirs. Recently Guyod quotes the results of some Russian work which indicates that n may vary from 1.7 to 4.3. No experimental details of this work are available. In connection with electric log interpretation it is important to know the value of the saturation exponent. For example, if in a given reservoir it is found that the resistivity is three time.; the resistivity observed when the reservoir is 100 pel. cent 'saturated with water, this fact would be interpreted as indicating a water saturation of 33 per cent if the saturation exponent were 1 and a water saturation of 6-1 per cent if the saturation exponent were 2.5. EXPERIMENTAL METHOD In the work to be described it was assumed that reservoir conditions are most nearly obtained when core plugs are desaturated by the capillary pressure technique referred to in numerous places in the literature, as for example. in Bruce and Welge's paper.' In this technique the core. saturated 100 per cent with brine, is placed in contact with a ceramic disc permeable to brine but not to the displacing medium for the displacement pressures used. Pres-ure is then applied to the displacing medium and brine forced out of the core through the ceramic disc. Fig. 1 shows the core plug in place in the cell in which resistivity and saturation measurements are made. Fig. 2 shows the schematic electrical diagram wed to make resistivity measurements on the core plug. A four-electrode type circuit is used, employing a Hewlett-Packard model 400A. AC vacnum tube voltmeter. The 60-cycle AC current througli the core is adjusted to 1 milliampere and measured by noting the voltage drop across the calibrated 100-ohm resistor. The vo1tages appearing at probes 1, 2, 3, and 4 are then successively measured. Voltage drops across the top, center, and bottom portions of the core are obtained by sublracting the voltages appearing at successive probes. This technique avoids any polarization or other high contact resistance phenomena which may develop at the current input electrodes. Resistances which may develop between the core and the probes, and which are small compared to the 1-megoam input impedance 01' the vacuum tube voltmeter will (obviously not affect the measurements allpreciably. Any very appreciable resistallces which may develop at any of the probe wires are detected and allowed for by inserting a 1-megohm resistor in series with the voltage measuring probe. If the probe resistance is actually zero, the new voltage measured after insertion of the I-megolim resistor will be approximately one-half of that previously measured. since the input impedance of the vacuum tube voltmeter is itself 1 megohm. If an! appreciable probe resistance has developed, the new voltage is found to be appreciably greater than one-half of the previously measured voltage. Such probe resistance; have been found to develop only occasionally and usually can be traced to poor connections betwern the core

