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By W. A. Klikoff, I. Fatt

The concept of fractional wet wattability is examined. Fractional water wettability of a reservoir rock is defined as the fraction of the internal surface urea that is in contact with water. Capillary pressure and relalive permeability of unconsolidated sand are shown to be functions of fractional wettability. INTRODUCTION The petroleum industry has long recognized that wettability of reservoir rock has an important effect on multiphase flow of oil, water and gas through reservoirs. As early as 1928 the American Petroleum Institute sponsored a study of wettability as part of API Project 27 at the U. of Michigan.' Despite 30 years of research, there is still little exact knowledge of the wettability of reservoir rocks. There are two parts to the wettability problem. After agreeing to a uniform nomenclature in regard to wettability,' the first question to be answered is, "What is the in situ wettability of a given reservoir rock?" If this can he answered the next question is, "What part does wettability play in determining the characteristics of multiphase fluid flow through the rock?" This paper represents an oblique attack on the problem of wettability. No attempt is made here to answer the basic question of wettability in situ. instead the consequences of the concept of fractional wettability are examined. Multiphase flow in sandpacks is shown to he highly influenced by fractional wettability. Jennings' has given 3 definition of wettability and the other terms used in discussing wettability. These terms must be applied to the physical situation existing In reservoir rock. A survey of the pertinent literature from 1928 to 1956 indicates that the concept of a contact angle was applied to reservoir rock in the same way it would be applied to a flat, homogeneous surface. Attempts were made to state quantitatively the wettability of a reservoir rock in terms of a contact angle which was presumably constant at all points on the very rough and heterogeneous interior surface of a porous rock. Calhoun, et al,3-6 prepared synthetic consolidated and un-consolidated porous media in which they claimed there was a known uniform contact angle. They then showed the effects on the capillary pressure and relative permeability characteristics of varying this angle. The API Project 47 at the U. of Texas' and others' have made extensive studies of an indirect approach to the contact angle through the use of heat of wetting data. Even if successful. however, this approach also states the wettability of porous rock in terms of a contact angle which is uniform over the entirc surface. If the angle varies from one part to another on the internal surface, there is no way of determining from the measurements the area distribution of contact angles. In 1956 Brown and Fatt5 suggested that the concept of a contact angle, as applied to reservoir rock, be abandoned. This suggestion was made because it is known that the internal surface of most reservoir rocks is composed of many different minerals, cach with a different surface chemistry and a different capacity to adsorh surface active materials from reservoir fluids. Furthermore, the operation of a contact angle in determining the form of a fluid-fluid interface is difficult to picture in the very complex geometry of a pore. Brown and Fatt proposed that the wettability of reservoir rock be stated in terms of the fractional internal surface area that is in contact with water or oil. All surfaces on which there is water are called water-wet; surfaces on which there is oil are called oil-wet. The fractional water wettability is then stated as a number which represents the fraction of the internal surface that is in contact with water. A symmetrical statement can be made for the fractional oil wettability. The concept of a fractional wettability as previously stated has in its favor the recognition of the heterogeneous mineral composition of most reservoir rocks. Another point in its favor is that fractional wettability can be measured quantitatively with relative ease. Hol-brook and Bernard10 se a simple dye adsorption test to obtain fractional wettability of reservoir rocks. Amott11 uses a combination of imbibition and displacement to arrive at a wettability index of reservoir rocks which seems related to fractional wettability in the range 0.25 to 0.75 fractional water wettability. Jennings" has shown the changes in relative permeability that take place when a porous material is changed from unity to zero fractional water wettability. He also shows that reservoir rocks in their natural state, but at room temperature and atmospheric pressure, have relative permeability characteristics which would indi-

