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By J. B. Goddard

In situ leaching of uranium by aqueous ammonium carbonate containing oxygen or hydrogen peroxide as oxidant results in the partial dissolution of sulfides. While some of the sulfide sulfur is oxidized to sulfate, a considerable portion is oxidized only to thiosulfate and polythionates. Polythionates poison the ion exchange resin used to extract uranium. At the Palangana operation in south Texas, the trithionate ion (S3062-) was found by infrared spectrometry to be the major resin poison. Treatment of ion exchange feed solutions with hydrogen peroxide only resulted in partial conversion of reduced sulfur species to sulfate. Trithionate conversion was particularly slow. Poisoning of the resin also occurred from the ammonium chloride eluant, which built up trithionate because of recycling. This was essentially eliminated by chlorinating the eluant before yellow cake precipitation.

Jan 1, 1986

By G. St. J. Perrott

AN explosive of, balanced composition might be expected, on first consideration, to develop maximum propulsive strength.1 This hypothesis is based on the assumption that an excess of oxygen would act simply as an inert material with a consequent lowering of flame temperature, also that a deficiency of oxygen would tend toward incomplete reaction of the combustible materials, thereby preventing development of the full strength of the explosion. Actually, however, it can be shown both theoretically and experimentally that an explosive having a certain oxygen deficiency will develop the greatest propulsive strength. This fact has been known to the technical staffs of explosives manufacturers for many years, but it has not always been recognized by explosives engineers in the field. For example: There: is a fairly widespread opinion that the wrapper of a stick of dynamite is merely a container for the explosive and that it plays little if any part in the development of propulsive strength. Actually, it can be shown that the wrapper enters fairly completely into, the explosive reaction. In the case of most gelatin dynamites, a given weight of explosive from which the wrappers have been removed will develop considerably less strength than the same weight of explosive plus wrapper, in spite of the fact that the latter combination contains less weight of the actual explosive ingredient. It can also be shown that a cartridge 7/8 in. in diameter may be stronger, weight for

Jan 1, 1928

The Institute maintains a dual reltionship with students: (1) an individual relationship with a Student Associate; and (2) a relationship with local organizations of students, known as Affiliated Student Societies or Student Chapters. 1. The conditions of Student Associateship are set forth in Section 9, Article I, of the Bylaws of the Institute (see page 60 and following pages). During 1934, sundry amendments were made for the purpose of improving the student relationship. Post-graduate students are now eligible; and associateship can be maintained, with the payment of the regular dues of $2 per year, for 18 months following graduation in. June. With his regular dues, each Student Associate is entitled to receive during the year his choice of MINING AND METALLURGY, METALS TECHNOLOGY, MINING TECHNOLOGY, PETROLEUM TECHNOLOGY, or two "classes" of Technical Publications; and on payment of an additional fifty cents. he can have both MINING AND METALLURGY and any one of the others. He is accorded the privilege of getting special publications such as "The Porphyry Coppers" and "Elements of the Petroleum Industry" at the reduced prices applicable to Members; he has the privileges of the Engineering Societies Personnel Service and the Engineering Societies Library; and he is not only invited but urged to attend all meetings of the Institute, its Divisions and its Local Sections. The Institute wants, to extend the hand of professional fellowship to students following mineral industries curricula.

Jan 1, 1941

By Emile Hiertz

THE first press was installed in June, 1910, and the second in March,1911. They produce 1,000 briquettes per hour, weighing 5 kg. (11.05 1b.) each, under a pressure of about 400 kg. per square centimeter (5,689.2 lb. per square inch). The chloride of magnesium is received from the potash mines at Hanover in tank cars in approximately a 35 per cent. solution. The quantity of solution added to the flue dust varies between 2 and 3 per cent., so that the briquettes contain about 1 per cent of MgCl2. To fresh dust as much as 10 per cent. of coke breeze may be added and bri¬quettes made that still have a crushing strength of from 25 to 30 kg. (377 to 426.6 lb. per square inch) after 36 hr., and 45 kg. (639.9 lb. per square inch) after six days. After having treated 140,000 tons of the material, the reports of the blast furnaces show that the briquettes improved the action of a furnace and produced less dust than did Minette ore. As much as 35 per cent. of briquettes is added to the furnace charge without bad effects on operations. The presence of chlorine did not produce any corrosion in the furnace, downtakes or other piping. The presence of a certain amount of chlorine in the dust reduces the amount of chloride of magnesium which it is necessary to add for briquetting.

