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By L. S. Darken

IN the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be repre-sented satisfactorily by the simple equilibrium expression K - (p1)p1 (p2)p2 . (R1)r1(R2)r2 . where (P) denotes the concentration of a product and (R) the concentra-tion of a reactant in the reaction r1R1 + r2R2 + . . . Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a com-ponent is not proportional to its true mol fraction, But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple com-ponents and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satis-factorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature as ionization or the occurrence of polar and nonpolar molecules-are presumably less effective in metal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By Giovanni B. Barla, Stefan H. Boshkov

The block caving method is examined in this paper on the basis of experimental results and observations in the field, and through the use of numerical modeling by the Finite Element Method. The Grace Mine, developed by a panel caving method, served as a reference case. However, the results obtained and the simulation techniques which have been developed may find useful application in more general conditions as encountered in other mining operations by block caving. Following a brief description of the Grace Mine and of the mining method, the problems associated with the behavior of underground drifts at the production levels, during undercutting and caving, are addressed. The most important results obtained through monitoring of strains and loads in the supports of a runway are discussed, while giving relevance to the sequence of mining operations in the immediate vicinity. The most important geomechanical data, as provided for subsequent modeling, are described with reference to: (a) rock mass characterization and (b) in situ state of stress. Then, the numerical modeling procedures, developed by the Finite Element Method in order to predict the caving phenomena and the behavior of underground openings during undercutting, are discussed. Finally, an attempt is made to compare the pre- dictions of the numerical analyses with, the measurements carried out at the instrumented site. Suggestions as to how to improve the results both qualitatively and quantitatively are also given.

Jan 1, 1984

By R. H. Cox, A. S. Allen, James Paone

The southwestern Illinois communities of Belleville and Maryville lie within the greater metropolitan area surrounding St. Louis. Missouri. They also lie within that part of the Illinois coal basin where the Number 6 coalbed has been mined for more than a century. About half the coal was left as pillars to support the ground surface. Years later, however, damaging movements are affecting buildings, streets, and public utilities in some areas. They are generally believed to be related to abandoned mine workings. The threat of continued or increasing incidence of damage raises the need to explore other subsidence-control measures for protecting affected areas with high population density. Because of experience gained in a subsidence-control program of backfilling abandoned coal mines in the Applachian region and in Rock Springs, Wyoming, the Bureau of Mines was called upon to investigate the subsidence occurrences at Belleville and Maryville, and recommend protective measures. Funds ware appropriated for the Bureau to initiate subsidence-control projects at two residential sites in Belleville and one in Maryville. Subsurface investigation of the sites by diamond core drilling revealed two conditions that differ from those encountered at most sites of previous subsidence-control projects. The mine workings were found to be dry and the mine floor consisted of soft underclay which characteristically loses strength with increase of moisture. It had been anticipated that water would have percolated into the mine workings at one .or more of the sites through cracks resulting from subsidence. Under such conditions Bureau engineers believed that injection of mine waste by the pumped; slurry technique3 would provide support and stabilize any movements initiated by the softening of the clay. With discovery that the underclay deposits at the three sites have apparently not been exposed to water since the mines were operating, hydraulic backfilling of any type was considered inadvisable on the basis of present knowledge. To avoid introducing water, a portable pneumatic system is being devised for injecting minus 0.01 27 m (1/2 in.) mine waste into the mine workings. Machines for pneumatic backfilling have been used in Europe not only for subsidence protection but also for strata control, for reducing spontaneous combustion and methane accumulation, and as a means of waste disposal. The Bureau experimented with a pneumatic machine in the Northern anthracite field of Pennsylvania in the 1950's. Previously pneumatic machines have been installed in active mine workings discharging from horizontal pipelines which conveyed air- borne material into rooms to be filled. In the present adaptation to abandoned mines, the machine and air compressor will be operating at the surface, to impel material vertically down injection boreholes with sufficient air pressure to disperse fill material laterally in mine workings at the base of injection holes. Large diameter access and ventilation boreholes will be provided at one site for entry into mine workings to observe backfilling progress. The Belleville and Maryville projects are part of the Mined Land Demonstration Program of the Bureau of Mines. The Illinois State Geological Survey and Department of Mines and Minerals are furnishing technical support.

Jan 1, 1979

By E. D. Gardner

The Synthetic Liquid Fuels Act (58 Stat., 190; 30 U.S.C. Sup., Secs. 321- 325) was approved by Congress April 5, 1944; it directed the Bureau of Mines to build demonstration plants to produce synthetic liquid fuels from coal, oil shale, and agricultural products. The most important oil-shale de- posits in the United States are in the Green River formation of Colorado, Utah, and Wyoming. The oil shale of western Colorado generally is more amenable to exploitation, more persistent, and apparently richer than elsewhere in the Rocky Mountain Region. It occurs at the top of a high plateau surrounded by bold, nearly vertical escarpments 500 to 600 ft in height. The top 400 to 500 ft of these escarpments comprises an oil-shale measure that averages 15 gal of shale oil per ton; the bottom 70 to 100 ft of the measure, called the Mahogany Ledge, averages over 30 gal per ton. The full measure in a 1000-square-mile area is estimated to contain 300 billion barrels of shale oil;' the Mahogany Ledge is estimated to contain 100 billion barrels of oil. These estimates are based on numerous surface samples and on core-drill holes drilled by the Government and by private enterprise. The oil-shale beds are undisturbed and lie nearly horizontal. The name

