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By Richard Moldenke

Note.—At the request of the American Society for Testing Materials, this paper wau presented at the New York Meeting, February, 1923, in connection with the "A. S. T. M. Tentative Specifications for Foundry Pig Iron" and The Physics of Cast Iron and Its Bearing on All Cast-iron Products and Specifications for Cast Iron," by William R. Webster. The discussion of this paper was not published by the Institute, having been referred to the American Society for Testing Materials, as these papers were again presented for discussion at the meeting of that Society at Atlantic Cit;, June, 1923. The result of these discussions is shown in the following abstract from the Committee A3 report on cast-iron specifications: During the past year, the adaptability of the tentative specifications for pig iron for the steel and the malleable foundry, in addition to the iron foundry proper, have been studied and suitable changes and rearrangements are being made which appear to cover the situation properly. In spite of the experience of foundrymen to the contrary, there is a persistent call from consumers of castinga for defixute compositions for given lines of castings. To respond to this call for information desired by the consumer—information every modern foundryman should have and guide his procedure with—the committee has requested the Sub-committee on General Cast!rigs to take up this matter with a view of constructing tables of analyses rang? for Important lines of foundry product. These analyses ranges however, are to be given as "recommendgd practice" and not intended for actual spkcification. In this way, the consumer of the foundry product will get the information he wants; the furnace-man will be gulded in the production of his pig irons to prepare for analyses ranges which are more closely standardized and have less of "freak" requirements made by Inexperienced metallurgists; and the foundryman will not be bound by chemical requirements he knows will not work out well with his particular reglonal supphes of melting stock. Doctor Moldenke's paper is published in full as it shows clearly the good results of the Institute's work in 1895 and a comparison of the same with the present knowledge of the metallurgy of cast iron—Bradley Stoughton, Chairman, Iron and Steel Committee. In MaRch, 1895, William R. Webster contributed a carefully prepared scheme for the study of the physics of cast iron to the American Institute of Mining Engineers at its Florida meeting. This summary of the interrelation of the chemical and physical characteristics of cast iron with the operations of daily foundry practice caused a wide discussion of the then little understood though universally used material. Mr. Webster has requested the author to bring the subject up to date and, while glad to comply, he must pay that with all the knowledge that has been gained in the quarter century that has passed since the subject was brought to the attention of the Institute—and we now are pretty familiar with cast iron in all its aspects—there is practically noth-

Jan 1, 1923

By Richard Moldenke

Note.—At the request of the American Society for Testing Materials, this paper wau presented at the New York Meeting, February, 1923, in connection with the "A. S. T. M. Tentative Specifications for Foundry Pig Iron" and The Physics of Cast Iron and Its Bearing on All Cast-iron Products and Specifications for Cast Iron," by William R. Webster. The discussion of this paper was not published by the Institute, having been referred to the American Society for Testing Materials, as these papers were again presented for discussion at the meeting of that Society at Atlantic Cit;, June, 1923. The result of these discussions is shown in the following abstract from the Committee A3 report on cast-iron specifications: During the past year, the adaptability of the tentative specifications for pig iron for the steel and the malleable foundry, in addition to the iron foundry proper, have been studied and suitable changes and rearrangements are being made which appear to cover the situation properly. In spite of the experience of foundrymen to the contrary, there is a persistent call from consumers of castinga for defixute compositions for given lines of castings. To respond to this call for information desired by the consumer—information every modern foundryman should have and guide his procedure with—the committee has requested the Sub-committee on General Cast!rigs to take up this matter with a view of constructing tables of analyses rang? for Important lines of foundry product. These analyses ranges however, are to be given as "recommendgd practice" and not intended for actual spkcification. In this way, the consumer of the foundry product will get the information he wants; the furnace-man will be gulded in the production of his pig irons to prepare for analyses ranges which are more closely standardized and have less of "freak" requirements made by Inexperienced metallurgists; and the foundryman will not be bound by chemical requirements he knows will not work out well with his particular reglonal supphes of melting stock. Doctor Moldenke's paper is published in full as it shows clearly the good results of the Institute's work in 1895 and a comparison of the same with the present knowledge of the metallurgy of cast iron—Bradley Stoughton, Chairman, Iron and Steel Committee. In MaRch, 1895, William R. Webster contributed a carefully prepared scheme for the study of the physics of cast iron to the American Institute of Mining Engineers at its Florida meeting. This summary of the interrelation of the chemical and physical characteristics of cast iron with the operations of daily foundry practice caused a wide discussion of the then little understood though universally used material. Mr. Webster has requested the author to bring the subject up to date and, while glad to comply, he must pay that with all the knowledge that has been gained in the quarter century that has passed since the subject was brought to the attention of the Institute—and we now are pretty familiar with cast iron in all its aspects—there is practically noth-