Jan 12, 1913

From L. K. Armstrong, Secretary of the Columbia Section of the Institute, we have received information as to the activities and plan of the Spokane Engineering and Technical Association, which was recently organized under the joint auspices of the local sections of the American Institute of Electrical Engineers, the American Society of Civil Engineers, and our own Institute. The first meeting was held on September 20, at which a program for the following year was adopted. The, meeting was then conducted by the Civil Engineers., the principal business being the reading of a report by Mr. Flinn, Secretary of the United Engineering Society. The second meeting was held on October 18, of which the Columbia, Section of our Institute took charge. According to the program adopted, meetings will be held regularly on the third Friday of each month, except June, July and August. It is understood that these meetings shall not interfere with nor abridge the independent activity of the participating societies. The proposed work of the Association is to be conducted by a large number of committees, whose attention will be devoted to such subjects as the following: Municipal, Highways, Resources, Manufacture and Industries, Legislative, Educational, National and State, Patents and Inventions, Americanization, Safety and Rehabilitation, Research, Emergency. When all of these committees shall have been filled, and their work begun, it is expected that the engineers of Spokane and vicinity may take a more active part in things affecting human welfare in that vicinity.

Jan 11, 1918

By Thomas H. Sheehan

The purpose of this paper is to present an application of computer technology to assist the mineral company financial executive in assessing exchange risks. The paper is divided into five parts: Background, Translation Approaches, Theory, Empirical Validation, and Conclusion. BACKGROUND Exchange risk results from a change in the rate of exchange between a host and a home country's currencies. Legitimate reasons exist for changes in the currency exchange rates among countries in a world with over a hundred different currencies. These reasons include: different economic growth rates, social factors, cultural heritages, and political motivations. The problem of exchange rate changes are perennial and exist whether the world operates on exchange rates or floating exchange rate practices. The cause of the problem is trade and international payment imbalances. If one accepts the premise that exchange rates fluctuate over time, then the mineral company financial executive faces a continual process of reassessment of the impact of exchange rate changes on the financial worth of his company. (1) The mineral company financial executive prepares balance sheets and income statements that are audited by certified public account- ants annually for shareholders, bankers, and tax authorities. The financial executive translates assets and equities denominated in foreign currencies into domestic dollars, e.g., Japanese firms convert to Yen, French firms convert to Francs, and so on. When figures from foreign subsidiary operations are consolidated into the balance sheets of the parent corporation, estimates of the company's finan-

Jan 1, 1977

By B. J. Dotson, P. N. McCreery, R. L. Slobod, James W. Spurlock

A core sample porosity-check program is described. A number of laboratories participated in the investigation. which comprised measuring the porosities of ten selected natural and synthetic core samples. Each laboratory employed its own method (or methods) of measurement. These included Boyle's Law, water-saturation. and organic liquid-saturation methods. Brief descriptions of each method employed are given. In general, the measured values of porosity were in reasonably good agreement. The average deviation of porosity from the mean or average values for the group of samples was ±0.5 porosity per cent. The results of these measurements are compiled and presented in graphical form. INTRODUCTION The total hulk volume of a porous sample is derived from the sum of two volumes, the void or pore volume and the solid* or grain volume. The porosity fraction of the sample ia defined as the ratio of the void volume to the bulk volume. Multiplication of this ratio by 100 converts it to per cent porosity. Distinction is made here between total porosity and effective porosity. The former includes all void space, both interconnected and isolated, while the latter includes only those voids which are interconnected. This investigation deals only with the effective porosity.* Numerous cases had been noticed in which there appeared to be appreciable discrepancies in the results of porosity determinations on core samples. Differences of as much as 10 to 15 porosity per cent had been reported from different sources