By A. Henry

THE manufacture of wheels of metal for locomotives and cars constitutes an important branch of the iron industry, and one closely related, moreover, to many of the conditions of railway practice, such as speed, safety of passengers, and economy of working. It has been, also, since the introduction of iron roads, a subject of constant study on the part both of engineers of construction and iron manufacturers. The car-wheels at first used in Europe had spokes of wrought iron and a hub of cast iron. Subsequently endeavors were made to make the wheels entirely of wrought iron, by forging successively the different parts which constituted the hub, spokes, and rim. By this treatment the expansion of the heated portions at the last forgings gave rise to interior ruptures in the already cold and finished parts. The metal was thus strained before use, and the wheels broke frequently in service. It was in consequence of these failures, doubtless, that the engineers of this country were led to employ exclusively wheels of cast iron. The railway companies are nevertheless greatly interested in the reduction of the weight of rolling stock, while preserving abundant strength, and by the employment of wrought-iron wheels one may attain this double end if the defects of manufacture which we have just mentioned are avoided. This may be accomplished by making the wheels in such a manner that the different parts are welded at the same time, whereby the interior strains which so frequently give rise to ruptures in wheels successively forged are avoided. This result has been attained by what is known in France as the Arbel process, of which I will give you a short description if you will kindly give me a few minutes' attention. The process may be briefly summed up as follows : A pile of puddled bars of the general form of the wheel to be made is prepared,

Jan 1, 1877

By Adolph Henry

The manufacture of wheels of metal for locomotives and cars constitutes an important branch of the iron industry, and one closely related, moreover, to many of the conditions of railway practice, such as speed, safety of passengers, and economy of working. It has been, also, since the introduction of iron roads, a subject of constant study on the part both of engineers of construction and iron manufacturers. The car-wheels at first used in Europe had spokes of wrought iron and a hub of cast iron. Subsequently endeavors were made to make the wheels entirely of wrought iron, by forging successively the different parts which constituted the hub, spokes, and rim. By this treatment the expansion of the heated portions at the last forgings gave rise to interior ruptures in the already cold and finished parts. The metal was thus strained before use, and the wheels broke frequently in service. It was in consequence of these failures, doubtless, that the engineers of this country were led to employ exclusively wheels of cast iron. The railway companies are nevertheless greatly interested in the reduction of the weight of rolling stock, while preserving abundant, strength, and by the employment of wroughtiron wheels one may attain this double end if the defects of manufacture which we have just mentioned are avoided. This may be accomplished by making the wheels in such a manner that the different parts are welded at the same time, whereby the interior strains which so frequently give rise to ruptures in wheels successively forged are avoided. This result has been attained by what is known in France as the Arbel process, of which I will give you a short description if you will kindly give me a few minutes' attention. The process may be briefly summed up as follows: A pile of puddled bars of the general form of the wheel to be made is prepared,

By J. J. Rutledge

On Sept. 4, 1914, Mine No. 1 of the Union Coal Co., Adamson, Oklahoma, suddenly caved, entombing thirteen miners whose bodies were never recovered. The seam of coal mined, the Lower Hartshorne, averaged 5 ft. in thickness and dipped at an angle varying from 22" to 30n. The strata overlying the coal seam were sandstones and shales. The mine was worked by the pillar-and-room method, the rooms being driven directly up the dip of the seam. All coal was blasted off the solid. Rooms were turned on short centers and room pillars were thin and irregular, as shown in Fig. 1. Fig. 2 is a cross-section of the form; showing the mine workings. Some cracks had been observed on the surface, it is said, at least a month before the squeeze occurred, but the collapse of the mine workings came very suddenly. As is usual when squeezes occur on such steep dips and the pillars fail, the crush progressed rapidly down the dip until it reached solid coal; there was a line of break, or draw, over in the solid coal. Several well-defined cracks appeared on the surface, after the mine had squeezed, but there was no appreciable subsidence of the surface, the weight seemed to be thrown entirely to the dip. About one year after the squeeze, and after the workings of the adjoining mine, NO. 4, had been retimbered and made safe, the writer inspected the tenth north (right) entry, or lift, off of No. 4 slope, which was below and fairly near the lowest caved portion of mine No. 1. The roof shale was composed of thin layers, which had been bent in somewhat the same manner as the leaves of a book having flexible covers are bent when the book is folded or rolled up in the hands. Though the mine workings are immediately beneath the streets and buildings of the mining town of Adamson, business was not disturbed by the squeeze, so far as any subsidence of the surface was concerned. No surface monuments were available and no elevations were taken, but the mine workings had been accurately surveyed and traversed, and the streets of the town overlying the mine workings had been carefully platted on the mine map, so that it was possible to locate accurately the cracks on the surface.

