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PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y.

Jan 4, 1914

E. K. Landis, Philadelphia, Pa. (communication to the Secretary) : Mr. Firmstone's paper is of great interest; but he has unfortunately otnitted to state the most important point, viz., the percentage of sulphur in the two materials he compares; and this omission vitiates the conclusions which he draws. Comparing by grade, instead of silicon-contents (as in his Table III.), the iron made using limestone with that made using dolomite, we find for gray-forge the average of four analyses under limestone to be, Si, 0.644; S, 0.089 ; while one analysis under dolomite gives Si, 0.508 ; S, 0.070. For No. 2 iron, the limestone flux gives, as an average of 19 analyses, Si, 1.107; S, 0.051; while the average of 4 analyses made with dolomite flux gives Si, 0.630; S, 0.056. It will be observed, that no No. 1 pig is given under limestone, while 14 analyses appear under dolomite, averaging Si, 0.950 ; S, 0.028. As nothing is said about changed conditions, it is Fair to presume that the ore and fuel, as well as the blast-temperature (which is stated to have been uniform at about 750' F.) remained practically the same; and since the sulphur in the two fluxes is not given, it is impossible to know whether the lower sulphur for equal silicon-contents is due to the use of dolomite or to other conditions. The use of dolomite would produce a more fusible cinder, and the furnace would be hotter than when using limestone; therefore, we might expect to see a grayer iron. The amount of So. 1 iron made with dolomite seems to confirm this supposition; and, under these conditions, we might expect more of the sulphur to be volatilized, and to pass off in the gases. The easier fusibility of the cinder would also permit more rapid driving; and this should reduce the amount of silicon and sulphur in the iron, as the amount of reduced metalloids in the pig is directly proportional to the length of time it remains in the reducing-zone.

Jan 1, 1895

PRESIDENT BENJAMIN B. THAYER,2 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS; NEW.-YORK, N. Y. TREASURER ' GEORGE C. STONE,1 .NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 8, 1914

PRESIDENT. CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP, 2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS. ROSSITER. W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 12, 1913

PRESIDENT CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND NEW YORK, N.Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 1, 1914

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y.. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 10, 1914

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N: Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORE, N. Y.

Jan 12, 1914

By Rush Greenslade

The oil and gas lease is the basic contract of the oil and gas industry; it is the foundation stone upon which the producing industry, particularly, is based. As the industry is precarious and highly speculative, the foundation contract should be of the utmost integrity and certainty. But right there an anomaly exists; the oil and gas lease is the most obscure, most uncertain, doubtful contract in the realm of law today. That is a condition that must be considered when taking oil and gas leases, and when buying, selling, and holding them. It may fairly be asked why should this industry rest upon so insecure a foundation. Why should not the oil industry rest upon the contract that is the basis of all industry, the warranty deed? There are many contributing reasons, but the principal one is business expediency. The Anglo-Saxon idea of ownership of land is that every land owner owns from the center of the earth to the sky—all that is above and all that is below—consequently the oil and gas are owned by the person who owns the surface. That idea is not exactly true with reference to oil and gas, for many states have adopted the doctrine that oil and gas are like wild animals; they are fugacious and migratory and belong to the man that traps them. But, except for that doctrine, we believe that oil and gas are owned by the owner of the surface, wherein we differ from the Latin-American countries where the mineral rights are owned by the government. The United States was settled largely by homesteading. The owners of land were, in the main, farmers, who did not have the means or the faith to drill for oil or gas. The operators or speculators did not want to buy the land on the mere possibility of finding oil; hence a compromise resulted by which the land owner gave the speculator or the operator what he called an oil and gas lease, or a right to go upon his land and drill for oil and gas. What is supposed to be the first oil lease placed on record reads as follows: Agreed this 4th day of July, a.d. 1853, with J. D. Angier of Cherrytree township in the county of Venango Pennsylvania that he shall repair up and keep in order the old oil springs on land in said Cherrytree township, or dig and make new springs, and the expense to be deducted out of the proceeds of the oil, and the balance, if any, to be

Jan 1, 1924

PRESIDENT. CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,' NEW YORK, N. Y. SECRETARY EMERITUS. ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY. BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 11, 1913

PRESIDENT. CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW. YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,' NEW YORK, N. Y. SECRETARY EMERITUS. ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY. BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 7, 1913

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST' PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F..RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY K. KENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y

Jan 6, 1914

PRESIDENT BENJAMIN B. THAYER,2 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 .NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY. BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 7, 1914