Jan 1, 1923

By W. P. Sykes

IN CONNECTION with a study of tungsten steels, Honda and Murakami1 reported an investigation of the system iron-tungsten. This report included a tentative equilibrium diagram, photomicrographs of various alloys in the series, and qualitative measurements of hardness and magnetic properties. The present investigation originally had as its object the study of the hardness and tensile properties of a series of carbon-free iron-tungsten alloys. But, as the work progressed it became evident that the system possessed other features of interest, so the scope of the investigation was enlarged. MATERIALS The iron powder used in preparing the alloys was obtained as follows: Iron oxalate was precipitated from a ferrous-sulfate solution by the addition of a solution of oxalic acid. This oxalate, after thorough washing, was ignited to iron oxide, which after reduction in hydrogen at about 1000° C. yielded iron powder containing but about 0.2 per cent. iron oxide and about 0.005 percent. carbon. Tungsten metal in the form of powder, such as is used in the manufacture of filaments for incandescent lamps, was the other constituent. This material analyzed 99.8 per cent. tungsten and contained no carbon, The metal powders, in the desired proportions, were mixed by tumbling and formed, under pressure of 20 tons per sq. in., into rods 3/8 by 3/8 by 10 in. To form the alloys without contamination, sections of the pressed rods were placed on alundum slabs and heated in an alundum tube wound with a tungsten resistor and packed in heat-insulating material. While the resistor was heated, a stream of hydrogen was continually passed through both the tube and the case containing it. The tungsten winding on the tube, as well as the material heated within the tube, was thus protected from oxidation. Such a furnace will operate constantly

Jan 2, 1926

By George Frederick Kunz

The manifold inconveniences resulting from the absence of a uniform standard of mass for determining the weight of precious stones have long been obvious. This lack has been keenly felt in commercial transactions, and those who have devoted time and research to the study of historic diamonds and precious stones have had frequent occasion to deplore the absence of such a standard in the past. In a paper read in Chicago in 1893, before the International Congress of Weights and Measures, held in connection with the World's Columbian Exposition, the writer suggested dividing the carat into 100 parts, and constituting a standard international carat of 200 mg.; that is, 5 diamond carats or 20 pearl grains to a French gram, making 5,000 carats or 20,000 pearl grains to a ki1ogram. He also called attention to the fact that while this would depreciate the present diamoiid carat or pearl grain only about 2.5 per cent., it would abolish the troublesome discrepancies between the various carat-weights now in use, and could be easily explained and understood everywhere.' The subject of the various diamond carats, their incongruity, and the resulting confusion as to the correct weights of historic gems when definite records of them are searched for, has been fully treated by me in an extensive study of this subject in The Book of the Pearl2 To the earnest and unremitting efforts of C. E. Guillaume, Director of the Bureau Internationale des Poids et Mesures at Sévres, is largely due the eventual success of this eminently desirable reform, which he has constantly urged both by articles on the subject and by addresses delivered in Paris before the International Committee for Weights and Measures.3 The general adoption of a uniform standard for dealings in pre-