Jan 1, 1949

By Jack D. Webber

The successful use of oil well packers requires, in part: an understanding of the pressures which exist at the packer in various applications and an understanding of the characteristics of the various types of packers. It is with these pressures, the resultant forces, and the characteristics of packers. that this paper is primarily concerned. An oil well packer may be defined as a mechanical device for blocking the passage of fluids in an annular space. In the more usual case, the annular space is that between the tubing or drill pipe in a well and the casing, and packers which block such an annular space are broadly referred to as casing packers. In the other case. the annular space is that between the tubing or drill pipe and the walls of an open hole, and packers for blocking this space are generally called formation packers. While the hydraulics involved are essentially the same for casing and formation packers. a greater variety of conditions are encountered in the use of casing packers and only casing packers will be discussed. After a packer has been set and a pressure seal effected between tubing and casing, the packer is comparable to a piston in a cylinder. Pressures acting upon a piston result in forces which will move the piston unless some means is provided to prevent such movement. In the same manner, pressures acting upon a packer will move the packer unless there is present a sufficiently great restraining force. PACKER CLASSIFICATIONS Packers may be classified according to the pressure conditions under which they are capable of blocking the annular space between tubing and casing. Fig. 1 shows schematically two types of packers in common use. These packers are capable of blocking the annular space against the passage of fluids under a differential pressure of significant magnitude only when the pressure in the annular space above the packing element is greater than the pressure below. It may be seen that in Fig. l-a. slips with teeth which bite into the casing and prevent downward movement are provided. In Fig. 1-h. an anchor prevents downward movement. In each case, there i-only the tubing to prevent upward movement when differential pressures act to move the packers upwardly. Packers which hold only a significant differential pressure acting downwardly have been in use since the early days of the oil industry and will hereafter be referred to as conventional type packers. In many packer applications operating conditions will 1.crult in differential pressures across the packer which will at times act to move the packer upwardly, and at other times, act to move the packer downwardly. For these applications, designs are available which will block the annular space and resist movement in either direction. Fig. 2-a shows schematically a packer of this type which is designed to be run into a well and set, and removed when desired by merely pulling the tubing. It will be noted that two sets of slips are provided-— one set above the packing element to prevent upward movement, and another set below the packing element to prevent downward movement. This packer is built around a mandrel which is essentially a part of the tubing. and which is free to move longitudinally within certain limits through the set packer. Fig. 2-b shows schematically a permanent type packer which is capable of holding pressures from either direction. Here again, two sets of slips are provided to prevenl movement of the packer. This packer is designed to become virtuallv a part of the casing when set and it is made of drillable material so that it may be drilled out when its removal is desired. The seal nipple shown effects a pressure seal between the tubing and the packer. This seal nipple is a part of the the tubing, and the nipple and tubing may be withdrawn from the well without disturbing the packer. It should be noted that these figures are not representative of all available packers which are designed to hold pressures from both above and below. Packers which resist movement in either direction will hereafter be referred to as universal type packers. There is a third type of packer in general use and this type is designed to block the passage of fluids when the pressure below the packing element ii greater than that above. This type is provided with slips which prevent upward movement of the packer and is somewhat similar to a conventional type packer run upside-down. Packers designed to hold pressure only from below are made in a variety of designs and are usually owned and operated by service companies.

Jan 1, 1949

By J. S. Billheimer, B. H. Sage, W. N. Lacey

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.' Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2'3'4'5'6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made' and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."' The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By Morris Muskat, J. M. McDowell

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By William Hurst, A. F. van Everdingen

For several years the authors have felt the need for a source from which reservoir engineers could obtain fundamental theory and data on the flow of fluids through permeable media in the unsteady state. The data on the unsteady state flow are composed of solutions of the equation Two sets of solutions of this equation are developed, namely. for "the constant terminal pressure case" and "the constant terminal rate case." In the constant terminal pressure case the pressure at the terminal boundary is lowered by unity at zero time, kept constant thereafter, and the cumulative amount of fluid flowing across the boundary is computed, as a function of the time. In the constant terminal rate case a unit rate of production is made to flow across the terminal boundary (from time zero onward) and the ensuing pressure drop is computed as a function of the time. Considerable effort has been made to compile complete tables from which curves can be constructed for the constant terminal pressure and constant terminal rate cases, both for finite and infinite reservoirs. These curves can be employed to reproduce the effect of any pressure or rate history encountered in practice. Most of the information is obtained by the help of the Laplace transformations, which proved to be extremely helpful for analyzing the problems encountered in fluid flow. The application of this method simplifies the more tedious mathematical analyses employed in the past. With the help of Laplace transformations some original developments were obtained (and presented) which could not have been easily foreseen by the earlier methods. INTRODUCTION This paper represents a compilation of the work done over the past few years on the flow of fluid in porous media. It concerns itself primarily with the transient conditions prevailing in oil reservoirs during the time they are produced. The study is limited to conditions where the flow of fluid obeys the diffusivity equation. Multiple-phase fluid flow has not been considered. A previous publication by Hurst' shows that when the pressure history of a reservoir is known, this information can be used to calculate the water influx, an essential term in the material balance equation. An example is offered in the literature by Old² in the study of the Jones Sand, Schuler Field, Arkansas. The present paper contains extensive tabulated data (from which work curves can be constructed), which data are derived by a more rigorous treatment of the subject matter than available in an earlier publication.' The application of this information will enable those concerned with the analysis of the behavior of a reservoir to obtain quantitatively correct expressions for the amount of water that has flowed into the reservoirs, thereby satisfying all the terms that appear in the material balance equation. This work is likewise applicable to the flow of fluid to a well whenever the flow conditions are such that the diffusivity equation is obeyed. DIFFUSITY EQUATION The most commonly encountered flow system is radial flow toward the well bore or field. The volume of fluid which flows per unit of time through each unit area of sand is expressed by Darcy's equation as where K is the permeability, the viscosity and aP/ar the pressure gradient at the radial distance r. A material balance on a concentric element AB, expresses the net fluid traversing the surfaces A and B, which must equal the fluid lost from within the element. Thus, if the density of the fluid is expressed by p, then the weight of fluid per unit time and per unit sand thickness, flowing past Surface A, the surface nearest the well bore, is given as The weight of fluid flowing past Surface B, an infinitesimal distance 6r, removed from Surface A, is expressed as