By J. D. Cooner

SINCE my working life of 32 yr has been spent in and about the anthracite mines of the Hudson Coal Co., and the previous 4 yr in a college school of mines, I can write best about the safety program of a coal mining company. However, most of the suggestions, statements and practices mentioned herein are applicable to the members of a safety organization and program of almost any industry. It is realized that industrial officials actually interested in real safety work are fully acquainted with the requirements of a practical safety program. Therefore, for such persons there may be nothing new in this paper. The Hudson Coal Co. of Scranton, Pa., employs 7,000 men and produces 5,000,000 tons of anthracite annually at nine collieries scattered for a distance of 40 miles throughout the Lackawanna and Wyoming valleys of northeastern Pennsylvania. For the past 17 yr of the above mentioned 32, I have been engaged in safety work as a safety inspector, assistant mine superintendent, and at present the safety engineer. I have also had the privilege of visiting coal and metal mines in other parts of the United States and Canada. We Americans are the most careless people in the world. If any one doubts this statement why are 100,000 of our people killed accidentally annually? Or why during the almost four years we were engaged in World War II were more of our people killed accidentally at home than were killed in our army, navy, marine corps, coast guard, and other services during the same period? We are careless everywhere in our homes, on the highway, at work and at play. The purpose of this paper is to outline the requisites of a safety department and its program to stop the accidents occurring to employees at work in mines or industrial plants. The first requisite for a safety program is that the management must be convinced of the need and value of a real safety program. By "management" is meant each department head from the president down. Otherwise a good safety department with a good safety program will not succeed because it will not have the proper personnel and equipment to work with, its rules and regulations will not be enforced, and the members of the safety department will be belittled in the eyes of most of the workmen and supervisors. Next, a safety engineer and his inspectors should have worked in the production end of the mines as workmen and also in an official capacity. They are then in a position to have practical and first hand knowledge of the accident hazards of the industry, how to prevent them, and in general the problems of both the workmen and officials. Some men are appointed as safety inspectors when they are physically unable to carry on as mine officials. Such men may know the safety end of the industry and even be safety-conscious, but if they are physically unable to be mine officials they are also physically unable to be safety inspectors, as a safety inspector in our mines must walk from 2 to 4 miles on each daily inspection-and visit each working

Jan 1, 1948

By T. A. Wright

The sampling of waste materials containing copper, lead and tin has taken on a new significance within recent years, and is of increasing importance, on account of the entry of some of the copper refineries into this field and the tendency towards consolidations among the smelters. In the past, such material was sold on the basis either of a rough or grab sample or of casual inspection of the lot. The two principal sources of this waste are the processes of fabrication and the scrapping of automobile, electrical, plumbing, railroad and other equipment. In both cases much material can be sorted, salvaged and sold by classification and grade to be melted "as is" or with the addition of new or virgin metal. The increasing care in classifying exercised in the large manufacturing plants tends to increase the proportion of this usable scrap; on the contrary, the increasing use of more complex and special non-ferrous alloys tends to make sorting and grading more difficult in turnings, borings, clippings, etc., and consequently is making sampling of more moment. In tin, lead, aluminum, and zinc furnace by-products such as ashes, drosses, skimmings, etc., the trade practice of evaluation has not varied much. For instance, tin drosses, battery lead, and aluminum skimmings are ordinarily sold on what is called "metallic button" or "metallic recovery" or ('metallic yield." Copper and lead waste, however, is being sold more and more on actual copper and lead contents based on sample and chemical analyses. This paper will be devoted chiefly to the sampling of materials suitable only for refining and recovery of one or more of the metals present. The methods described are often based on the fact that but one metal, such as copper, is to be paid for. The loss of volatile constituents in melting does not appreciably affect the final copper result, as the "after-melting" assay can be readily calculated to the "before-melting" basis, but if smelter efficiency continues to increase, so that in time zinc, for instance, may be recovered on a paying basis, the method of sampling dirty brass, for example, will have to be changed also. As a matter of fact, we may expect that improved refining processes will make possible the partial recovery of lead and tin which are now lost.