Jan 1, 1951

By P. N. McCreery, R. L. Slobod, B. J. Dotson, James W. Spurlock

A core sample porosity-check program is described. A number of laboratories participated in the investigation. which comprised measuring the porosities of ten selected natural and synthetic core samples. Each laboratory employed its own method (or methods) of measurement. These included Boyle's Law, water-saturation. and organic liquid-saturation methods. Brief descriptions of each method employed are given. In general, the measured values of porosity were in reasonably good agreement. The average deviation of porosity from the mean or average values for the group of samples was ±0.5 porosity per cent. The results of these measurements are compiled and presented in graphical form. INTRODUCTION The total hulk volume of a porous sample is derived from the sum of two volumes, the void or pore volume and the solid* or grain volume. The porosity fraction of the sample ia defined as the ratio of the void volume to the bulk volume. Multiplication of this ratio by 100 converts it to per cent porosity. Distinction is made here between total porosity and effective porosity. The former includes all void space, both interconnected and isolated, while the latter includes only those voids which are interconnected. This investigation deals only with the effective porosity.* Numerous cases had been noticed in which there appeared to be appreciable discrepancies in the results of porosity determinations on core samples. Differences of as much as 10 to 15 porosity per cent had been reported from different sources

Jan 1, 1951

By William Garrett

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

Jan 1, 1886

By William C. Cooley

INTRODUCTION Considerable research has been conducted on the use of steady and pulsed jets of water at high pressures to produce slots or holes in rock, and to fracture rock. The primary objectives of prior research have generally been to determine the feasibility of excavating or drilling rock or minerals and to determine the optimum jet parameters for this purpose. The present study was undertaken in order to identify the pertinent dimensionless parameters involving jet and rock properties which characterize the liquid jet penetration process and to develop empirical correlations of the existing test data which would permit engineering prediction by means of scaling relationships. The present paper is in the nature of a progress report, because not all the existing test data have been processed. Also effort has been concentrated on correlation of data on the specific energy (jet kinetic energy per unit volume of rock removed or broken), rather than correlation of jet penetration depth, hole diameter, kerf depth or kerf width. However, it is clear that this method of correlating data on specific energy in terms of dimensionless parameters shows great promise and provides insight into the nature of the physical processes of jet erosion and fracture. It therefore can help to avoid drawing incorrect conclusions from limited experimental data. DIMENSIONAL ANALYSIS The method of dimensional analysis is particularly valuable where the mathematical relationships controlling a physical process are unknown or complex. The grouping

Jan 1, 1971

By S. M. Brisbane

The life of refractory linings in rotary cement kilns can be shortened by uneven or inadequate support of the kiln and its shell and by variations in the conditions of operation. Alteration of these factors may, according to their nature, bring about mechanical deterioration of the lining or promote chemical attack. Chemical attack has been described elsewhere. The distortion of cement kilns has been discussed in a general manner by Rochow, who indicates the amount of distortion which may occur in an unlined shell, and by Rosenblad; who states that the deformations of the shell are greatest above the trunnions. The present article indicates the extent of the distortion of a kiln to an oval shape in certain selected positions and the deviation from a straight line of the kiln along its length between two supports. The cement kiln is a long, hollow, rotating cylinder consisting of steel plates which may be either welded or riveted together. This shell is supported on tires, frequently 60 ft apart, which roll on trunnions. The large mass of the kiln causes distortion of its cross-section; it becomes slightly oval, i.e., diameters lengthen as they become horizontal and shorten as they become vertical. There is also a tendency for the shell to bow between supporting tires; this bowing may be upwards or downwards depending on the position of the weight forces and the supports. The extent of the deviations from the ideal kiln shape was investigated.