Jan 1, 1914

By E. Stansfield

IT. has long been known that coal is unstable and oxidizes in air, even at ordinary atmospheric temperatures; also, that such oxidation affects the analysis of coal. Nevertheless little or no precaution is taken to prevent oxidation in the ordinary methods of analysis, and the possibility of error due to oxidation is sometimes ignored even in researches on coal. Although the general nature of coal oxidation is well known, and many workers have made careful studies of the rate of oxidation of different types of coal exposed to oxygen at different temperatures, yet the amount of oxidation coals undergo in the ordinary process of analysis, and its influence on the determined analysis, is not well known, and the published data are widely scattered through the literature. This paper is a collec-tion, from this laboratory, of data that bear on the subject, together with a brief summary of three methods employed here to evaluate the oxidizabil-ity of coal. The post-Carboniferous coals of Alberta range all the way from anthracite down to lignite. As some of them are notably susceptible to oxidation, the necessity for care was early forced upon our attention, and oxidation has been reduced either by the removal of air with a vacuum pump or by the displacement of air with natural gas (methane). The two routine analytical operations most liable to involve oxidation are the preliminary, partial drying of the crushed coal (called air-drying) and the determination of moisture. The first is a prolonged operation on coarse coal at ordinary temperatures, and the second a short treatment on powdered coal at higher temperatures. Oxidation also occurs in coal samples stored in ordinary sample bottles. In order to gain information for this study, determinations were recently carried out on the same samples in air, in natural gas, and in vacuo. Sixteen coals were tested; three would be classed in the United States as coking bituminous coals, two as noncoking, nonslacking, bituminous coals, and the rest as subbituminous. Table 1 gives typical analyses of these coals as mined.

Jan 1, 1934

By B. M. Larsen

AN increasing amount of attention is being paid to the possible influence of oxygen, in its several modes of occurrence in steel, upon some of the properties of the metal; but clearly investigations along this line are unlikely to yield significant results until reliable analytical methods for the determination of oxygen have been established. This paper presents some results of a study of an improved Ledebur method which aims to determine a definite portion of the oxygen; namely; that which presumably is present in diffusible form in the. solid steel. These more or less preliminary results lead us to believe that the oxygen so determined has some significance; their presentation at this time will, we hope, stimulate discussion of, and focus attention upon, certain rather neglected aspects of the problem. Considerable work has been done recently on methods of estimating inclusions and on the vacuum-fusion method for oxygen; with results which, however, are of somewhat questionable significance. It is commonly presumed that the oxygen in a bath of molten steel in a furnace is present partly as a separate phase consisting of suspended particles of oxides or silicates, partly in solution, the latter being probably the more important. Upon addition of a deoxidizer, it reacts with some portion of the dissolved oxygen and precipitates it as additional suspended particles; the oxygen not eliminated in this way, which remains in solution in the liquid steel, may be regarded indifferently either as dissolved oxygen or as dissolved FeO. When the steel is poured, some of the suspended particles rise towards the surface, others remain trapped in the finished steel, appearing as nonmetallic inclusions in amounts corresponding usually to about 0.01 to 0.03 per cent 02 in the steel. The dissolved oxygen may be partly eliminated as CO during freezing of the ingot, but some remains either in solution or in part precipitated as FeO. Finished steels may thus contain oxygen in several forms: (1) In non-metallic inclusions which are probably quite insoluble in the solid metal at all temperatures; (2) in solid solution which at lower temperatures may be supersaturated; (3) in FeO particles produced by relief of this