Jan 1, 1923

By J. J. Rutledge

On Sept. 4, 1914, Mine No. 1 of the Union Coal Co., Adamson, Oklahoma, suddenly caved, entombing thirteen miners whose bodies were never recovered. The seam of coal mined, the Lower Hartshorne, averaged 5 ft. in thickness and dipped at an angle varying from 22" to 30n. The strata overlying the coal seam were sandstones and shales. The mine was worked by the pillar-and-room method, the rooms being driven directly up the dip of the seam. All coal was blasted off the solid. Rooms were turned on short centers and room pillars were thin and irregular, as shown in Fig. 1. Fig. 2 is a cross-section of the form; showing the mine workings. Some cracks had been observed on the surface, it is said, at least a month before the squeeze occurred, but the collapse of the mine workings came very suddenly. As is usual when squeezes occur on such steep dips and the pillars fail, the crush progressed rapidly down the dip until it reached solid coal; there was a line of break, or draw, over in the solid coal. Several well-defined cracks appeared on the surface, after the mine had squeezed, but there was no appreciable subsidence of the surface, the weight seemed to be thrown entirely to the dip. About one year after the squeeze, and after the workings of the adjoining mine, NO. 4, had been retimbered and made safe, the writer inspected the tenth north (right) entry, or lift, off of No. 4 slope, which was below and fairly near the lowest caved portion of mine No. 1. The roof shale was composed of thin layers, which had been bent in somewhat the same manner as the leaves of a book having flexible covers are bent when the book is folded or rolled up in the hands. Though the mine workings are immediately beneath the streets and buildings of the mining town of Adamson, business was not disturbed by the squeeze, so far as any subsidence of the surface was concerned. No surface monuments were available and no elevations were taken, but the mine workings had been accurately surveyed and traversed, and the streets of the town overlying the mine workings had been carefully platted on the mine map, so that it was possible to locate accurately the cracks on the surface.

Jan 1, 1923

INTERNATIONAL GEOLOGICAL CONGRESS. (For further particulars apply to the Secretary, 12th International Geological Congress, Victoria Memorial Museum, Ottawa, Canada ; cable address, Geocong, Ottawa.) The Coal Resources of the World.-Three quarto volumes of about 400 pages each, 8 1/4 by 10 3/4 in., and an atlas of about 70 maps in colors, 13 1/3 by 19 1/2 in., bound in heavy paper cover. Edition limited to 3,000 copies, One thousand copies will be reserved for members of the International Geological Congress, and the remainder of the edition will be distributed in the order in which applications are received. Price, $35 per set. Ready in July, 1913. This book is an inquiry made upon the initiative of the Executive Committee of the Twelfth International Geological Congress, with the assistance of geological surveys and mining geologists of different countries, published by: Morang & Co., Ltd., Toronto, Canada. Headquarters During Session at Toronto. The headquarters will be a t the University of Toronto, where there will be a branch post-office open at all hours and at which registered mail may be received or despatched, money orders sent or cashed, etc. A hank will be established at which money may be exchanged. A typewriting service will be maintained, also a telephone service and messenger service. Railway and steamship agents will also be in attendance. A restaurant service providing luncheon in the middle of the day will be arranged.

Jan 8, 1913

By Joseph Newton

MUCH the same story can be told about the copper industry for the year 1944 as for the three preceding years. Operators report few or no technical changes at their plants and the main endeavor has been to maintain high production with existing equipment. No large new installations have been made to increase plant capacities and apparently over-all copper production has passed its maximum. The present decline in copper production results partly from the severe labor shortage. As is true of most industries; the outstanding fact about the copper industry during the past few years has been its tremendous and sustained production which has been maintained in spite of serious shortages in material. labor, and technical personnel. The figures in Table I give a concrete example of how production has been increased at one large smelter in the United States-the Garfield plant of the American Smelting and Refining Co. at Garfield. Utah. These figures, reported by W. G. Rouillard. superintendent. give the production of the Garfield plant for the five years 1940-44 inclusive. The total blister production