Feb 1, 1956

By Takahide Wakamatsu, Yoshiaki Numata, Charn Hoon Park

INTRODUCTION A technique is needed to apply the flotation method successfully to apply the flotation method successfully to low grade and complex ore bearing hard-to-float oxide minerals. Thus it is necessary to find a new selective, powerful collector or to develop a new flotation process. Some attempts to use two or more kinds of collectors combined in flotation have been made but the principle of the reaction between the collectors used and the surface of mineral as well as the effect of combined collectors on flotation has not yet been fully understood. As part of the study on the improvement of selective collection in flotation, we have been investigating the flotation of minerals using two kinds of organic reagents, one of which is a conventional collector. We found xanthates were able to adsorb even onto the surface of oxide mineral, with the help of another organic reagent, e.g. a chelate compound (1). Furthermore, a notable effect of combined reagents such as the xanthate-amino acid combination (2) was found on the reagent adsorption phenomena and the collection phenomena, depending on the combination of reagents. The present study was carried out to clarify the effects of adding two kinds of collectors to the collection of mineral in flotation in the following two cases: (1) joint use of xanthate and di-alkyl dithiophosphate for galena collection and (2) joint use of a cationic collector with xanthate for scheelite collection.

Jan 1, 1980

By P. St. J. Perrott

AN explosive of balanced composition might be expected, on first consideration, to develop maximum propulsive strength.1 This hypoth¬esis is based on the assumption that an excess of oxygen would act simply as an inert material with a consequent lowering of flame temperature, also that a deficiency of oxygen would tend toward incomplete reaction of the combustible materials, thereby preventing development of the full strength of the explosion. Actually, however, it can be shown both theoretically and experimentally that an explosive having a certain oxygen deficiency will develop the greatest propulsive strength. This fact has been known to the technical staffs of explosives manufacturers for many years, but it has not always been recognized by explosives engineers in the field. For example: There is a fairly widespread opinion that the wrapper of a stick of dynamite is merely a container for the explosive and that it plays little if any part in the development of propulsive strength. Actually, it can be shown that the wrapper enters fairly completely into the explosive reaction. In the case of most gelatin dynamites, a given weight of explosive from which the wrappers have been removed will develop considerably less strength than the same weight of explosive plus wrapper, in spite of the fact that the latter combination contains less weight of the actual explosive ingredient. It can also be shown that a cartridge 7/8 in. in diameter may be stronger, weight for

Jan 1, 1928

For the first time in its history the Institute will hold a meeting in the State of Arizona. A few years ago Arizona stood third in the copper-producing districts of the United States. Since that time, with the development of porphyry mines, the output has gone up with great rapidity until it not only is the leading district, but its output at the present tune is at the rate of nearly double the Montana output; which now stands second in the list. In connection with this development, most interesting departures have been made in methods of mining, concentration and smelting. Principles of mining and metallurgy of the greatest interest will be covered by papers which will appear in the Bulletin and be presented at Technical Sessions, while ample opportunity 'will ,be- afforded for those who go to the meeting to see all the points of interest to them. In addition, members will be well rewarded by the marvelous natural features to be seen on the trip, including the petrified forests, the cliff dwellings on the Apache Trail and the Grand Canyon of Arizona. It is planned to start the special train from New York, but members and guests may join the special at other points en route as indicated by the following schedule: ITINERARY Thursday; September 14th, Lv New York Grand Central Terminal 5.30 p.m. Dinner in dining car, a la carte

Jan 9, 1916

By V. Damiano, M. Herman

CELLULAR substructure observed in metal crystals grown from the melt. has been studied extensively'-' and is attributed to the existence of a constitutionally supercooled zone in the liquid ahead of the solidifying interface. The mathematical description of this process has been given in terms of the concentration of solute in the liquid phase, the rate of solidification, and the temperature gradien.t in the liquid as the only variables.5 This technical note presents some evidence of 1) the effect of crystal orientation on some aspects of cellular growth, and 2:) the degeneracy of these cells into dislocation arrays. The zinc single crystals used in these studies were alloyed with cadmium sufficient to produce the constitutional supercooled cellular substructure. Crystals containing 0.05 pct Cd exhibited substructure formation for a growth rate of 10 cm per hr and a temperature gradient of 15°C per cm in accord with the theory. The growing liquid-solid interface was examined after we liquid had been decanted away in a fashion similar to that described by Rutter and Chamers.' The cellular substructure was also observed after polishing and etching the surface directly behind the decanted interface with a solution of HNO, and water. Fig. 1 is a photomicrograph of a typical polished and etched surface revealing substructure, the cleavage plane, and twins. The crystal has been grown with its basal plane parallel to the direction of growth and the plane of the micrograph is per-