Jan 1, 1932

By D. A. Dahlstrom

In the paper, a comparison was made between flowsheets using the screen bowl centrifuge and disc filters, respectively, as the primary dewatering device. The authors very effectively show that by raising feed temperature, mechanical dewatering is enhanced through reduced viscosity of the water. When a final coal moisture of 10% is required, the net effect of heating the feed is a reduction in thermal requirements because of the lower evaporated load on the dryer. The flowsheet comparison on this, however, was not completely correct. Disc filters do not generally utilize enhanced mechanical dewatering through increased temperature. Horizontal belt filters, through the optimal use of steam heating of the filter cake, have shown significant cost reductions over disc filters where steam is not used. In addition, the authors forgot to mention that there is a certain fraction of the feed that is so fine that it cannot be recovered by the centrifuge economically. That is the function of the filtration device shown in [Fig. 4]. In subbituminous pipeline coals, this fraction represents more than 10% of the feed. Even after flocculation and belt pressing, the moisture content in the fine fraction is 30%-40. Recent tests on a subbituminous pipeline coal slurry, compared an Eimco-Extractor horizontal belt filter with the screen bowl centrifuge flowsheet shown in [Fig. 4]. Mechanical dewatering was enhanced through the use of a steam dry zone after the initial dewatering zone. Vacuum pump horsepower was reduced by more than 50% through the use of condensers, and heat recovery was utilized to minimize thermal costs. Thermal drying to 10% moisture by weight was required in both flowsheets. The 0.5 wt% fines in the filtrate were flocculated and recycled to the filter, thus eliminating the belt press and solids mixers. When the three major operating costs (which normally account for 50%-75% of the coal operating costs) of steam, electricity, and flocculants at current prices were calculated, the flowsheets utilizing the Eimco-Extractor had cost savings vs the centrifuge flowsheet of 89c/t (81c per st) of surface dry coal. This advantage increases with increasing thermal and electricity prices. I congratulate the authors for the strides made with the screen bowl centrifuge. However, filtration flowsheets continue to be improved and their simplicity and low thermal and electrical requirements should not be so quickly dismissed.

Jan 1, 1984

By C. F. Jr. Nagel

THIS paper is written primarily for those who are familiar with the processes mentioned but who desire a further insight into some of the fundamental principles. It does not give a complete description of the various practices employed in the working of aluminum and its alloys, but presents a few illustrations of the essential respects in which aluminum differs from other common metals, and emphasizes the controlling factors of the processes under consideration. HEAT TREATING Certain aluminum alloys are capable of having their mechanical properties greatly altered by a heat-treatment process. The degree of this improvement may be illustrated by the typical properties of duralumin (Table 1). It is essential that the material be in the wrought condition in order to obtain maximum heat-treatment effects.

Jan 1, 1927

By Arthur Knapp

NEARLY every technical man is called upon at some time in his life to deliver a paper before a technical audience or to write a technical paper for publication. It is not necessary to be an accomplished public speaker to deliver a technical paper successfully; it is only necessary to bear in mind a few obvious points. Poorly presented papers are nearly always the result of a few errors of deportment, but they are vital and at the same time so obvious that they are often overlooked. Experience is a good teacher but a little study and careful preparation will moderate the suffering of both an amateur speaker and his audience. An author's paper suffers, through poor delivery, in direct proportion to the suffering of his audience. The best test of a paper is to have it read aloud to the author. This will bring out faults not apparent when read silently by the author. Some of the things which will probably need correcting are improper phrasing, noneuphonic sequences, and long or involved sentences. Frequently authors write their papers in short crisp sentences for oral presentation, then rewrite them for publication.

Jan 1, 1942

As REVISED IN CONFERENCE FEB. 17, 1931 REPORT OF SUBCOMMITTEE ON MINE VENTILATION CODE OF A, I. M. E. COMMITTEE ON VENTILATION ALFRED W. HESSE, Chairman THOMAS G. FEAR GEORGE S. RICE E. A. HOLBROOK WILLIAM A. ROWE HOWARD ECKFELDT R. V. NORRIS CADWALLADER EVANS, JR. H..1. SMITH, Secretary REALIZING, from the safety and health standpoint, the need of furnishing air of good quality to workers underground and of diluting and carrying away dangerous and noxious gases, the following code is offered to unify regulatory measures in coal mine ventilation, so far as is practicable, in the United States of America.

Jan 1, 1931

By HENRY FA

HENRY FAY (communication to the Secretary*).-In reply to the discussion of my paper, I wish to take this opportunity to express my appreciation to the Chairman and the various gentlemen who have taken part. I regret that others have not offered criticism, for honest differences of opinion often lead to the truth, and suggest new lines of work. An experiment has been made which bears on Prof. Sauveur's discussion and which helps to emphasize the conclusion that cementation is not a factor in the hardening of: the surface. Dr. Langenberg, of the Watertown Arsenal, has heated for me, in vacuo at 1,000° C., a piece of the metal containing a hard surface. The microstructure shows uniform distribution of carbon throughout the metal, showing that no carbon has been added to .the surface and heating in vacuo has prevented any oxidation of the surface.