Jan 1, 1945

By J. Norman Bulkley

As electrical power is used to a greater extent on the Rand than in any other mining center, it is thought that a short description of the methods used and results obtained may be of interest. In comparing Rand practice with that on other fields, several general factors should be borne in mind: First, the mines are all working on large tonnages of low-grade ore (average $6.50). The annual crushing rate is about 27,000,000 tons. Second, the mines are all grouped under the financial and engineering control of mining houses, so that the results of a group, rather than an individual mine, are open for study, and practice follows more uniform lines. Third, coal of fair quality (about 12,000 B.t.u.) can be obtained for $2 to $3 per ton. Good supplies of condensing water are, however, scarce, and have to be carefully stored. Power Supply Power is supplied by the Victoria Falls & Transvaal Power Co., Ltd., and its subsidiary, the Rand "Mincs Power Supply Co. Both companies, which are practically one from an engineering point of view, operate the following stations, all fecding into the same system. Capacity Installed Turbo Capacity Installed Steam-Tur- Station Alternators bine Dliven Centrifugal Compressors Brakpan............... Two 12,500-kw. sets Two 3,000-kw. sets Simmer Pan............... Six 3,000-kw. sets Rosherville................ Two 11,000-kw. sets Six 3,500-kw. machines Five 9,600-kw. sets Three 7,000-kw. machines Verckniging ............. Two 9,600-kw. sets Two 12,000-kw. sets 162,200-kw. sets Total steam-tkbine capacity installed, 204,200 kw. There are also at the Robinson Central air station six motor-driven centrifugal compressors, each of 3,500 kw., equal to 22,000 cu. ft. per minute at 120 Ib. capacity at 3,000 r.p.m. Power is supplied from these stations as 50-cycle, three-phase current generally at 40,000 volts,

Jan 1, 1916

By R. C. Allen

About four years ago the writer proposed a revision of the correlation of the Huronian formations in Michigan, and noted the bearing of the question on the correlations of the Huronian rocks in Wisconsin and Minnesota.1 Dr. C. K. Leith opposed this revision and argued for the retention of the correlations of the United States Geological Survey, published in 1911,2 for which he and Dr. Van Hise were mainly responsible. As late as June, 1917, Harder and Johnson, following Leith, thought it "premature to change radically a correlation based on years of careful field work."3 The work of Wolff on the Mesabi and Cuyuna Ranges, of Hotchkiss on the Gogebic Range (unpublished), and of the writer and assistants on the Michigan ranges, together with data developed by exploratory and mining operations, has introduced so many new facts not recognized in the scheme of the U. S. Geological Survey that the correlations of 1911 must be considered, in some important respects, obsolete. Indeed, new data are accumulating so rapidly that any classification, which for the moment may seem best to explain the facts, is almost immediately modified or refined by further observations. The problem of Huronian correlations is difficult, but interesting and important. With the aid of fossils, stratigraphers of the post-Algonkian formations have been able to show that slight disconformities mag separate strata of vastly different ages, and that within physically conformable strata may be concealed a hiatus of great magnitude. In the non-fossiliferous Huronian group, minor physical breaks in the strata are only beginning to attract attention, and it is too early to discuss what bearing these will have in correlating the formations of one area with those of another, but it is safe to say that the "lost intervals" which are not disclosed by physical relationships will remain forever lost; therefore we may not hope to discover the ultimate truth concerning the

Jan 1, 1920

By James Douglas

In discussing the waste upon which hinges, or is supposed to hinge, so largely the preservation of our national resources, the conclusions reached would be more reliable if actual experience were consulted, and fewer deductions were drawn from general statements, which are often the product of the imagination. It cannot be questioned that the value of by-products has .not been sufficiently appreciated by us, and that our tardiness in recovering the useful ingredients of the escaping gas of our coke-ovens is one of the most glaring instances of shortcoming in that direction. And yet even for that sin there is some palliation in the immature condition of affiliated industries. I presume that it is admitted, without argument, that, except under very exceptional conditions, all the elements cannot be recovered from most of the ores or natural products which we treat. While it is a shame that the by-products from our coke-ovens should be dissipated, Edward W. Parker's report to the U. S. Geological Survey for 19061 supplies a fairly good excuse in justification of this appalling waste. He says (pp. 773 to 774.): " What has been already commented on in previous reports about the slowness of manufacturers to change from the better known but wasteful beehive practice to the by-product recovery method of coke manufacture is particularly emphasized in the statistics presented in this chapter. For it would appear from the table following that the construction of by-product ovens had about come to a standstill, especially when the records for the preceding five years are taken into consideration. At the close of 1901, when there were only 1,165 by-product ovens completed in the United States, there were 1,533 in course of construction, 498 of which were completed during the following year. At the close of 1902, 1,346 retort ovens were building, 293 of which were added to the completed plants in 1903. At the close of 1903, 1,335 new ovens were building and 954 of these