Jan 1, 1949

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs.' Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster" and was first reduced to practice by the experimentation of Welge. In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid Phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always ereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By Walter Rose

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs. Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster and was first reduced to practice by the experimentation of Welge . In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize Welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always gereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By R. Ingerson

Bore surfaces of used guns commonly show a pattern of cracks in various degrees of development. It has been suggested that these cracks may aid erosion by providing channelways for the gases, eventually leading to the tearing out of blocks of metal. Under the general studies of gun erosion conducted at the Geophysical Laboratory it appeared desirable to consider this factor, and to determine the resistance to surface cracking offered by gun steel and by various other materials that might be used in the bores of guns. Method and Apparatus In order to make such a determination it is necessary to have (I) an arrangement in which the surface to be studied can be subjected to conditions similar to those in a gun with respect to temperature, pressure (developed by explosion gases), composition of the gases and length of time the surface is exposed to the gases; and (2) a specimen that can be examined readily after any number of shots, and then fired again, if necessary. The first of these conditions can be met by using an explosion vessel designed by H. S. Roberts of the Geophysical Laboratory. Fig I shows a cross-section of the apparatus. The "gun" G from which the charge is fired is made from the receiver of a caliber 0.30 army rifle, M1903, and the charges are prepared in caliber 0.30 cartridge cases. The test specimen S is held in place by a cone-shaped plug P and by a steel bridge B which is bolted to the outside of the explosion vessel on either side of the section shown. The plug, in turn, is held in place by a screw collar C. Maximum pressure is controlled by a brass rupture disk R. Part of the explosion gases flow past the two flat areas on S. Temperature and composition of gases, and the time before the rupture disk breaks, can be controlled by amount and kind of powder used, and pressure can be controlled by using rupture disks of different thickness. While the explosion vessel used was not designed so that temperature and pressure could be measured, in other vessels of closely similar size and shape containing proportionate charges of the same kind of powder as that used for standard testing procedure, values of 2700°K and 50,000 psi were obtained. Since the orifices past the flat areas on the plug are small compared to the rupture disk hole (I:I6), most of the gas goes out through the rupture disk when it breaks. The amount that goes by the plug depends on (I) the pressure attained before the rupture disk breaks and (2) the time it takes for this pressure to be built UP. The second condition (examination at will after any firing) is met by using for specimens short rods that have flat areas ground on opposite sides. These flat

Jan 1, 1949

By C. B. Clark, W. H. Bruckner

Since the end of World War II interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Mun-roe more than 50 years ago (in 1888). Details of their design have been explained elsewhere.1,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense Pressures exerted when the explosive charge is detonated. Among the conclusions reached in research On shaped explosive charges, the following have been established concerning cavity liners:1'2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the 'One as well as On the base diameter of the charge. Acute apex angles require thinner walls for optimum perfmnance and more obtuse angles require thicker walls for the same base diameter' 2. Cones were more effective in forming a penetrating jet when the walls were tapered; that is, the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical properties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, tensile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2, Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45° cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1949