Jan 6, 1917

By Carle Hayward

AT THE February, 1916, meeting of the Institute, a paper presented by Hayward and Raymond gave the results of a study on the effect of time in tempering medium-carbon steel, when the following conclusions were reached: It is not fair to consider the question settled when only three specimens were used for each treatment, but the results obtained indicate that for reheating quenched medium-carbon steel to temperatures below 500° it is only necessary to heat it through. Longer heating has little or no effect on the tensile strength, ductility, or hardness. At temperatures above 500°, increasing the time of treatment causes a slight falling off in hardness and tensile strength with a corresponding increase in ductility. In the discussion of the paper these conclusions were attacked and evidence presented that seemed to throw doubt on their accuracy. The authors, however, showed that this evidence was based on high-carbon or alloy steels and no facts regarding medium-carbon steel were presented. During this study the heat treatment was carried out in a small electric resistance furnace. It held nine specimens, but when these were placed in the furnace the temperature was lowered to such an extent that 30 to 40 min. were required to reach the desired heat. The authors pointed to this as a weak point in the investigation and it seemed wise to supplement the research by work on similar steel but using a different method of heating. This has been done and the results are given in the present paper. The Rhode Island Tool Co. cooperated by furnishing the steel and turning the tensile specimens.

Jan 1, 1922

By K. Adam

Grinding in steel mills adversely affects the flotation of pyrrhotite. The electrochemical nature of inter action between pyrrhotite and active metals was investigated by contacting pyrrhotite with platinum at different applied potentials. Flotation tests, scanning electron microscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy were wed to examine the surface properties of pyrrhotite. The formation of hydroxide or oxide and sulfate species of iron through the oxygen reduction reaction at the cathodically polarized surface of pyrrhotite was shown to be the mechanism responsible for the reduced floatability of pyrrhotite.

Jan 1, 1985

By Clyde Williams

IF you would allow me some liberties, I would restate the title of this talk as "Scientific Research, Our Greatest Resource," because that title would represent more clearly a present-day conception of the metals and minerals situation. It is a subject worthy of careful consideration. Canada and the United States are so similar and interdependent in their national economies that, in the following discussion, examples of conditions in the United States may be interpreted to apply to Canada as well. Moreover, it is a striking fact that the per capita value of mineral production in Canada and the United States in 1940 was almost the same. Therefore, in the consideration of this subject, I have made no attempt to differentiate between the two countries. Consumption of the world's mineral resources in the last few decades. and particularly during World War II, has been so enormous as to require some form of magic to ensure the continued progress of civilization in the face of a diminishing supply of these resources which are so critically essential. As C. K. Leith pointed out, in 1941, indus-

Jan 1, 1947

By A. O. Dady

PRODUCERS of both bituminous and anthracite coal have for many years been worrying about the gradually decreasing consumption of their product in the United States. Twenty years ago production had climbed to a peak of 569,000,000 tons of bituminous and around 90,000,000 tons of anthracite. In 1939 it was about 393,000,000 tons of bituminous and 51,000,000 tons of anthracite. This does not mean that the country is using less polver than it did twenty years ago, or that we are living in colder buildings. As a matter of fact, about three times as much electric power is now being consumed as in 1920. In general two factors are responsible for the drop in coal consumption: (1) greater efficiency in the use of coal, and (2) increased competition from hydro power, internal-combustion engines, and substitution of oil and gas for coal in conventional furnaces. As to the first factor, it took 3 Ib. of coal to generate a kilowatt-hour of electricity in central stations in 1920 and it takes 1.4 Ib. now; it took about 175 Ib. of coal in railroad locomotives to haul 1000 long tons a mile in 1920 where it talces about 120 lb. now: and marked economies have also been made in the use of coal in steel plants: in by-product coke ovens, and in other large uses. As to the second factor, three times as much electricity is produced from water power now as was produced in 1920; three times as much oil is being consumed in various ways; and likewise, the consumption of natural gas has tripled- whereas coal consumption in the same period has dropped by 40 per cent