Jan 1, 1928

By Rush Greenslade

THE oil and gas lease is the basic contract of the oil and gas industry; it is the foundation stone upon which the producing industry, particularly, is based. As the industry is precarious and highly speculative, the foundation contract should be of the utmost integrity and certainty. But right there an anomaly exists; the oil and gas lease is the most obscure, most uncertain, doubtful contract in the realm of law today. That is a condition that must be considered when taking oil and gas leases, and when buying, selling, and holding them. It may fairly be asked why should this industry rest upon so insecure a foundation. Why should not the oil industry rest upon the contract that is the basis of all industry, the warranty deed? There are many contributing reasons, but the principal one is business expediency. The Anglo-Saxon idea of ownership of land is that every land owner owns from the center of the earth to the sky all that is above and all that is below-consequently the oil and gas are owned by the person who owns the surface. That idea is not exactly true with reference to oil and gas, for many states have adopted the doctrine that oil and gas are like wild animals; they are fugacious and migratory and belong to the man that traps them. But, except for that doctrine, we believe that oil and gas are owned by the owner of the surface, wherein we differ from the Latin-American countries where the mineral rights are owned by the government. The United States was settled largely by homesteading. The owners of land were, in the main, farmers, who did not have the means or the faith to drill for oil or gas. The operators or speculators did not want to buy the land on the mere possibility of finding oil; hence a compromise resulted by which the land owner gave the speculator or the operator what he called an oil and gas lease, or a right to go upon his land and drill for oil and gas. What is supposed to be the first oil lease placed on record reads as follows: Agreed this 4th day of July, A.D. 1853, with J. D. Angier of Cherrytree township in the county of Venango Pennsylvania that he shall repair up and keep in order the old oil springs on land in said Cherrytree township, or dig and make new springs, and the expense to be deducted out of the proceeds of the oil, and the balance, if any, to be

Jan 8, 1924

By M. J. Spendlove, H. W. St. Clair

An automatic surface-follower mechanism was used to measure the surface temperature and the rate of evaporation of molten zinc while undergoing distillation at low pressure. At pressures of 50 to 100 microns Hg, the rate of evaporation may be 60 to 80 pct of the theoretical maximum corresponding to the measured temperature. The rate decreases rapidly at pressures above 100 microns Hg, to only 7 pct of the theoretical maximum at 2000 microns Hg. Measured temperature gradients at the surface are in agreement with theoretical gradients calculated from the heat of vaporization, rate of evaporation, and thermal conductivity of molten zinc. THIS paper covers a series of careful measurements of the rate of evaporation of molten zinc at low pressures, undertaken as a part of a general investigation on the separation of metals by distillation.' Preliminary results on the rate of evaporation of zinc were described in a previous publication.' The results of the preliminary study are as follows: 1—The observed rates of evaporation of zinc were as high as 0.60 g per sq cm per min, corresponding to 75 pct of the maximum rate as determined by the temperature of the metal. 2—The evaporation rate was decreased from 0.30 g per sq cm per min at a pressure of 25 microns to only 0.09 g per sq cm per min when the pressure was increased to 5 mm. 3—The temperature of the surface during rapid evaporation may be 35" to 100°C less than the main mass of metal. Observed temperature gradients at the surface are consistent with those calculated from the heat of vaporization and the thermal conductivity of liquid zinc. In the preliminary experiments, the rate of evaporation was determined from the loss in weight of the metal in the crucible during the test. This was compared with the weight of the condensate. Obviously, this method was subject to error because of some uncertainty as to the period of evaporation that should correspond to the loss in weight. Furthermore, this method did not permit taking into account probable variations in the rate of evaporation during the test. A more serious shortcoming was that the temperature at the evaporating surface was not known, so the maximum theoretical rate of evaporation could not be calculated accurately. To improve the precision of rate measurements and to allow accurate measurements of the surface temperature, a refined experimental technique was developed whereby the temperature and position of the surface could be measured accurately. This was done by an automatic surface-follower mechanism that gave a continuous record of the surface temperature and the amount of zinc evaporated. These data permitted an instantaneous determination of the actual rate of evaporation and the surface temperature throughout the test. Pure zinc (99.99 pct Zn) was used in all experiments. Description of Distillation Furnace The details of construction of the distillation furnace are shown in Fig. l. The furnace is enclosed in a large quartz tube open at one end. The open end of the quartz tube is sealed by means of a water-cooled head. The entire enclosure is vacuum tight. The connection between the water-cooled head and the quartz tube is sealed by means of a rubber gasket which fits tightly against the smooth end of the tube. The metal is heated by induced current set up in the molten zinc and the walls of the graphite crucible by means of a water-cooled induction coil outside the quartz tube. High frequency current is passed through the induction coil from a 6 kw mer-