Jan 1, 1910

By Richard B. Moore

The successful commercial production of helium during the last few years has added greatly to its scientific interest. When the quantity of an element available for experimental purposes increases within a few years by 200,000 per cent., both public and scientific interest in the element are greatly stimulated. Before the war, probably, there was not more than 10 or 15 cu. ft. of helium in existence. The larger part of this was owned by Prof. Kam-merlingh Onnes, and was used by him in connection with his low-temperature work at Leiden. By experimental work during the war and immediately afterwards, the Canadians, under Prof. J. C. McLennan, produced about 60,000 cu. ft. of helium of various grades of purity. Up to Dee. 1, 1921, when the plant at Fort Worth was shut down because of lack of funds, there had been produced during the experimental work by the U. S. Government, during the war and afterwards. 2,300,000 cu ft. of helium averaging between 92 and 95 per cent. purity. After the new appropriation was made in 1922, the production plant was again started and at the time of writing was making about 15,000 cu. ft. of helium a day. Only three of the five units were being operated because of the inability to get sufficient gas to run at full capacity. The gas supply is owned by two companies and on account of a disagreement between them, it has been possible for some time to get gas from only one. It is expected that when all five units are running steadily, the daily production will be between 30,000 and 40,000 cu. ft. of gas averaging from 93 to 95 per cent. purity. All three experimental plants used during the war have been shut down. The Air Reduction plant, using the Claude system, and the Linde

Jan 1, 1923

By Richard B. Moore

The successful commercial production of helium during the last few years has added greatly to its scientific interest. When the quantity of an element available for experimental purposes increases within a few years by 200,000 per cent., both public and scientific interest in the element are greatly stimulated. Before the war, probably, there was not more than 10 or 15 cu. ft. of helium in existence. The larger part of this was owned by Prof. Kam-merlingh Onnes, and was used by him in connection with his low-temperature work at Leiden. By experimental work during the war and immediately afterwards, the Canadians, under Prof. J. C. McLennan, produced about 60,000 cu. ft. of helium of various grades of purity. Up to Dee. 1, 1921, when the plant at Fort Worth was shut down because of lack of funds, there had been produced during the experimental work by the U. S. Government, during the war and afterwards. 2,300,000 cu ft. of helium averaging between 92 and 95 per cent. purity. After the new appropriation was made in 1922, the production plant was again started and at the time of writing was making about 15,000 cu. ft. of helium a day. Only three of the five units were being operated because of the inability to get sufficient gas to run at full capacity. The gas supply is owned by two companies and on account of a disagreement between them, it has been possible for some time to get gas from only one. It is expected that when all five units are running steadily, the daily production will be between 30,000 and 40,000 cu. ft. of gas averaging from 93 to 95 per cent. purity. All three experimental plants used during the war have been shut down. The Air Reduction plant, using the Claude system, and the Linde

