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By A. Raman

The Nb-Co system was nuestigated in the range 10 to SO at. pct Co with X-rays. A pt phase with the W6Fe.r-type structure occurs in the system between 46 and 52 at, pct Co. Its unit-cell dimensions are nearly identical to those of the p Phases found in the Nb-Fe and Nb-Ni systems. Two Laves phases, one having the MgZnz-type structure and the other the MgCuz-type structure, already t-eported in the literature, are found to exist in the system. The ,l.IgZnz-type phase occurs between 62 and 64 at. pct Co. A MgNi2-type Laves phase, reported in the literature, is no! obtained. A binalry phase is found to exist belozv I000C around 82 at. pct Co. THE cobalt-rich side of the system Nb-Co has been repeatedly investigated by previous inestiators" and the following intermediate phases are known to occur: NbCo, which crystallizes in the MgCu2-type structure and Nbc03,' reported originally by Wall-bam, which has the MgNiz-type structre. Jordan and uwez' as well as lliott' were unable to find the MgNiz-type phase. Two phases, designated as x and y, were reported by Saito and eck.' The phase x was inferred to have a narrow composition range near 77 at. pct Co. No published work is known to the author which reports the investigations in the niobium-rich portions of the system. This paper presents the results of an investigation in the Nb-Co system between 10 and 80 at. pct Co. EXPERIMENTAL PROCEDURE Two or three grams of the alloys under investigation were prepared using niobium (99.9 pct +) and cobalt (98.8 pct + with 0.14 pct Fe and and 0.03 pct C) in a tungsten-electrode arc furnace under commercial argon atmosphere. They were then wrapped in molybdenum sheets and annealed for a period between 5 days and 1 week at 1300°C in high vacuum (10-" orr) or in evacuated quartz amules for 2 weeks at 1000°C. Powders of -325 mesh size were prepared for X-ray work by crushing and grinding the specimens. Subsequent reannealing of the powders was not undertaken since most of the alloys were brittle and broke easily. X-ray powder patterns of the as-cast and annealed samples were prepared in a Siemens cylindrical camera (57.3 mm radius) with Cr-K, radiation. A Siemens diffrac to meter was used to get the X-ray patterns of some new phases. Metal log raphic examination of the alloys supplemented the X-ray findings. RESULTS The results of the X-ray and microstructural analysis Of the alloys are in in Table I. The lattice parameters of the phases are listed in Table 11 for quick reference. A set of micro photographs in Fig. l(n) to (j) show the microstructures of some alloys. A probable equilibrium diagram is drawn in Fig. 2

Jan 1, 1967

By L. F. Coffin

Monotonic tension and controlled cyclic-strain tests have been conducted on an annealed steel at various strain rates and temperatures in the weep range. Evidence of a strain-induced precipitate reaction abozle 500°C was determined from pronounced cyclic-hardening effects, increase inflow stress, inter granular fracture, drastic decrease in low-cycle fatigue resistance, and loss in tensile fracture ductility, as well as through electron-microscopy examination. It was found that strain rate as well as temperature had a pronounced effect on these observations. A parameter of the form P = T(7.95 - log ip) was determined, which was directly related to the ductility, defined either as the true strain at fracture in the case of simple tension, or as 2N 1/2 ? E p in the case of cyclic plastic strain. A highly satisfactory comparison of the cyclic life as measured and as computed from the ductility predicted by this parameter was obtained for a range of temperatures from 400° to 650°C and for crosshead speeds of 0.002 to 0.2 in. per min. MANY metals subjected to sustained loading at elevated temperatures derive resistance to creep from solid-state reactions of various alloying constituents. These reactions can be many and varied, and occur as a consequence of time and temperature according to reaction-rate principles. Strong evidence exists that many of these reactions are influenced by plastic strain, the argument being put forth that dislocations act as sites for nucleation and growth for the new phase.' Many examples can be cited where plastic strain during transformation influences the structure, and as a consequence affects the properties.2 The low-alloy steels serve as particularly good examples for investigating the effect which aging reactions have on resulting properties. Alloying elements such as carbon and nitrogen, and carbide formers such as manganese, chromium, molybdenum, and so forth, can, by the particular aging reaction which occurs, produce strengthening effects at various temperatures, and so endow strength to the alloy over a broad range of temperatures. These effects have been systematically studied by Glen both during creep3 and for constant strain-rate tension testing.4,5 The work of Glen is of considerable interest in connection with the present study, particularly in regard to the effect of various alloying additions on the true stress-strain curve and on fracture ductility at various elevated temperatures. He has shown that strain-age hardening occurred during plastic straining, which was quite specific both to the temperature of the test and to the alloying element involved. When strain-age hardening was noted at a particular temperature, a .minimum in reduction of area was also obtained. Provided the temperature for the minimum reduction of area exceeded 300°C, all minimum ductility fractures were found to be inter-crystalline in nature. For carbon steels containing molybdenum, two minima in reduction of area were noted, one occurring at 200° to 250°C, the precise temperature depending on the percentage of molyb-