Jan 1, 1952

All the TECHNICAL PUBLICATIONS and PREPRINTS published in 1932 are available at Institute headquarters. They are also on file in public,, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS. Copies of the TECHNICAL PUBLICATIONS have been mailed to those members of the Institute who are registered in the different classes: A-Metal Mining; B-Milling and Concentration; C-Iron and Steel Division; D-Nonferrous Metallurgy; E-Institute of Metals Division; F-Coal Division;. G-Petroleum .Division; H-Nonmetallic Minerals; I-Mining Geology; K-Mining Administration; L-Geophysical Prospecting. Other members may obtain copies by writing to the Secretary. Copies of PREPRINTS may also be obtained from the Secretary's office. Additional copies are sold at the rate of 1 cent per page; minimum charge, 25 cents. Nonmembers may purchase the papers at the prices mentioned. METAL MINING TECH- NICAL PUBLI- - TITLE AUTHOR MEETING TRANS. CATION VOLUME No. AND PAGE* 484-A.45 Propeller Type Mine Fan at Moose A. S. Richardson New York 102, 86, 93 F.52 Shaft, Butte, Montana (13) Feb., 1932 487-A.46 Progress in the Improvement of Max H. Barber New York, Methods and Equipment at Feb., 1932 Open-pit Iron Mines on the Lake Superior Iron Ranges (9) Pre. Sand Filling through Pipes and Lucien Eaton New York, 102, 33, 41 Boreholes (9) Feb., 1932

Jan 1, 1932

By Walter Rose

In a recent technical note, Owen Thornton&apos; suggests that wetting liquid relative permeability may be derived from the relationship: where Pd/Pc is the ratio of displacement pressure to capillary pressure at the wetting liquid satdration Sw, and I is the resistivity index at this saturation. Thornton shows that this expression gives values for relative permeability in good agreement with those experimentally determined by Leverett. We have recently developed another expression for krw which seems preferable to Equation 1 since it requires fewer experimental data for its verification. This equation may be derived in the following manner. Making use of the analogy between mass transfer of fluid in a porous medium and electrical conductivity through the fluid in the same medium, we can postulate a hydraulic formation resistivity factor analogous to an electrical formation resistivity factor. From Poiseuille&apos;s Law the resistivity to flow in a tube of radius R is of the form 8u/R², where is the viscosity of the fluid. Similarly7 the resistivity to flow in a porous medium of the same dimensions as the tube is given by D&apos;Arcy&apos;s Law as where k is the permeability of the medium. The hydraulic formation resistivity factor, Ff, is thus the quotient of these two resistivities, or: But permeability is defined by the KO-zeny equation as: where: r is the average pore radius of the porous medium, L. is the average tortuous length of the average pore, + is the porosity, and L is the bed length. This gives Fr as a function of the (La/L) .-.-.tortuosity ratio and porosity, or in explicit form: where: T = (La/L)&apos;, and N is the number of pores of radius, r, which will be found in any cross sectional area, x R&apos;. That is, N = R²/r². It will be clear from the foregoing considerations that the hydraulic formation fat. tor should be dependent on the value of R which in every case must be arbitrarily selected. By analogy, the hydrauiic formation factor, Fcf, characterizing the porous medium at Sw<1,will be given by: R² NT. where ke is the effective wetting liquid permeability obtaining at Sw<l, and Te is the square of the (Las/L) ratio defined by Thornton. Therefore, the hydraulic resistivity index, If, is: However, Thrnton gives I as: and it follows that: Equation 2, when checked against the data of wyckoff and Botset² and some of the Morse et al data³, gives comparisons as shown at the bottom of this page. Computations based on Leverett&apos;s data, quoted by Thorntaon, gives computed krw values somewhat lower than the experimental values. Moreover, other instances can be cited where we find that neither Equation 1 nor Equa tion 2 is checked by experimental data. The work of Botset&apos; on the Nichols Buff sandstone and Morse et a1 on oil wetted Bradford sandstone are such instances. A reason for these discrepancies may lie in the fact that if both Equations 1 and 2 are presumed always to give accurate values for krw, it follows that PC = Pd/Sw". Such an expression, it is well known, is too simple to describe accurately the capillary pressure behavior of all porous media. However, it is believed that a particular advantage resides on the use of Equation 2, since it is not dependent for its utility on a knowledge of the capillary pressures obtaining in dynamic flow svsterns. No practical technique for measuring the capillary pressures characterizing the fluid distributions in dynamic flow systems has yet been proposed. Acknowledgment is given to Dr. Paul D. Foote, executive vice-president of the Gulf Research and Development Company, for permission to publish this note. 1. Owen F. Thornton, "A Note on the Valuation of Relative Permeability," J. Pet. Tech., 1:7, Section 1, July, 1949. 2. R. D. Wyckoff arid H. G. Botset, "The Flow of Gas-Liquid Mixtures through Porous Media," Physics, 7:325-345, 1936. 3. R. A. Morse, P: L. Terwilliger, .and S. T. Yuster, "Relative Permeability Measurements of Small Core Samples," Oil and Gas J., 46:109-125, Aug. 23, 1947. 4. H. G. Botset, "Flow of Gas-Liquid Mixtures Through Consolidated Sand," Trans. AIME, 136:91, 1940.