Jan 1, 1923

By E. R. Morgan

A series of manganese-rich ferromagnetic alloys has been studied. The alloys are based upon an interstitial solution of carbon in manganese. In each of the systems investigated, the ferromagnetic phase was found to be face-centered-cubic in structure. This magnetic phase is based upon the composition (Mn, X)4C; where X is a metallic element which has both a positive size factor with respect to manganese and a high positive valence. Typical elements of this type are aluminum, indium, and tin. Preliminary magnetic measurements indicate that the effective magnetic moment of manganese in the alloys is at least 1.0 Bohr magneton per atom. It is emphasized that the critical atomic separation beyond which ferromagnetism can occur will be governed by the electronic configuration of the manganese atoms. Lattice parameter measurements show that the ferromagnetic condition in the present alloys is associated with an increased atomic separation of only 3 to 6 pct compared with a hypothetical face-centered-cubic lattice of pure manganese. MANGANESE which is paramagnetic and not ferromagnetic in the pure state can become ferromagnetic if suitably alloyed. Under favorable conditions manganese can have an effective ferromagnetic moment of the order of 3.41,2 or even 4.0 compared with a moment of 2.2 Bohr magnetons for iron. The incidence of ferromagnetism is believed to be controlled by the degree of atomic separation.4,5 This is consistent with the fact that the atomic separation, when considered in terms of the ratio of the atomic diameter R to the diameter r of the 3d-shell, is larger in the ferromagnetic metals. The values of R/r calculated by Slater,' for metals of the iron group are given in Table I, and Slater has suggested that the critical ratio of R/r is 1.5. Consideration of the criterion of atomic separation alone would suggest that there are three classes of possible ferromagnetic manganese alloys: 1— Ordered structures, of either solution or compound types, such that manganese atoms are not near neighbors; 2—Structures in which the separation of near-neighbor manganese atoms is sufficiently increased by the presence of suitable solute atoms; and 3—Dilute solutions of manganese. Typical ferro- magnetic alloys of types 1 and 2 are the Heusler alloys and Mn4N, respectively. There are no recognized ferromagnetic alloys of type 3. In view of the proximity of the ratio R/r for manganese to the critical ratio of 1.5, the present work was concentrated on manganese-rich alloys rather than on ferromagnetic alloys of low manganese content, several examples of which are already known. Calculation of the distance of closest approach of manganese atoms in each of its allotropic forms, Table 11, indicates that the high temperature ? phase provides the most suitable basis for ferromagnetic alloys of high manganese content. However the high temperature forms of pure manganese cannot be retained on quenching, although a face-centered-tetragonal form apparently can be produced by electrodeposition. Since the critical separation which must be exceeded in order to obtain ferromagnetism is dependent upon the number of electrons in the d-shell, no exact critical value of R/r can be assumed. Not only will this separation vary from one pure metal to another, but it will also vary with the valency of the given type of atom when it is in an alloy. Raynor8 has shown that metals of the iron group probably

Jan 1, 1955

By AIME AIME

I would like to ask Bob Merrill whether he considers that horizontal concave curvature of a slope has any stabilizing effect, such as Jenike 1 suggested several years ago. The stabilizing effect is due to the restraint offered to radial movement by the curvature. We found in laboratory tests that if we constrained the rock with the same stresses as those measured in the pit then it would sustain a maximum stress about two or four times greater than when the same rock type was unconstrained. We are therefore definitely of the opinion that a constrained situation in a slope is favorable towards stability.

Jan 1, 1967

By L. F. Rooney

In June 1964 the Indiana Geological Survey discovered gypsum beds more than 10 ft thick in rocks of Devonian age in La Porte County, Ind. Although the extension of the Michigan Basin evaporites into northern Indiana has been recognized for some time, the gypsum beds have been regarded as either too thin or too deep for exploitation. Current Survey research, however, indicates that exploration by industry might find commercial deposits of gypsum less than 50 miles from Chicago. In four cores taken by the Survey within 1 sq mile in La Porte County, the maximum thickness of inter-bedded gypsum and anhydrite is 35.8 ft. Both gypsum and anhydrite beds contain irregular masses of limestone and dolomite that average a few inches in cross section and total about 20% of the rock by weight. The maximum thickness of gypsum in one minable unit verified by core is 12.5 ft, and its purity is 81.3%. Chloride content of the gypsum beds is less than 0.005%. Depth to the gypsum in La Porte County is 330 to 500 ft, about the same depth as the gypsum being mined in Martin County, Ind. In June 1964 the Indiana Geological Survey discovered gypsum deposits of probable commercial thickness near La Porte, Ind. (Fig. 1). This article presents preliminary data on the distribution, thickness, depth and chemical composition of the gypsum, the possible causes of gypsification, and economic considerations of immediate interest to industry. Because of the preliminary nature of the work, only a few geologic relationships concerning the genesis of the deposits will be mentioned. DEFINITIONS The following terms used throughout this article have been restricted to the following definitions: evaporites: anyydrite (CaSO4) or gypsum (CaSO4 . 2H2O). minable evaporites: any evaporite unit which may contain more than 80% evaporites, which is more than 10 ft thick, and which in places may be completely gypsified. PREVIOUS WORK The presence of gypsum and anhydrite in the Devonian rocks of northern Indiana has been recognized for at least 70 years1-4 and can be inferred from a number of reports on the geology of Michigan. For example, in a cross section from southwestern to central Michigan, Ells5 indicated the presence of