Jan 1, 1964

Jan 1, 1942

Jan 1, 1942

Jan 1, 1939

Jan 1, 1939

R. H. Sweetser.—Mr. Reinartz spoke of slag containing 18 per cent FeO. I think he expressed the iron as oxide. I should like to ask at what point, in iron contents, it is usual practice to quit sending that open-hearth slag to the blast furnace? L. F. Reinartz.—NO problem is involved in disposing of open-hearth slag to our blast furnaces because, on account of the grades of iron and steel made by our company, the iron oxide in the slag is sufficiently high to make it very acceptable to the blast-furnace operator. I have been told that if the total iron oxide in the slag is under 18 to 20 per cent, it is not economical to use such slag in a blast furnace. J. T. Mackenzie,* Birmingham, A1a.—Mr. Reinartz mentioned sulfate in the limestone. I wonder if he did not use the wrong word. We always have assumed that the sulfate sulfur is practically harmless. Most limestone carries some pyrite (sulfide sulfur) which we thought was what gave the sulfur pick-up. L. F. Reinartz.—I have had no experience, personally, in the use of limestone high in sulfates. I have been told, on several occasions, by other open-hearth men, that the sulfates will be reduced and increase the sulfur content of the metal. We have never found any pyrite in our limestone. A. Hayes,† Middletown, Ohio.—I should think that sulfates would be readily reducible to sulfites, and possibly to sulfides at various distances through the slag layer, from the top down to the interface between the bath and the slag, because reducing conditions are certainly sufficiently strong next to the bath in the slag to reduce sulfates to sulfides. A. L. Feild,‡ Baltimore, Md.—What is Mr. Reinartz's theory as to the effect of silica in the slag on the iron oxide content of the metal? L. F. Reinartz.—I have no particular theory as to the effect of silica in the slag on the iron oxide content of the metal. I know from practical experience that it does have an influence on reduction of iron oxide in the metal. We know that if the silicon content of the charge, and, therefore, the silica of the slag is increased, the iron oxide in the slag will be decreased. Based on Dr. Herty's work, we assume that the iron oxide is correspondingly decreased in the metal. C. H. Herty, JR.,§ Bethlehem, Pa.—In the theory of iron oxide control, we have tackled the matter from the physical standpoint, rather than the chemical standpoint or from the slag itself, and we worked on the basis that the change in iron oxide content in a slag—that is, whether the slag increases or decreases in iron oxide—is due to the simple fact that if you put more iron oxide into the slag from the gas than you put oxygen from the slag into the metal, the slag must increase in iron oxide;