By Terkel Rosenqvist

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations

Jan 1, 1949

By Reno H. Sales, Charles Meyer

AT Butte, successive zones of sericitized and argillized quartz monzonite occur around every ore-bearing fracture regardless of its size, attitude, or relative age. The two types of alteration always occupy the same relative positions; sericite adjacent to the ore-bearing vein, clay minerals always between the scricitized rock and fresh quartz monzonite, except where overlap of alteration effects between adjacent fissures has eliminated the lower grade mineralogical products, as is the case in much of Butte's Central zone of pervasive sericitization. As long as active circulation continued in the channel, each zone migrated away from the fissure, that is, it grew at its outer edge and simultaneously receded at its veinward edge because of encroachment by the next innermost zone. The different mineralogical and chemical responses within the wall rocks to the attack by the ore fluid are dependent not on a drastic about-face change of composition of the fluid in the channel relative to its ability to alter the quartz monzonite but on continuously varying conditions of physico-chemical environment within the wall rock outwardly from the vein.' Introduction From the economic viewpoint it is highly desirable that much effort be expended for the purpose of increasing our knowledge of ores and their origin. It has been the observation of the senior writer, many times expressed, that the mining companies have spent too little money in research on the geology of nature's deposits of copper, lead, and zinc, which we know to be of limited extent and which, when exhausted, must be replaced by new discoveries. Experience at Butte and elsewhere has forced the conclusion that observation and mapping in the field must be supplemented by laboratory work if we are to arrive at a reasonably correct understanding of the geology of ore bodies and their environments. It is only through the medium of such correct understanding of geology that we shall be able to accomplish the maximum toward aiding mine operations and at the same time provide a proper background for field examination work whether it be geological or geophysical. The Anaconda Copper Mining Company's answer to the need above expressed has been to equip a geological laboratory at Butte. The reason why Butte was selected is obvious, for situated there is one of the world's largest and geologically most interesting concentrations of copper and zinc. Furthermore, because of the great extent of underground workings both laterally and vertically, the opportunities for observation and study of ore occurrences probably are unequaled anywhere. The laboratory was established with five principal objectives in view. These were: 1. As an aid to Anaconda Company mine operations at Butte and elsewhere, this work to supplement that of the mine geologists. 2. To aid in acquiring as complete an understanding as possible of the behavior of Butte veins and ore bodies laterally and in depth.

Jan 1, 1949

By W. H. Emmons

Many mineral veins occupy faults, and movements on certain warped fault planes have resulted in openings. On normal faults the steeper parts have the widest openings, and on reverse faults the flatter parts have the widest openings. Theoretically the width of the opening is the sine of the angle of deflection times the amount of movement on the fault plane, but actually the widths of some of the openings are probably less because of readjustments of walls along joints or of other readjustments. The first treatment of the subject seems to have been in a book on mineral veins by John Leithart, published in Newcastle, England, in 1838. Later the subject was treated in various texts published in Germany, in England, and elsewhere. The subject was not given much prominence in the earlier American literature on economic geology, but has interested several workers in that field in the past decade. In this paper examples of districts showing ore shoots on warped faults, with relations noted, are described. Fault veins of the three depth classes of veins are noted. Many epithermal veins are in normal faults, and commonly the larger ore shoots are in their steeper portions. Many mesothermal veins are in reverse faults and, many others are in normal faults. The flatter parts of veins in reverse faults are commonly wider than the steeper parts, although they are not always as rich as the steeper segments of the veins. There are not many hypothermal veins in faults of measured displacement. Introduction When faults are followed along dip or strike, many of them are found to have curving or warped surfaces, and cross sections through them in most directions show sinuous or waving intersections. Openings are formed where one wall moves away from the other (Figs. I,2). Where there is a bend in the fault, movement in any directions except along the axis of the bend will