Jan 1, 1941

By John Boardman

THE Anaconda company has never indulged in any employee activities at Butte which might be termed paternalistic, but it has exerted a vast amount of effort in care of its employees during working hours. The reason for this policy is not lack of interest or that the company does not feel the effect of employees' activities while they are "off the job"; it is that the company and the city of Butte have grown up together and, each has been adequate in its own sphere, the company in providing employment at the highest possible wage and the city in providing housing, sanitation, commercial services, medical services, schools, churches, amusements and entertainments. The one exception to this independence between the company and the community is the Butte Water Co., which is a wholly owned sub-sidiary of the Anaconda Copper Mining Co. Mention of this relationship is made here because the water supply of such a city as Butte is one of the principal factors in determining the health of the people. Very early in the development of the Anaconda company an adequate and dependable water supply for the operations became necessary, therefore the company took over this important community function. So well has this activity worked out that during the whole period of time covered, in which the company has expanded to become practically the sole mine operator and the community has grown from a small mining camp to the status of a modern city, there has been no shortage of water or any outbreak of water-borne, epidemic disease.

Jan 1, 1938

By A. S. Emanuel

A correlation has been developed for calculating the phase behavior of, gas-condensate systems at reservoir conditions. The correlation is based on the principle of corresponding states and has been coded for an IBM 7094. Experimental K-values were determined for several gas-condensate systems at reservoir conditions to evaluate various semi-empirical parameters of the correlation. The approximate range of application of the correlation is 150 to 300F and 1,500 to 6,000 psi. INTRODUCTION The rapid development of digital computers during the past several years has made feasible the calculation of hydrocarbon phase behavior by methods based on rigorous thermodynamic principles. Good correlationsl have been developed for low to moderate pressures, but these techniques have not yet been extended successfully to reservoir fluids at high pressures. Consequently, the determination of phase behavior of oil and gas systems at reservoir conditions is still based almost entirely on generalized data correlations or on experimental studies of the fluid in question. While these methods have been used successfully many times, they do have inherent limitations that restrict their applicability. Generalized correlations, such as the NGShlA K-charts, are limited to the range of pressure, temperature and components for which the data were determined. The accuracy of these correlations is often questionable because the effect of total system composition is not well defined. Experimental studies offer a reliable method for determining phase behavior, but usually the studies are costly and time consuming. Recently, Leland and co-workers presented a new approach to calculating phase behavior from the principles of corresponding states.6-8 Corresponding states methods determine the thermodynamics properties of a given system by comparison with a reference substance whose properties are known. The accuracy of this approach depends on close chemical and structural similarity between the reference substance and the system in question and between components within the system itself. For high accuracy, it is usually necessary to correct for chemical and structural dissimilarities. In principle, however, the corresponding states method should be no less accurate at high pressures than at low pressures, provided reference substance properties are known. This paper describes an empirical modification of the basic correlation proposed by Leland, et al.6 for the specific purpose of calculating the phase behavior of gas-condensate fluids at reservoir conditions. The modified correlation, which has been programmed for an IBM 7094, may be used for either approximate or precise determination of fluid behavior depending on the amount of analytical and, experimental data available for the system. BASIC THEORY The basic theory of the corresponding states phase equilibria correlation was first published by Leland, Chappelear and Gamson.6 Subsequently, Leland, Chappelear and Leach published methods for improving the accuracy of the original theory.7-9 The aim of the correlation is to calculate the K-value of each component of a given system as a function of pressure, temperature, and over-all composition, where Once the K-values are known, the phase behavior may be determined directly by an appropriate flash calculation. The basic equation for calculating component K-values was taken from the work of Joffe. 4 For any component i of a mixture, the K-value is given by