Jan 1, 1960

It is claimed that the first mining of copper by Americans in Arizona was done at Ajo, near the Mexican border, in 1854,* a year after this region had been added to the United States, under the terms of the Gadsden purchase. A group of adventurers, organized at Los Angeles under the name of the Arizona Mining & Trading Company, came, to the district. This party of prospectors consisted of 20 men, led by Major B. Allen, J. D. Wilson, and William Blanding. † They went first to Yuma, where the party divided, some of them going southward into Mexico while the remainder took the trail to Tinaja Alta, where they heard of the copper deposits of Ajo, which is 85 miles southeast from Yuma.‡ They found attractive outcrops of copper ore, and set to work energetically, but their operations suffered many interruptions, because that part of the country was still controlled by the Mexicans, who were uncertain about the exact position of the new international boundary. The Mexicans tried to expel them, but they held their ground. The first shipment of ore, consisting of native copper and cuprite, came from what is now the western end of of the New Cornelia workings; it was hauled in ox-carts to San Diego, 400 miles across the desert. § Later shipments were hauled to Yuma and floated on barges down the Colorado river to the Gulf of California, whence the ore was loaded on

Jan 1, 1932

By W. C. Lilliendahl, G. Meister

Uranium metal with a purity of about 99.9 pct was produced on a large scale by fused salt electrolysis with a material efficiency of about 90 pct. The material efficiency depends mainly on bath composition, electrolysis temperature, electrode smothering, and elutriation during washing of the powder. RESEARCH and development work on fused salt electrolysis carried on by the Westinghouse Lamp Div. Bloomfield, N. J., was done under the Manhattan District Corps of Engineers and later under the Atomic Energy Commission for the commercialization of uranium production for the first atomic pile at the University of Chicago in 1942. From the conception of the atomic bomb project it was recognized that metals with impurity levels having little metallurgical significance would be required. Permissible impurity levels were based on neutron absorption. Of particular significance was boron, which could not be present in amounts exceeding 1 ppm. The electrolytic method as developed in 1930 by Driggs and Lilliendahl,1,2 and later improved, yielded uranium of very low boron and other deleterious impurity content. No other method was capable at that time of producing uranium metal of the required purity.' The low boron content of uranium produced by the electrolytic process resulted from the availability of the reactants which were low in boron content, and from the inherent elimination of boron in the fused salt bath. Since the heart of any electrolytic process is the electrolysis cell, this paper will deal with the development of the original bath composition for the efficient production of uranium from a batch process to one of continuous operation. Emphasis also will be placed on other factors which will affect the material efficiency of the process. With the laboratory cell the material efficiency of uranium powder recovery in the early electrolysis was relatively low, about 35 pct based on the ratio of uranium recovered to uranium added. This early process also had other defects. The electro- lytic bath could not be used continuously. After three runs from a freshly charged crucible, the deposit showed a tendency to slip off the electrode as it was raised from the bath. This condition necessitated pouring the charge every fourth run and preparing a new bath. It was assumed at that time that this condition was caused by the increasing fluoride concentration with each addition of uranium salt, which adected the mobility of the uranium ions. Experimental The electrolysis cells differed in size only. They were of the floating cathode type. The laboratory cells were 21/2 in. ID and 6 in. deep and operated at 30 amp and 5 volts. Production was about 150 g metal powder per 8 hr. The plant cells (5 units) were 9 in. ID x 21 in. deep and operated at 1800 amp at 12 volts. The total production unit was designed to produce 250 lb of uranium powder per 8 hr day. Because of the tendency of uranium fines toward spontaneous combustion, material efficiencies were based only on the recovery of useful coarser metal which could be safely handled. The reported efficiencies are of particular significance only as related to the same group of experimental procedures. At the start of the project no changes were contemplated until previous data could be definitely confirmed. Therefore, the first experiments were with the 50 pct CaCl2-50 pct NaCl mixture. The material efficiency of uranium deposition as a function of the number of electrolyses is shown in Table I. In Table I, the decrease in efficiency at 800°C with number of runs is apparent and confirmed the earlier data. Operating at 900°C enabled the number of runs to be doubled, but before pouring the charge the efficiency of recovery became poor. This test indicated that the improved efficiency might have been caused by an increase in the fluidity of the bath.

