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By J. S. Ll. Leach, L. R. Rubin, M. B. Bever

The energies of formation of ordered and disordered solid solutions of composition CusAu and the energy of ordering in this alloy were determined by tin solution calorimetry. The degree of order was measured by X-ray diffraction and electrical resistance and microhardness measurements were made on ordered and disordered specimens. AMONG the phenomena associated with the order-disorder transformation of a solid solution, the change in internal energy is of special interest because of the part it plays in the various theories of ordering. Published values for the decrease in internal energy accompanying the formation of a superlattice from a disordered solid solution of composition CuAu range from —370 to —2260 cal per gram-atom. Some of these values represent calculations based on theory and others are the results of experimental measurements. The distinction between the change in internal energy, AE, and the change in enthalpy, AH, can here be neglected, because they are approximately equal for solid-state reactions at normal pressure. An analysis of ordering by Bragg and Williams' predicts an energy change of —605 cal per gram-atom for the formation of a superlattice in the alloy Cuau from a completely random solution. Peierls" application to Cuau of Bethe'sb earest-neighbor theory yields —560 cal per gram-atom for the formation of a superlattice from a matrix which initially contains short-range order. Cowley' extended the nearest-neighbor approach to include as many as five shells of neighbors; on this basis a change in energy of —500 cal per gram-atom is expected. Eguchi," using a quantum-mechanical treatment, calculated a value of —2260 cal per gram-atom for the difference in the energy of completely disordered and completely ordered Cu,Au. Sykes and Jones- eated a completely ordered alloy and measured its heat capacity as a function of temperature. This measured heat capacity agrees closely with the corresponding value found by the Kopp-Neumann (or mixture) rule up to about 250°C and above this temperature exceeds it, especially near the critical temperature for ordering. The difference between the integrals with respect to temperature of the observed and the Kopp-Neumann heat capacities was considered to be the energy of ordering. By this method Sykes and Jones found a value of —530 cal per gram-atom. This value is not adjusted for the short-range order remaining above the critical temperature. The pres- ence of such short-range order is suggested by the difference between the measured heat capacity and the extrapolated Kopp-Neumann heat capacity immediately above the critical temperature. Values reported by Weibke and von Quadt' and by Hirabayashi, Nagasaki, and Maniwaa were obtained in the course of investigations primarily aimed at other objectives. Weibke and von Quadt measured the temperature coefficient of the electromotive force of a Cu-CuAu cell. They obtained a value of —1010 cal per gram-atom for the heat of formation of the alloy at 500°C, at which temperature there is no long-range order. They also obtained —1380 cal per gram-atom as the heat of formation of the ordered alloy at 370°C. Considering the heat of formation of the disordered alloy to be independent of temperature, they estimated the energy of ordering at 370°C as —370 cal per gram-atom. At this temperature long-range order is incomplete and the degree of order changes rapidly with temperature. Hirabayashi, Nagasaki, and Maniwa," using an annealing calorimeter, investigated an alloy containing 23.4 rather than 25.0 atomic pct Au and thus could not obtain complete order. Thelr value of the energy of ordering was —490 cal per gram-atom. Orianis has recently investigated the Au-Cu system by the galvanic emf technique. He reports values for the heats of formation of Cu-Au alloys, from which the heat of formation at 427 OC of an alloy of composition CuAu may be found by interpolation. This value is —1080 cal per gram-atom. In the work here reported, disordered and ordered alloys of composition CuAu and corresponding mixtures of gold and copper were dissolved in liquid tin and the heat effects measured. These heat effects are small, since the dissolution of gold in tin is exothermic and the dissolution of copper is endothermic. The method, therefore, yields fairly precise values of the heats of formation of disordered and ordered alloys and of the energy of ordering. Experimental Procedure The calorimeter consisted of a long-necked Dewar flask immersed in a constant temperature salt bath and has been described by Ticknor and Bever." The chief changes in this equipment were an improvement in vacuum and the replacement of the mercury thermoregulator by a resistance thermometer control circuit. The solvent, which was maintained at a constant temperature near 350°C, consisted of 500 grams of 99.99 pct pure tin. The solute samples were mixtures of gold and copper in the proportion corresponding to the composition Cu,Au or solid solutions

Jan 1, 1956

By Frederic P. Dewey

The Bureau of the Mint of the United States Treasury maintains 13 ofEces for the purchase of gold-bullion, and this paper describes an investigation to establish the reasonable differences in the assay-results at the various institutions which may be commercially allowable in the settlements between them. Beginning with the comparative assay of proof-gold at the Philadelphia mint and the Utrecht mint, which shows 0.00002 as the closest agreement now possible, nine tables of comparative results, taken from the regular work of the service, are given..These tables begin with very fine gold, produced in an electrolytic refinery, showing close agreement in the assay-results, and follow through decreasing gold fineness and increasing amounts and complexity of base metals to very impure and complex bars produced at cyanide-mills, some of which give widely-varying results. Next is given a series of results on samples, prepared and sent out to various laboratories in the service, to test the influence of different metals and various combinations upon the agreement of the assay-results ; 11 samples were sent out and each one was assayed from 44 to 71 times, making a total of 623 assays. To these ire added 107 assays of identical samples of coin-gold. On a previous occasion,' I have endeavored to show the degree of accuracy that may be expected in the ordinary everyday analysis of various materials, and on another occasion,2

Jan 1, 1910

By AIME AIME

A PAPER prepared by James A. Adams, development engineer of the fitline & Smelter Supply Co., and presented at the last Annual Meeting of the A.I.M.E. in New York City, de- scribed a new automatic pulp density controller which has had a most favorable reception. Manual control has until now been the universal practice in spite of its shortcomings; samples of pulp for density determination were often improperly taken, and only at the operator's convenience, so that the trend in density changes was frequently missed, and the grinding circuit al- lowed to operate under something less than the most efficient conditions.