Jan 1, 1965

William B. Phillips, Birmingham, Ala.: The analysis of Pratt coal made by myself, and given by Mr. Ormsbee in his paper (p. 113), is likely to mislead the reader as to the real nature of this coal. It represents the very purest coal that I have been able to get, and does not represent the average composition of the lump-coal as prepared for market. I wish it were true that the coal had no more than 2.50 ash and 0.83 sulphur. The analysis of McCalley is nearer the real figures than any of the others. There is no use in giving an

Jan 1, 1896

By J. E. Dutrizac, R. J. C. MacDonald, T. R. lngraham

When sintered disks of synthetic chalcopyrite (CuFeS2) were leached in acidified aqueous solutions of ferric sulfate, the following reaction stoichiometry was obtained: CuFeS2 + 2Fe2(SO4)3 = CuSO4 + 5FeSO4 + 2S Over the temperature range from 50º to 94ºC, the reaction displayed parabolic kinetics. The parabolic rate constant for the dissolution of copper is given by the equation: log.k(mg2/cm4-hr)= 11.850 - 3780/T The activation energy for the dissolution process is 17 ± 3 kcal per mole. The parabolic kinetics have been attributed to the progressive thickening of a sulfur film on the surface of the chalcopyrite. When the leaching solutions contain less than 0.01 molar Fe+3 , the Fe concentration influences the rate of leaching, probably through a mechanism involving the diffusion of ferric sulfate through the sulfur layer. At higher Fe+3 concentrations, the rate control in the leaching. reaction has been attributed to the diffusion of ferrous sulfate through the sulfur. The rate of reaction is insensitive to changes in acid concentration and in disk rotation speed. ThE reaction of acidic ferric sulfate solutions with various sulfide minerals is of practical interest for both bacterial and heap leaching. This leaching medium is generally used with low-grade ores that cannot be treated profitably by conventional means. In both bacterial leaching1-3 and heap leaching, the active agent for sulfide dissolution is ferric sulfate. Although the reactions of ferric sulfate with chalcocite, covellite, and bornite have been investigated,4*7 the kinetics of leaching chalcopyrite with ferric sulfate have not been thoroughly studied. This paper reports a study of that reaction. EXPERIMENTAL Reagent-grade sulfur was purified by the method of Bacon and FanelliB and then it was vacuum-distilled to remove any soluble magnesium salts that had been introduced during the purification procedure.9 From stoichiometric quantities of the purified sulfur and hydrogen-reduced electrolytic copper sheet (99.90 pct Cu), CuS was synthesized at 450°C in a vacuum-sealed, pyrex vessel. About 24 hr was required for the completion of the reaction. A similar procedure involving hydrogen-reduced iron wire (99.90 pct Fe) was used to synthesize FeS1.002. A 2-furnace arrangement was required. The iron was heated to 800°C while the sulfur was maintained at about 400°C. Although the reaction to consume the sulfur was rapid, the material required additional heating (1 week) in a sealed silica ampoule at 800°C before it was homogenized. X-ray powder diffraction analysis confirmed that the copper sulfide was covellite and that the iron sulfide was troilite. The composition of the iron mineral was confirmed by wet chemical analysis. The two sulfides were ground to minus 100 mesh, weighed in equimolar amounts, mixed thoroughly, and pressed into pellets at 80,000 psi. The pellets were vacuum-sealed in pyrex ampoules and then sintered for 3 days at 550°C after an initial heating at 450°C for a few hours. The pellets were then cooled, polished with 3/0 emery paper, rinsed in acetone, and stored. The material had the characteristic brassy color of chalcopyrite and was shown by X-ray diffraction to be CuFeS2. Microscopic examination of the polished surfaces revealed small inclusions of pyrite (approximately 0.5 vol pct) as the only impurity. The presence of small amounts of a second iron compound will not alter the amount of dissolved copper but might increase the amount of ferrous ion slightly. It was calculated that dissolution of all of the pyrite and 100 mg of Cu (a typical value) would change the expected ferrous concentration by only 4 pct. Microscopic examination of a pellet after leaching revealed that the pyrite was not preferentially solubilized; only those pyrite grains at the surface were attacked. Hence, the pyrite is unlikely to alter the rate of copper dissolution. The chalcopyrite disks were about 1.7 mm thick and 27 mm in diam. They were about 80 pct of theoretical density, and for this reason their true reaction area was somewhat larger than the 5.8 sq cm area presented by the polished face. The disks were cemented to lucite cylinders in such a way that only the polished face was exposed. The disks were then leached by methods previously described.6,7 RESULTS AND DISCUSSION Stoichiometry and Kinetics. The initial experiments were directed to the problem of resolving the stoichiometry of the leaching reaction. Disks of CuFeS2 were leached at 80°C for various periods of time in acidified ferric sulfate solutions that were protected from oxidation by a cover of flowing nitrogen. When the disks had been partly leached, they were removed, their soluble salts were washed out, and then they were treated with CS2 in a Soxhlet extraction apparatus. The ratio of elemental sulfur to dissolved copper thus obtained was approximately 2 to 1. After the extraction of elemental sulfur from the pellet, the residue consisted of unreacted chalcopyrite only. For runs in which an appreciable amount of copper was dissolved, the ratio of ferrous ion to cupric ion in the solution was