Jan 1, 1969

By J. S. Hegwer, P. M. Dunlap

An improved acid for the treatrrzent of sulfate-con-raining limestones and dolomites is described. The acid is designed to reduce he reprecipitation of dissolved calcium sulfate and the possibility of plugging permeable flow channels. In addition, this improved acid has a much lower reaction rate than that of regular acid; the advantages of a "retarded" acid are obtainable. Field testing of the acid has shown it suitable for use in sulfate-containing formations. Substantial improvements in productivity generally resulted. INTRODUCTION Acid treatments of limestones, dolomites and other formations bearing carbonate deposits are frequently unsuccessful when the calcareous formation contains sulfate, either as anhydrite (CaSO,) or gypsum (CaSO4. 2H2O). Preliminary dissolution in acid followed by redeposition of calcium sulfate appears to be a major factor contributing to poor well performance after acidizing. The precipitate is usually the gypsum form of calcium sulfate, but in higher temperature formations it may be anhydrite. The freshly precipitated crystals are nearly always very small and needle-like. They may occupy a gross volume many times that of the original anhydrite crystals and will obviously constitute an impediment to flow through newly enlarged flow channels. It is believed that the redeposition problem is most severe when anhydrite lines the fracture systems and large pores which supply the effective permeability of a formation. Microscopic inclusions of calcium sulfate also present large sulfate surface areas for dissolution in acid. In either case, great amounts of calcium sulfate may dissolve before the acid can be spent on formation carbonates. For regular spent acid (originally 15 per cent hydrochloric acid) the precipitate could be as much as 270 Ib gypsum/1000 gal acid. Two techniques have been applied by the industry for reducing sulfate plugging during acidizing. The method'.' commonly employed in the field is the attempted removal of a quantity of regular treating acid before it has reacted completely with the formation. This is practiced because the solubility of calcium sulfate is greater in a solution that is still acidic than in one which has been largely spent on the formation rock. The chance of precipitative plugging is therefore reduced if the withdrawal is successful. However, it is often impossible to get the acid out of the formation before precipitation occurs. A second possible method, which at first glance appears practical, involves addition to the acid of sequestering agents which form strong soluble complexes with calcium ions. These chemicals do increase the "solubility" of calcium sulfate in fresh acid, but to a lesser extent in spent acid. The sequestering agents have, therefore, proved unsatisfactory because the amount of sulfate eventually deposited from the spent acid may be greater than that from regular acid. Another logical approach to the problem of calcium sulfate reprecipitation is the prevention of the initial dissolution of calcium sulfate by the common ion effect. This may be accomplished by adding a soluble calcium salt to the fresh acid. The use of calcium salts in treating acids is not entirely new. An earlier suggested use of a soluble calcium salt in hydrochloric acid apparently failed to recognize the full extent to which the solubility of calcium sulfate could be suppressed. The present study extends this earlier work and adds certain improvements toward the development of a practical anti-anhydrite acid. LABORATORY DEVELOPMENT Calcium Sulfate Solubility Table 1 shows the results of a laboratory study performed to establish the effect of calcium chloride concentration on gypsum solubility. Because of the strong tendency of calcium sulfate to form supersaturated solutions, accurate solubilities are difficult to determine. These solubility data probably are reliable to within ± 15 per cent. The solubility of calcium sulfate in 15 weight per cent hydrochloric acid increases with increasing temperature. This trend is also followed in hydrochloric acid which cantains calcium chloride. This is contrary to the solubility behavior of calcium sulfate in water, wherein the solubility decreases with increasing temperature.