Jan 1, 1940

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 G. J. Benard

In the 1970’s, several plants have been built and others are in the design stage which use solvent extraction for recovery of copper from acid leach solutions. Other plants are presently being built for the recovery of nickel and cobalt from laterite ores by prereduction and ammonia leaching. A review will be given on the materials of construction for these leaching and solvent extraction processes. Many plants have factors in common which permit selection with a greater degree of accuracy. Based on pilot plant corrosion data, effective use of materials of construction includes proper selection of materials, substitution of lower cost plastics for alloys, and selection of materials resistant against chloride stress corrosion cracking.

Jan 1, 1974

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 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 Jack M. Jodrey, Neil D. Donnell, O&apos

Bituminous sands of the Lower Cretaceous McMurray Formation in northern Alberta constitute the ore for the surface mining operation at Syncrude Canada Ltd. These sediments represent a complex succession of fluvial, estuarine and marine depositional environments. Grade prediction is realized through a combination of geological interpretation, computer modeling, and reference to past mining experience. Accurate forecasts of feed grade permit reliable predictions of volumes for removal to meet budgeted synthetic crude oil production. This planning facilitates efficient allocation of mining equipment and resources. The feed grade to the Extraction Plant is monitored at various points along the delivery system.

Jan 1, 1985

The necessary funds have been provided for the award in 1915 of three prizes, respectively of $50, $30, and $20, for the best essays, or other papers, submitted in competition by Junior Members and Members of Affiliated Student Societies. The following rules for the competition are therefore established in accordance with the instructions of the Board of Directors May 22, 1914: (1) A competitor for the President's Prizes must be, at the time of submitting his essay, either a Junior Member or a Member of an Affiliated Student Society of this Institute.

Jan 1, 1917

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 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 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 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 A. D. Schwope, L. R. Jackson, A. M. Hall

In the course of an extensive investigation of the comparative properties of several types of copper, data were obtained on the cold working and subsequent recovery and recrystallization of the copper. In this paper, relations between the degree of cold work and the course of re-crystallization are developed. In particular, it is shown that the course of recrystallization over long periods of time and at low temperatures can be predicted with reasonable accuracy from short-time high-temperature recrystallization data. Materials Used in The Investigation Three types of copper were used in this investigation; these were tough pitch, OFHC, and OFHC copper with 15 oz per ton of silver added identified herein as Lots C, D, and F, respectively. The material was supplied by the American Metal Co. Ltd., and processed by the Rome Cable Co. The analyses of the three types of copper are given in Table I. Originally, it started as wire bars 4 X 4 X 54 in. These bars were heated to 871° C in air and hot rolled to % in. rod. This rod was cold drawn to 0.204 in. rod (70 pct reduction) in three passes and annealed at 427°C for 4 hr. A portion of the 3/8 in. rod was saved for more detailed cold-drawing experiments. Starting with the annealed 0.204 in. rod, hard-drawn wires were produced by cold drawing to 0.081 in. wire in 7 passes (84.4 pct reduction in area). Half-hard wires were made by cold drawing the 0.204 in. rod to 0.102 in. wire, (75 pet reduction) in 6 passes and annealing at 427'C for 4 hr. This annealed wire was then drawn to 0.081 in. wire, (37.1 pet reduction) in 2 passes. Square rod was made by hot rolling wire bars to Re in. rod in 8 passes. This rod was then cold drawn to 0.445 in.-diam rod and annealed for 346 hr at 538°C. It was then cold drawn to 0.325 in. rod and again annealed at 538°Cf or 3 1/2 hr Hard square rods were then made by cold rolling this material to 0.257 X 0.257 in. rod, a reduction in area of 20.5 pct. Half-hard square rods were made by cold rolling to 0.268 x 0.268 in. square, annealing for 3 1/4 hr at 538°C and cold rolling to 0.257 x 0.257 in., a reduction of 8.5 pct. Soft wire or rod was made from all types of copper by annealing the hard-drawn material at 343°C for 3 hr in steam. The grain size of the annealed 0.081 in. wire varied slightly among the three lots: from o.o15+.oz5 mm in the silver-bearing OFHC to 0.035-0.045 mm in the OFHC copper. The annealed 0.257 in. wires were more uniform in grain size, averaging about 0.035-0.045 mm. Representative structures are shown in Fig I. Effect of Cold Drawing and Tensile Strain on Strength of Copper Conventional tensile tests were performed on the three types of copper in the various degrees of hardness described above. Results of these tests are tabulated in Table 2. The results in Table 2 are 6

Jan 1, 1949

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 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

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 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.