Jan 1, 1970

By Edward W. Parker

At the Cleveland meeting of the Institute, October, 1912, I had occasion to call attention to the general though erroneous impression that the principal mining activities of the United States lie west of the 100th meridian of longitude. Few, I believe, realize that the States east of the Mississippi river, which comprise only 28.8 per cent. of the total area of the United States, exclusive of Alaska, contribute about two-thirds of the total mineral production, computing by values. In 1910 the percentage of the production credited to the Eastern States was 67; in 1911 it was 65. When I have, with becoming modesty, ventured to speak of these comparisons, I have usually been met with the rejoinder, " But you include coal." I surely do, for whereas coal (m petroleum, as natural gas, as limestone) is not in the strictly technical definition of the word, a " mineral," it is legally mineral, is certainly a mineral substance, and contributes by far the largest tonnage and approximately one-third of the total value of all mineral products. The production of coal-mines in 1911 weighed approximately 500,000,000 tons. In 1912 it exceeded that record by nearly, if not quite, 50,000,000 tons. According to H. D. McCaskey, of the U. S. Geological Survey, the total weight of all the metallic ores mined in the United States in 1911 was 105,000,000 tons (a little more than one-fifth that of coal). In 1910 Mr. Lindgren estimated the total weight of all metallic ores at 120,000,000 tons. The products of the quarries, clay-pits, oil-wells, phosphate-mines, and other non-metallic products, taken all together, did not in 1911 weigh in excess of 300,000,000 tons, so that the output of coal exceeds by 25 per cent. the combined tonnage of all other mineral products. The coal-mines give to

Jan 1, 1914

By Alfred H. Bell

The year 1937 has been outstanding in the history of the Illinois oil industry. During the course of the year the state's daily production has been trebled, increasing from 12,000 bbl. per day at the beginning to 37,000 bbl. per day at the end, and the year's total, 7,426,000 bbl. is 66 per cent above the previous year's production of 4,475,000 bbl. The production in January was 368,000 bbl.; in December it was 1,085,000. Production from the old fields increased slightly. Most of the new production is from fields in the central part of the Illinois Basin, an area that for many years was considered unfavorable to the occurrence of oil and gas. The principal producing horizon of the new fields is the McClosky "sand," an oolitic limestone in the Ste. Genevieve formation of lower Mississippian age. Although development has not yet gone far enough to permit accurate estimates of oil reserves in the new fields, it is believed that they are of the order of 100,000,000 barrels. The following are the oil fields discovered in 1937 listed in order of amount of daily production at the end of the year; Noble (Richland County), Clay City, including Southeast Clay City (Clay and Wayne counties), Patoka (Marion County), New Centralia (Clinton County), Olney (Richland County), Cisne (Wayne County),.Beecher City (Fayette County), and Rinard (Wayne County). One gas field, the Russellville, in Lawrence County, was discovered in 1937. For locations of the new fields see Fig. 1. A generalized geologic column for Illinois, showing producing horizons in the new fields, is given in Fig. 2. The total productive area of the new fields at the end of 1937 was 1712 acres, in which 230 wells were producing. Thisrty-five dry holes were drilled within 1/4 mile of producing wells. At the end of the year there were 19 drilling wells, 28 rigs standing, 18 rigging up and 4 new locations in these fields. In the whole state 447 wells were completed, of which 284 were oil producers and three gas producers. Total initial daily production of

Jan 1, 1938