Jan 1, 1935

By J. T. Norton, J. G. McMullin

An 1820°C isothermal cross section of the Ti-Ta-C ternary diagram was prepared from X-ray diffraction and metallographic data. No phases other than those appearing in the three binary diagrams were observed. At temperatures above the titanium transition temperature titanium and tantalum form a complete series of solid solutions containing up to 2 atomic pct C. The phases Tic and TaC also form a continuous series of solid solutions extending across the diagram. PREVIOUS work on this alloy system was very limited. Of the three binary constitution diagrams involved, only one, the Ta-C system was available in the literature. Preliminary data on the other two systems was received from the investigators during the course of the investigation and both have been published in recent months. It had been shown that Tic and TaC formed a continuous series of solid solutions, but the range of carbon content in this phase was not known. While Ta2C had been described, its solubility for or reactions with other carbides had not been reported. It was not known whether or not any ternary compounds occurred in the system. The present program was undertaken to determine experimentally the general form of the ternary diagram. It is hoped that the results will be of value in furthering the development of sintered carbide cutting materials and high temperature ceramets, many of which contain combinations of Tic and TaC. The Binary Systems Of the three binary diagrams involved only that of Ta-C was available at the time this project was started. The diagram of Ellinger¹ redrawn in Fig. 1, shows a hexagonal phase Ta2C having a very small composition range and a cubic TaC phase having a composition range of from 40 to 50 atomic pct C. The authors made a separate determination of the composition range of TaC using lattice constant values and found the range to extend from 40 to 49.7 atomic pct C in good agreement with Ellinger's diagram. Two determinations of the Ti-Ta system have appeared recently.2,3 These two diagrams are in good agreement and show that ß titanium and tantalum form a complete series of solid solutions. The Ti-C diagram by Cadoff and Nielsen4 shows a very limited solubility of carbon in both a and ß titanium. The single carbide formed persists over a wide range of carbon contents. Several values for the upper limit of carbon content of this phase have been reported."' The highest value obtained in the M.I.T. Laboratory was 47.5 atomic pct C with a lattice constant of 4.328?.5 Fattinger7 describes a gas carburization method which he claims produces stoichiometric Tic although he does not present any data showing that he actually had 50 atomic pct combined carbon. Several complete analyses on

Jan 1, 1954

R. H. Sweetser.—Mr. Reinartz spoke of slag containing 18 per cent FeO. I think he expressed the iron as oxide. I should like to ask at what point, in iron contents, it is usual practice to quit sending that open-hearth slag to the blast furnace? L. F. Reinartz.—NO problem is involved in disposing of open-hearth slag to our blast furnaces because, on account of the grades of iron and steel made by our company, the iron oxide in the slag is sufficiently high to make it very acceptable to the blast-furnace operator. I have been told that if the total iron oxide in the slag is under 18 to 20 per cent, it is not economical to use such slag in a blast furnace. J. T. Mackenzie,* Birmingham, A1a.—Mr. Reinartz mentioned sulfate in the limestone. I wonder if he did not use the wrong word. We always have assumed that the sulfate sulfur is practically harmless. Most limestone carries some pyrite (sulfide sulfur) which we thought was what gave the sulfur pick-up. L. F. Reinartz.—I have had no experience, personally, in the use of limestone high in sulfates. I have been told, on several occasions, by other open-hearth men, that the sulfates will be reduced and increase the sulfur content of the metal. We have never found any pyrite in our limestone. A. Hayes,† Middletown, Ohio.—I should think that sulfates would be readily reducible to sulfites, and possibly to sulfides at various distances through the slag layer, from the top down to the interface between the bath and the slag, because reducing conditions are certainly sufficiently strong next to the bath in the slag to reduce sulfates to sulfides. A. L. Feild,‡ Baltimore, Md.—What is Mr. Reinartz's theory as to the effect of silica in the slag on the iron oxide content of the metal? L. F. Reinartz.—I have no particular theory as to the effect of silica in the slag on the iron oxide content of the metal. I know from practical experience that it does have an influence on reduction of iron oxide in the metal. We know that if the silicon content of the charge, and, therefore, the silica of the slag is increased, the iron oxide in the slag will be decreased. Based on Dr. Herty's work, we assume that the iron oxide is correspondingly decreased in the metal. C. H. Herty, JR.,§ Bethlehem, Pa.—In the theory of iron oxide control, we have tackled the matter from the physical standpoint, rather than the chemical standpoint or from the slag itself, and we worked on the basis that the change in iron oxide content in a slag—that is, whether the slag increases or decreases in iron oxide—is due to the simple fact that if you put more iron oxide into the slag from the gas than you put oxygen from the slag into the metal, the slag must increase in iron oxide;