Jan 1, 1958

By H. Kurushima, S. Tsunoda

An investigation of the hydrometallurgy of Cu-Zn concentrates by The Dowa Mining Co. of Japan is described and a detailed flowsheet of the Kosaka hydro-metallurgical plant is given. Sufficient operating experience has shown that the Dorrco FluoSolids system has proven successful for recovery of both zinc and copper by roasting in a fluidized bed. At present, 2400 metric tons of concentrates per month are being treated and recoveries of 93 pct Cu and 65 pct Zn are being effected. A SURVEY of the Japanese chemical industry in 1949 revealed, among other things, that sulphur-bearing blast furnace gas from the Kosaka smelter of The Dowa Mining Co. Ltd., Kosaka, Japan, was being exhausted to the atmosphere as waste. In addition, it was costing that company an average of ten million yen ($28,000) annually for damages to the surrounding property caused by the sulphur dioxide in the gas. It was recommended by this survey that the gas be utilized for the production of sulphuric acid by the contact process. Mr. Kurushima visited the United States in May 1950 to investigate the engineering, construction, and operation of a contact acid plant. Any acid produced at Kosaka would necessarily have to be 98 pct H,SO, to prevent corrosion in railroad tank cars transporting it to the point of use. However, the production of 98 pct acid requires constant volume and SO, content of the gas. As the converter gas at Kosaka fluctuates in both volume and quality, it was decided to evaluate the smelting process with relation to other methods of recovery. This evaluation revealed a relatively new type of roaster, the Dorrco FluoSolids reactor, which was reported to be capable of roasting the copper sulphide concentrate in an excess of air with the production of an SO1 gas strong enough for acid production and a water-soluble copper sulphate calcine. The copper sulphate then could be leached from the roasted ore and electrolytic copper recovered from the leach solution in much the same manner as practiced by the Chile Exploration CO. for treating naturally occuring copper sulphate ores. Use of a reactor of this type would eliminate the need for a blast furnace and converter and, in addition, would effect savings in labor and fuel. The Kosaka ore is a microscopically fine mixture of copper, zinc, and lead sulphides. The lead and a small amount of the barite present can be separated by flotation, but any separation of copper and zinc proved extremely difficult. In blast furnace operation at Kosaka, zinc had been slagged off until a stockpile of about 12,000,000 tons containing 5 pct Zn had been accumulated. Mr. Kurushima felt that if any of the zinc in the concentrate was sulphat-ized and leached with the copper, it also could be recovered electrolytically. The Dorr Co., sponsors of fluidization technique in the metallurgical field, suggested that sulphate roasting be tested out on a laboratory scale and that, if successful, a commercial Dorrco FluoSolids system be constructed. They indicated that the results from such laboratory tests could be transposed to a commercial scale without pilot planting the roasting operation. It was therefore decided to send samples of flotation concentrate to the West-port Mill, laboratories of The Dorr Co., for testing. The objective of Mr. Kurushima's visit to the United States thus had changed from investigation of sulphuric acid plants to a fundamental examination of the hydrometallurgy of copper and zinc. Testing Program In February 1951, Mr. Tsunoda went to the United States to witness the application of the FluoSolids system to sulphate roasting at The Dorr