Jan 1, 1949

By J. C. McCarthy, J. B. Stone

At Fresnillo a series of veins that has yielded very large quantities of silver and other metals has been developed over a length of 6500 ft. and to a depth of over 3000 ft. In the course of this work striking changes in the mineralogy and metal content of the principal veins have been disclosed and are well illustrated by assay data and ore reserve calculations. This paper describes those changes and suggests their bearing on theories of ore deposition. Location The Fresnillo mines and the adjacent city of Fresnillo are in the central part of the state of Zacatecas, 35 miles northwest of the capitol city of Zacatecas, once a great silver-mining center whose total production is said to place it fourth in. the world. Another famous old silver district, Sombre-rete, lies northwest of Fresnillo. Fresnillo is connected by a 5-mile branch with Fresnillo On on the Mexican National Railways line from Juarez to Mexico City. Lying near the southwestern edge of the central plateau of Mexico, Fresnillo is Surrounded by a semi-arid rolling plain from which rise widely scattered low hills. One of these is Proano hill, an inconspicuous elevation rising barely 300 ft. above the plain, but in and around Proano hill are the Fresnillo mines, and it is marked now by a great gash cut by glory-hole mining. According to an account written in 1834 by Francisco Garcia, then Governor of the state of Zacatecas, Fresnillo was discovered in 1554, and a presidio was established there in 1568 to protect travelers on the road between zacatecas and sombreretea Little is known of the earliest mining at Fresnillo, which seemingly began soon after its discovery, but by piecing together various accounts, it appears that mines there were working in 1717 and were notably active in 1751 under an administrator named Murguia, who left detailed notes describing them. In I757, however, the mines became inactive because of dificulties with creditors and no doubt also because of increasing water troubles, and they remained abandoned until 1830. In 1830 the mines at Fresnillo became the property of the State of Zacatecas because the interest of Governor Garcia had been aroused by the long disregarded notes of Murguia. Under Garcia's energetic leadership the mines were reopened, and silver production began in 1832 in spite of serious difliculties, including abnormal rains and an epidemic of cholera. In 1835 English capital was sought to allow installation of steam-driven is pumps at the two principal shafts and to build the great hacienda de beneficio (the present Proano hacienda). The company formed in 1835 (Cia. Zacatecano-Mexicana) operated successfully until 1872, when its career was brought to an end by the political and economic disturbances

Jan 1, 1949

By Harrison Schmitt

The definitions of the terms commonly used in connection with metamorphism at elevated temperature near igneous contacts are re-examined. As the study of tactite zones associated with igneous contacts progresses, more and more emphasis is put on the localization of the ore by structural forms. The generally early age of the silicates and late age of the sulphides is well established. Postsilicate structural deformation is likely to localize ore bodies. The silicates are often replaced by the ore minerals. we may not be far from proving that the elements involved in the formation of silicate aureoles are merely normal "volcanic" emanations, that silica, lime, magnesia, and alumina, and probably soda and potash, are likely to undergo local transfers only. The work of Newhouse suggests the agents of the formation of sulphides in deposits of various classifications are the volcanic emanations. Introduction The purpose of this paper is to define the terms commonly used in connection with the subject, to briefly review and discuss the broad features of the aureoles, to indicate some of the features lately recognized: to discuss the genesis, and to suggest how the associated ore deposits can best be studied and developed. When developing a subject in mining geology one is soon conscious of the vast amount of pertinent literature and that most relevant ideas, no matter how obscure, have been considered. One can only hope to make some small contribution in point of view, a few confirmatory observations, or, perhaps, suggest a small new idea indebted to the most recent data. It is nearly impossible, also, to give specific credit, and adequate credit, to all the contributors to a given subject. This study, furthermore, was not intended to cover the field exhaustively, nor is the bibliography complete. Definition OF Terms There is much confusion in the use of the broad terms concerned. Needless to say, metamorphism means change of form; metasomatism, change of substance. The term contact metamorphism, however, has been widely misused possibly by a majority of economic geologists and engineers. As originally adopted by European investigators it meant changes effected largely by heat (thermal effects) in the rocks invaded by plutonic intrusives, but did not include those local changes usually at the immediate contact brought about by the addition of substance, i.e., by metasomatism. The term has become clouded. In Europe it has