The pressure of the gas in equilibrium with sphalerite has been determined in the temperature range of 680' to 825°C, using the Knudsen orifice method. A comparison of these experimental pressures with those calculated from thermal data and from other equilibrium measurements shows that the vapor above sphalerite is predominantly dissociated ZnS. Equations have been given for correctly calculating dissociation pressures using the Knudsen orifice method. It has been shown that the experimentally determined pressure is the same, whether the zinc sulphide is sphalerite or not, or a mixture of wurtzite and sphalerite. CONFLICTING points of view appear in the literature on the constitution of the vapor in equilibrium with solid zinc sulphide in the vicinity of 800°C. By comparing the dissociation pressure calculated from thermodynamic data and the vapor-pressure determination of ZnS by Veselovski,1 Lumsden2 has concluded that the vapor consists largely of dissociated ZnS. Sen Gupta,' however, concludes from his spectroscopic determinations that the vapor is largely ZnS molecules. In view of the fact that the thermodynamically calculated' dissociation pressure is higher than that experimentally measured by Veselovski, it seemed in order to repeat Veselovski's measurements. Experimental Procedure The method used for the determination of the pressures in this papel- is the Knudsen effusion cell. The apparatus and procedure were described in a previous paper- from this laboratory on the determination of the vapor pressure of silver. The only difference is that the Knudsen cell in this work is made from platinum and there is no external cover around the cell. The cell is an ordinary platinum crucible of 2.2 cm top diameter with a capsule cover. It was thought that platinum might stand up at these temperatures to the solid and gaseous ZnS, since it was found that the weight of the platinum cell itself did not change appreciably on heating ZnS in it at the working temperatures. To insure that reaction of the zinc sulphide with the cell was not giving' a false value, a stabilized zirconia cell was employed for check runs. Fig. 1 shows the comparison, which is satisfactory. Veselovski previously had measured the vapor pressure of ZnS using a silica Knudsen effusion cell. On repeating his experiment in this laboratory, it was found that ZnS at-tacked the silica cell, giving it a marked frosty appearance. This led to the belief that Veselovski's result:; may be in error. Also, he was operating at pressures above the range ordinarily considered safe for the Knudsen method. The effusion rate was measured by weighing the cell before and after each run. The weight loss during heating to temperature and cooling down was measured and subtracted from the weight loss during the actual run. The zinc sulphide used in this investigation was from two sources: Fisher cp grade, and a sample of pure sphalerite supplied by Mr. E. A. Anderson of the New Jersey Zinc Co. Before and after the series of runs with Fisher ZnS, X-ray analysis showed that both wurtzite and sphalerite were present. However, the ratio of sphalerite to wurtzite increased. All measurements were made below the transition temperature which has been reported" to be 1020°C. The data obtained in this investigation are tabulated in Table I. The pressure was calculated by the usual Knudsen formula" on the assumption that ZnS molecules were effusing. From these data, using pure sphalerite in the platinum Knudsen cell, the vapor pressure of ZnS, in mm of Hg, as a function of temperature is given by the solid line in Fig. 1. The best straight line, as determined by the method of least squares, is given by 14405 logpzns =-14405/T +11.032. A comparison of these results with Veselovski's shows that his results are about 50 pct lower. Discussion The vapor in equilibrium with solid zinc sulphide in the temperature range of this study will consist of Zn, S2, and ZnS mol, since other species of zinc and sulphur' are relatively unstable. The question to be settled is whether or not ZnS is largely dissociated. The derivation8 which follows gives the method of calculating the pressure of zinc and sulphur over solid ZnS, assuming complete dissociation, from Knudsen cell data. The free energy of the reaction 2 ZnS(solid) ? 2 Zn(gas) + S2(gas) is given by ?F?° = -RT In K = —RT In p12p2 where p1 is the zinc pressure and p is the sulphur pressure. If dissociation occurs in a closed system,

Jan 1, 1955

By Harry H. Power

The relative merits of air and natural gas as propulsive agents in pressure drive operations have been discussed for a number of years. When air or gas is introduced into the sand, various factors lead the operator to the selection of what he believes to be the proper propelling medium; but when the question of relative drive effect is raised, several physical and chemical premises must be taken into consideration in arriving at a conclusion as to the superiority of one medium over the other. Dow and Calkins1 and Beecher and Parkhurst2 have contributed fundamental experimental work on the effect of dissolved gas in lowering the viscosity and surface tension of crude oil. Herold; and Tickell' have indicated that whatever type of reservoir control obtains, gas plays other important parts in the movement of oil towards the well, namely: 1. The propulsive and expansive force of the gas. 2. The "Jamin effect," or resistance to the movement of oil in a porous media due to the formation of gas bubbles. When quantitative studies are made, parallel conditions must be selected whereby we may say definitely whether air is superior to gas as a driving medium, or vice versa. Examples of similar conditions are not easy to find in the field. However, in the laboratory we can make determinations which may lead to general conclusions when applied to the field. The experimental and research work described here was started at the laboratories of the University of California in January, 1927, and completed in private laboratories at Tulsa, Okla., in February, 1928. The apparatus used was designed especially for the work.

Jan 1, 1929