Jan 1, 1935

By David Turnbull

In most reactions involving solids the transformation kinetics may be represented by the combination of two processes —those of nucleation and of growth. For example, Mehl and his coiq-orker in their studies on the transformation of austenite to pearlite in steels have been able to describe the kinetics in terms of the rates of nucleation and of growth. By micrographic examination of their specimens they determined the nucleation rate (rate of appearance of pearlite colonies) as a function of time, of percent transformation, and of temperature. They observed that after an incubation period in which no nuclei are observed, the number of nuclei appearing per unit time per unit of untransformed grain boundary area, increases at an increasng rate with time. When recrystallization rates have been interpreted in terms of rates of nucleation and growth and the rate of nucleation determined, an incubation period followed by an increasing rate of nucleation has also been reported. Among the studies in which this phenomenon has been observed are those of Kornfeld and coworkers3 on cold-drawn aluminum wire, of Anderson and Mehl4 n the recrystallization of aluminum sheet, and of Stanlcy and Meh15 on the recrystallization of silicon ferrite sheet. The existence of an incubation period during which no nuclei are observed does not appear to have been reconciled with the generally accepted Volmer-Becker theory of nucleation in condensed systems. This theory ostensibly requires the rate of appearance of nuclei to be independent of time. Volmer-Becker Theory In order to form a stable nuclcus of a new phase B in a mother phase A, the molecules or atoms of the mother phase must surmount a free energy barrier whose height is determined by the volume free energy change accompanying the transformation and the energy of the surface separating the two phases. The free energy difference between nuclei of various sizes and the molecules or atoms of the mother phase is plotted schematically in Fig I as a function of the radius of the nucleus r. This free energy difference is plotted for two values of the change of free energy per atom, (Jb — ja) accompanying the transformation when the volumes of the two phases are infinite. One of these values of (Jb—Ja) corresponds to a temperature above the temperature To at which the phascs A and B are in equilibrium, and the other to a temperature below To. In order for a nucleus of phase B to be stable at a temperature T² < TO, its radius must be equal to or greater than the critical value r* for which the free energy of formatioil of the nucleus is a maximum, the of phase B having radii equal to or less than r* will be called embryos hfehl and Jetter," in discussing the kinetics of nucleation in solid systems, suppose that embryos of critical size are formed

Jan 1, 1949

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&apos;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 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&apos;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 1706°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 days 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 day, 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 J. R. Jargon, H. K. van Poollen

Non-Newtonian fluids may be injected into a reservoir during secondary recovery operations. The non-Newtonian fluid used in this work is a power-law type of fluid that is, the viscosity of the fluid decreases as the flow rate or rate of shear increases. This paper presents equations for steady-state linear and radial flow of such fluids, transient behavior results from a finite difference model of a radial system, and transient behavior results from a field test. The equations that describe the flow of a non-Newtonian fluid are non-linear and are solved numerically. Finite difference solutions are presented as curves of dimensionless pressure drop at the wellbore us dimensionless time for a constant injection rate. Solutions were obtained for 5-percent, 10-percent and 100-percent PV of a non-Newtonian fluid for injection rates of 1, 10, 100 and 1000 cc/sec and for a 5 percent PV of non-Newtonian fluid located at T = Tw&apos; 3, 10, 20, 50 and 100 ft for a flow rate of 1 cc/sec. The buildup curves do not exhibit a stmight-line portion as is the case for Newtonian flow through porous media. Correlations also are shown for the productivity index vs rate for the computer model study and the field tests. INTRODUCTION During various secondary recovery operations non-Newtonian fluids are injected. Such fluids, in general, include thickened water and gelled fluids. The term "non-Newtonian" implies that the viscosity is not only dependent upon temperature and pressure, but also on the rate of shear that is applied to the fluid. For example, water, which is a Newtonian fluid, will have essentially the same viscosity no matter what rate of shear is applied. A pseudo-plastic fluid exhibits a decreasing viscosity when higher rates of shear are applied; a dilated fluid has an increasing viscosity with increasing rates of shear. The objective of studies performed and described in this report is to obtain relationships and mathematical and empirical descriptions of the flow of non-Newtonian fluids through porous media. Simple mathematical relationships, computer studies that include the unsteady-state behavior of such fluids, and field tests are used. PREVIOUS LABORATORY STUDIES Laboratory studies have been performed by several investigators. The fluids used in one investigationl were surfactant-stabilized dispersions of water in hydrocarbons. Its Fig. 6 is reproduced as our Fig. 1. This effective-viscosity vs frontal-velocity diagram shows that this fluid is of the power-law type over a fairly large range of frontal velocities. Gogartyl developed an equation for the effective viscosity as a function of shear rate that reduces to Eq. 2 for frontal velocities greater than about 2 ft/D. The fluid characteristics used in the present study are similar to those reported by Gogarty. Christopher and Middleman2 performed experiments with power-law fluids flowing through pipes packed with glass beads. They used a modified Blake-Koteny