Jan 1, 1949

By Edward F. Fitzhugh

Quantitative appraisal of the chances of finding various tonnages and grades of ore clarifies any exploratory development proposal. Ways are discussed of appraising chances in conformance with probability principles, and graphs are suggested to show tonnages, grades and the corresponding judged expectancies. Introduction When exploratory development of a mineral deposit is contemplated, three interrelated questions normally must be answered before a sound decision can be reached. How much will the program cost? How much will the anticipated ore add to the immediate value of the mine? And what is the chance of developing this ore? To justify development, the deposit should present a favorable disparity between the three factors, cost, chance and return. If, for example, there is a 50-50 chance of success, the ore that is sought should have an immediate worth (after deducting all subsequent charges that it must bear) of more than twice the cost of the development. Likewise, if the chance of finding the ore is but one in five, that ore should enhance the immediate value of the mine by more than five times the cost of developing it- With sound economic and operating assumptions, the cost of exploratory development and a present value of anticipated ore may be estimated within reasonable limits. Less general attention has been given to appraising ore chances in comparable terms. The exploratory experience of the mining industry is broad enough that knowledge, vision and judgment may be combined to yield more tangible evaluations of Ore expectancy than are now customary' A way of making such appraisals is suggested herein. The mathematics of probabilities cannot be applied directly to the search for ore. By coupling applicable principles of probability, however, with pertinent experience gained in mineral exploration, an estimate often can be made of the chance of finding a certain tonnage and grade of Ore in a specific location. Such estimated, or judged, expectancies for the several blocks of ground in a deposit may be combined in a simple chart to show the relationship of the various exploratory possibilities and the potential magnitude of the deposit' An engineer or geologist may find that the quantitative thinking required for an appraisal of this type is an aid in clarifying and coordinating his views and recommendations. For a person wishing to understand these views, an ore-expectancy

Jan 1, 1949

By E. B. Hughes, F. G. Norris

Oxidation is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a compound such as Con or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is intro- duced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steel-making," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath.

Jan 1, 1949

By G.A. Moore, C. E. Sims

In previous publications of the writers4-7 it has been shown that vacuum extraction of steel can be carried as close to quantitative completion as desired provided the steel is in the austenitic state and sufficiellt time is allowed. For precise work, the method claims preference because the equipmelit for holding and heating the sample can be made simple, and because crucibles, boats, and other unnecessary materials can be eliminated and the blanks thus made very small. It is well known that the evolution rate of hydrogen is smaller just above the trans. formation than immediately below, as would be expected from the increase in solubility when passing into the gamma state. Many attempts have been made to obtain analyses by extraction just below the transition, using times of approxi. mately 2 hr. while it is true that the rate of evolution drops nearly to zero under these conditions, it has repeatedly been shown that the process is incomplete since on raising the temperature into the austenitic range, evolution will be resumed, usually after a, considerable induction period. The low-temperature evolution process appears to be useful in some cases for comparative tests where the residual crror may be more or less constant between samples, For general use, however, there is no guarantee that the error caused by incomplete extraction is constant; hence, the more laborious but more reliable high-temPe'atu'e Process must be used. At high temperature, an original flash evolution, similar to that at lower temperature, is first observed. After not more than an hour, the flash subsides and cvolution settles down to a regular first-order reaction rate for which the half-life* is usually of the order of a few hours for the 5/8-in. diam cylinder at 1050°C. The regular evolution may be followed for whatever period appears justified, after which the residual gas may be estimated as equal to that which was evolved in the last observed half-life period. Tests have shown that the composition of the evolved gas does not vary greatly during the progress of evolution; therefore the residual gas may safely be taken to have the same composition as the portion col-

Jan 1, 1949