Jan 1, 1956

By I. Fatt

Networks of resistors are used as analog computers to obtain relative permeability and resistivity index curves for networks of tubes. These curves have all of the characteristics of those obtained on porous media and, therefore demonstrate the validity of the network of tubes model. INTRODUCTION In paper I' of this series the network model was shown to give information on the structure of porous media that could not be obtained from the bundle of tubes model. The agreement between the capillary pressure characteristics of a network of tubes and those of typical porous media does not prove the validity of the network made. The bundle of tubes model, although it gives less information, also shows this agreement. In this paper the flow properties of a network of tubes are shown to be in agreement with flow properties of porous media. The flow properties of the bundle of tubes model are not in adequate agreement with those of porous media. The dynamic properties of porous media, such as fluid permeability and electrical conductivity, have been found experimentally to be more sensitive functions of structure and pore size distribution than are the static properties such as porosity and capillary pressure characteristics. The network model can, therefore, be best tested by comparing the dynamic properties of a network of tubes with the observed properties of porous media. All static and dynamic properties of a completely valid model must agree with the observed properties. The most commonly measured sensitive dynamic properties are the relative fluid permeability and the relative electrical resistivity. Experimental measurements of these dynamic properties on sandstone, sintered glass, sintered alumina, and soil are reported in the petroleum and soil science literature. These properties were chosen, therefore, for the test of the network model. In the network model, relative permeability is the permeability of the network when some of the tubes are not conducting fluid, relative to the permeability when all tubes are conducting fluid. Similarly, the relative resistivity is the electrical resistivity of the network of tubes when some of the tubes are filled with a nonconductor. relative to the resistivity when all tubes are filled with the electrical conducting fluid. Single Size Tube Network The simplest porous medium is one in which all pores are of the same size. Such media can be approached by packing beds or columns of uniform size particles of sand, glass, or metal. The model of such medium in this study is a network of single size tubes. The network form, the ß factor, is usually not known for real porous media. If the validity of the network model can be established, then the study of the flow properties

Jan 1, 1957

By O. L. Culberson, J. J. McKetta

INTRODUCTION The equilibrium constants for methane and for water, and for ethane and water have been calculated from experimental data for the two binary systems.2,3,11,12 These constants are for the two-phase systems for the temperature range of 100" to 340°F and the pressure range of 200 to 10,000 psia. The constants for ethane are greater than those for methane. Equilibrium constants for a natural gas from a natural gas-water system6 are about the same as those for methane. Equilibrium constants for water in all three systems are very nearly the same over the greater part of the range of temperatures and pressures studied. In ideal solutions, the vapor-liquid equilibrium constants for a component should be the same in all such solutions at a given temperature and pressure.5 Few solutions are ideal, and consequently the use of generalized constants often leads to error in situations where they do not actually apply. In decidedly non-ideal systems, it is desirable to have equilibrium constant data for the specific system. Vaporization equilibrium constants may be calculated either by thermodynamic methods or from experimental vapor-liquid equilibrium data. In the thermodynamic calculation. the equilibrium constant K may be shown to be" K = fP,/fl'..........(1) where fPi is the fugacity of the pure component i at the given temperature and at the vapor pressure of the pure component, and fp is the fugacity of pure i in the gaseous state at the temperature and total pressure of the system. At best the thermodynamic calculation results in a K applicable to ideal solutions. Equilibrium constants calculated from Equation (1) have been found to have only limited agreement with experimental values, even though the solutions for which they were calculated approached ideality."'" If the more volatile component is at a temperature above its critical, the accuracy of the equilibrium constant for the component is made more doubtful by the use of the vapor pressure term under such conditions. In order to make the thermodynamic calculation on a component above its critical temperature, one must resort to one of the empirical methods of extrapolation of the vapor pressure to conditions above its critical point.13 Application of the thermodynamic equilibrium constant then to the methane-water or the ethane-water systems would be risky since the systems are non-ideal, and the methane and ethane are above their critical in most petroleum operations. ETHANE-WATER SYSTEM In the temperature range of from 100° to 340°F and for pressures up to 10,000 psia, the vapor-liquid equilibrium data 'References given at end of paper. Manuscript received in the office of the Petroleum Branch March 16, 1951.

Jan 1, 1951