Jan 1, 1970

Jan 1, 1934

Jan 1, 1937

Jan 1, 1931

Jan 1, 1882

By S. C. Sircar, B. K. Dhindaw

KINETICS and mechanism of sulfation reactions have been studied extensively. Qualitative and quantitative data are reported for the kinetics and mechanism of sulfation reaction of copper oxide pellets;&apos;&apos;2 yet it remains a controversial Subject. The mechanism and kinetics of the sulfation of zinc oxide powder (B.D.H. analar quality) were studied by gravimetric technique. A spring of high-carbon steel wire with accuracy well within 0.2 mg was used for measuring weight change. The sample was taken in a Pyrex glass bucket, hanging freely inside a Pyrex glass tube reactor, with a gold wire attached to the spring, the reactor being surrounded by a movable furnace (double wound type) with a temperature control within *5"C. Flow of oxygen, 60 cu cm per min, and sulfur dioxide, 45 cu cm per min, were measured through calibrated flowmeters and the mixture dried over PZ05 before entering the reactor. The experimental results are presented in Figs. 1 and 2. The plot of weight change of zinc oxide, giving the amount of zinc sulfate formed, was found to be linear over the temperature range of 500" to 700° C and up to a conversion of approximately 60 pct, as beyond it they divert from linearity.&apos; The rate of sulfation was found to be affected by total flow rate of gases at a fixed ratio of SO2/O2, up to 60 cu cm per min, and was found to be linearly dependent on quantity of total powdered sample taken. The plot of rate of sulfation of zinc oxide, 70 mg, with varying amounts of vanadium pentoxide, at a constant ratio of gases as mentioned above, and at a constant temperature of 625"C, was also found to be linear as seen in Fig. 2. Extrapolation to zero V2O5 addition gives the same rate of sulfation, as in case of pure zinc oxide, 70 mg. Vz05 was prepared by heating ammonium vanadate at 600°C for 15 min in a muffle furnace. The available literature points out that the theory of sulfation that has received the maximum support postulates the following mechanism for sulfation of ZnS: 2ZnS + 30, = 2Zn0 + 2SOZ; the ZnO formed acts as a catalyst for the reaction, 2 S02 + O2 = 2S03. This SO3 reacts with ZnO to give zinc sulfate. It is suggested here that the above widely supported mechanism is operative in the sulfation reaction and that the rate-controlling step in the sulfation reaction of ZnO is the formation of SO3 from SO, and 0,. The authors are carrying on further work in this line, and the details will be published later. The authors wish to acknowledge the facilities provided and the help extended by Prof. P. R. Dhar, Head, Department of Metallurgical Engineering, and the permission granted to publish this note by the Director, I. I. T., Kharagpur.