Jan 1, 1949

By Walter Rose

In a recent technical note, Owen Thornton&apos; suggests that wetting liquid relative permeability may be derived from the relationship: where Pd/Pc is the ratio of displacement pressure to capillary pressure at the wetting liquid satdration Sw, and I is the resistivity index at this saturation. Thornton shows that this expression gives values for relative permeability in good agreement with those experimentally determined by Leverett. We have recently developed another expression for krw which seems preferable to Equation 1 since it requires fewer experimental data for its verification. This equation may be derived in the following manner. Making use of the analogy between mass transfer of fluid in a porous medium and electrical conductivity through the fluid in the same medium, we can postulate a hydraulic formation resistivity factor analogous to an electrical formation resistivity factor. From Poiseuille&apos;s Law the resistivity to flow in a tube of radius R is of the form 8u/R², where is the viscosity of the fluid. Similarly7 the resistivity to flow in a porous medium of the same dimensions as the tube is given by D&apos;Arcy&apos;s Law as where k is the permeability of the medium. The hydraulic formation resistivity factor, Ff, is thus the quotient of these two resistivities, or: But permeability is defined by the KO-zeny equation as: where: r is the average pore radius of the porous medium, L. is the average tortuous length of the average pore, + is the porosity, and L is the bed length. This gives Fr as a function of the (La/L) .-.-.tortuosity ratio and porosity, or in explicit form: where: T = (La/L)&apos;, and N is the number of pores of radius, r, which will be found in any cross sectional area, x R&apos;. That is, N = R²/r². It will be clear from the foregoing considerations that the hydraulic formation fat. tor should be dependent on the value of R which in every case must be arbitrarily selected. By analogy, the hydrauiic formation factor, Fcf, characterizing the porous medium at Sw<1,will be given by: R² NT. where ke is the effective wetting liquid permeability obtaining at Sw<l, and Te is the square of the (Las/L) ratio defined by Thornton. Therefore, the hydraulic resistivity index, If, is: However, Thrnton gives I as: and it follows that: Equation 2, when checked against the data of wyckoff and Botset² and some of the Morse et al data³, gives comparisons as shown at the bottom of this page. Computations based on Leverett&apos;s data, quoted by Thorntaon, gives computed krw values somewhat lower than the experimental values. Moreover, other instances can be cited where we find that neither Equation 1 nor Equa tion 2 is checked by experimental data. The work of Botset&apos; on the Nichols Buff sandstone and Morse et a1 on oil wetted Bradford sandstone are such instances. A reason for these discrepancies may lie in the fact that if both Equations 1 and 2 are presumed always to give accurate values for krw, it follows that PC = Pd/Sw". Such an expression, it is well known, is too simple to describe accurately the capillary pressure behavior of all porous media. However, it is believed that a particular advantage resides on the use of Equation 2, since it is not dependent for its utility on a knowledge of the capillary pressures obtaining in dynamic flow svsterns. No practical technique for measuring the capillary pressures characterizing the fluid distributions in dynamic flow systems has yet been proposed. Acknowledgment is given to Dr. Paul D. Foote, executive vice-president of the Gulf Research and Development Company, for permission to publish this note. 1. Owen F. Thornton, "A Note on the Valuation of Relative Permeability," J. Pet. Tech., 1:7, Section 1, July, 1949. 2. R. D. Wyckoff arid H. G. Botset, "The Flow of Gas-Liquid Mixtures through Porous Media," Physics, 7:325-345, 1936. 3. R. A. Morse, P: L. Terwilliger, .and S. T. Yuster, "Relative Permeability Measurements of Small Core Samples," Oil and Gas J., 46:109-125, Aug. 23, 1947. 4. H. G. Botset, "Flow of Gas-Liquid Mixtures Through Consolidated Sand," Trans. AIME, 136:91, 1940.

Jan 1, 1949

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9&apos;22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970