Jan 1, 1969

By Frank A. Herald

Through the generous cooperation of the authors of the papers in this chapter, a great wealth of fundamental data is being made available. The same plan of securing and submitting data will be carried forward next year, with the hope of making a nearer approach to complete presentation of the data contemplated in the plan. In order to conserve space, we are printing below such footnotes as have general application to Table 1 in the papers in this chapter: Footnotes to Column Headings Table I In areas where both oil and gas are produced, unless gas is marketed outside the field, such areas are included in column headed "Oil." Manufacture of casinghead gasoline and carbon black is interpreted as outside marketing of gas. Production per acre is determined by dividing into the number of barrels of oil the sum of the number of acres assigned to "Oil" plus such number of acres of the total assigned to "Oil and gas" as represents the portion thereof occupied by oil. Wells producing both oil and gas are classified as "Poducing oil only" unless gas from them is marketed off the lease. W. water; G. gas; A, air. Bottom-hole pressures are preceded by "e." All other figures represent pressures at casinghead with well closed. P, paraffin; A, asphalt; M, mixed. 0 Cam, Cambrian; Ord, Ordovician; Sil, Silurian; Dev, Devonian; Mis, Mississippian; MisL, Lower Mississippian; MisU, Upper Mississippian: Pen. Pennsylvanian; Per. Permian; Tri, Triassic; Jur. Jurassic; CreL, Lower Cretaceous; CreU. Upper Cretaceous; Eoc, Eocene; Olig, Oligocene; Mio. Miocene; Pli. Pliocene. 6, sandstone: SH, sandstone, shaly; Ss, soft sand; H, shale; L, limestone; LS, limestone. sandy; C, chalk; A, anhydrite; D, dolomite; Da. arkosic dolomite; GW, granite wash; P, serpentine. Figures are entered only for fields where the reservoir rock is of pore type. Figures represent, ratio of pore space to total volume of net reservoir rock expressed in per cent. "Par" indicates that the reservoir rock is of pore type but said ratio is not known by the author. "Cav" indicates that the reservoir rock is of cavernous type; "Fis," fissure type. A, anticline; AF, anticline with faulting as important feature; Af, anticline with faulting as minor feature; AM, accumulation due to both anticlinal and monoclinal structure; H, strata are horizontal or near horizontal; MF, monocline-fault; MU, monocline-unconformity; ML, monocline-lens; MC, monocline with accumulation due to change in character of stratum; MI, monocline with accumulation against igneous barrier; MUP, monocline with accumulation due to sealing at outcrop by asphalt; D, dome; Ds, salt dome; T, terrace; TF, terrace with faulting as important feature; N, nose; 9, syncline. Information will be found in text as indicated by symbols: A, name of author, other than above. who has compiled the data on the particular field; C, chemical treatment of wells; G, gas-oil ratios; P, proration; U, unit operation; R, references; W, water; 0. other information.

Jan 1, 1934

By N. A. Gokcen

EQUILIBRIA in the reactions between gases and liquid metals have been the subject of many interesting investigations. The experimental realization of true equilibrium, however, is questionable in certain cases due to the lack of conclusive studies in reaction rates. It -will be shown here that a systematic interpretation of rate studies with the analysis of prevailing experimental conditions leads to valuable practical information. The reactions of particular interest are: H2(g) +S(inFe) - H2S(g) [1] H2(g) +O (inFe) =H2O(g) [21 2H2(g) + SiO2(s) = 2H2O(g) + - (inFe) [3] The usual and perhaps the most convenient method of investigation may be illustrated with reaction 1. A stream of gas mixture consisting of H2 + H2S is passed over or bubbled through the liquid metal at constant temperature. The ratio of H2S/H2 in the entrant mixture is fixed in each experimental run, and, therefore, the composition of melt varies until the establishment of equilibrium. The purpose of this paper is to derive a formula expressing the minimum time required for the establishment of equilibrium and to compare the calculated values from such a formula with the available data. Equations Reaction 1 is used for the purpose of illustrating the derivation. Let E represent the equilibrium and X the nonequilibrium sulphur in weight percent at any time t in minutes. For the sake of simplicity, it is first assumed that E > X although the results are of general applicability without restriction. It has been shown by Morris and Williams&apos; that within a difference of 1 pct S or less, i.e., E-X5 1.00, the value of K&apos;1 = Ph2s/Ph2.S% is very nearly constant. The maximum ratio of available Ph2s/Ph2 = H,S/H,, from which sulphur can be absorbed by metal, is equal to H2S/H2 in equilibrium with E (which equals H2S/H2 in the entrant gas), minus H,S/H, in equilibrium with X. Thus: Available H2S/H2 = EK&apos;1 - XK&apos;1 [4] Eq. 4 expresses that sulphur can be absorbed by metal from the H2S/H2 in the entrant gas until the gas leaving the metal assumes a value of H2S/H2 which is in equilibrium with the dissolved sulphur X at that time. H,S constitutes up to approximately 1 pct of the gas mixture. Its disassociation into H2 and SL is about 1 pct at 1600°C, hence, the H2S/H2 impinging on the surface of metal is very close to that in the entrant gas. The rate of flow of hydrogen entering the reaction chamber is kept constant experi-

Jan 1, 1954