Jan 1, 1949

By T. H. Aldrich

THE Aldrich Mining Co. holds under lease from the Illinois Central R. R. Co. about 14,000 acres, in the East half of Township 12, Range 12 `V., in Marion county, Alabama, and owns other lands, of which about 1,000 acres adjoin this leased tract, making a total area of about 15,000 acres, all of which is underlain by the coal-seam upon which the company is operating. This seam is nearly horizontal ; and a ravine, diagonally crossing the tract, exposes the outcrop on either side for about 2 miles. The territory has been so divided that nearly the whole of it can be worked out by two collieries. The mines at Brilliant were opened in the Fall of 1898, and shipments began in the following spring. The original plan was to furnish steam-coal for locomotives to the Illinois Central R. R. Co.; and upon this expectation the investment of capital was made. The field was entirely new; and the softness of the coal at the outcrop induced the belief that it could be very cheaply mined. A contract for the delivery of a large quantity of coal to the railroad was accordingly executed. But with the advance of the entries to increasing distances from the outcrop, the coal proved so hard that it could no longer be drilled with a breast-auger; and the expense of mining became so great that the contract for cheap steam-coal had to be cancelled. It became evident that the work must be done with machinery and explosives, if it could be profitably done at all. On the other hand, the excellent quality of this coal opened, at the same time, a possible market not specially contemplated at the outset-namely, that of a first-rate coal for domestic and general uses. Since no other deposit of such coal was known to exist on the line of the Illinois Central, or any other railroad

Jul 1, 1906

By Albert Hill Fay

IN giving a sketch of the geology and mining of the tin-deposits of Cape Prince of Wales, a short description of the geographic and climatic conditions may be of special interest on account of this being a part of the world of which very little is known, even by the reading public. As shown in Fig. 1, the location of the Cape is lat. N. 65° 35' and long. W. 168°. It is bounded on the north by the Arctic ocean ; on the west by Bering strait and on the south by Bering sea. It is the western-most point of the mainland of North America, and to the west, across the strait, one can see East Cape, Siberia, which consists of a rugged, steep coast of granite cliffs. The climatic conditions are of interest because of the part they have had in the surface geology, and also because they affect mining from an economic standpoint. In connection with the climate and geography, it does not seem out of place here to quote a few lines from the prologue of The Wandering Jew, written by Eugene Sue, under the caption '1 The Land's End of Two Worlds."

Sep 1, 1907

THE shipments of high-grade manganese ore, con-taining 35 per cent or more of manganese, from the mines in the United States in 1926 were slightly less than half as large as similar shipments in 1925, accord-ing to the United States Bureau of Mines, Department of Commerce. The shipments in 1926 by 45 producers amounted to 46,258 long tons as compared with 98,324 long tons by 42 producers in 1925. This decrease was due to the falling off of the shipments from Montana. The domestic production of metallurgical ore in 1926 was 26,530 tons; that of chemical ore, 19,728 tons. Montana was the largest shipper with 5713 tons of metallurgical ore and 17,904 tons of chemical ore. The largest individual shipper of metallurgical ore was the Crescent Mine in the Olympic Mountain Region, Clallam Co., Washington, from which the shipments for the year were 3162 tons. The mine was operated by lessees and reverted to the owners in July, and thereafter to the close of the year no .ore was shipped.

Jan 6, 1927

By W. H. Morris

I have been requested to present a paper on the slag from the basic Bessemer process, as prepared for fertilizing. Since Professor W. B. Phillips presented at the Birmingham meeting, in May, 1888, an able paper* on this subject, as it had been developed up to that time, there is little for me to add. Perhaps later practice may be best expressed by the homely proverb, " The proof of the pudding is in the eating." As the Pottstown Iron Company is the only concern manufacturing basic Bessemer slag in this country, the writer's personal experience in the use of it may be interesting. Our slag averages: P2O5, 21.37; SiO2,, 5.10; MgO, 5.90; Al2O3, 4.01; MnO, 5.56 ; FeO, 12.00; Na2O and K2O, 0.80; CaO, 45.26; total, 100.00. This gives over 76 per cent. of phosphoric acid and lime. In using this material for several years past on my lawn and garden, I have found it better than anything else I have ever tried ; and I am sure that any of you who had seen my green grass last month (January), wherever the ground was bare from snow, as bright as in early fall, would be forced to acknowledge the advantages of this soil-enricher. The grass on my private lawn, and around the company's office, is green the whole winter; and we have raised very good sod, by the use of this phosphate, where, without it, we were unable to get the grass to grow either from seed or by repeatedly sodding. The same statement applies to garden-truck; when the soil was first broken up, a good crop of vegetables was easily raised. My own gardener has had several premiums from Philadelphia seedsmen (notably, last year, the first premium for sugarcorn raised in the first part of July, being the first sample sent them). Our method of applying this material is to grind the slag very finely, so that at least 60 per cent. of it will go through a 150-mesh screen (i.e., say, 22,500 meshes to the square inch), and 90 per cent. through a 100-mesh screen (i.e., 10,000 meshes to the square inch). This fine grinding seems to be the main condition of success.

Jan 1, 1893

By David B. Reger

Extensive drilling for gas and increased pipe-line building were the major petroleum activities in West Virginia during 1937. According to the West Virginia Department of Mines, 1034 permits to drill were issued. A running account of operations from trade journals and other reports shows that 1041 wells were drilled, resulting in 193 oil wells with 1238 bbl. of daily production; 680 gas wells with 1,048,057,000 cu. ft. of daily open flow; and 168 dry holes. The new oil-well average is 6.4 bbl. per well per day; the gas-well average is 1,541,260 cu. ft. per well per day; the ratio of dry holes to completions is 16.13 per cent. Very little attempt was made to develop new supplies of oil. Because of the continued low price, operators evidently considered it good business to leave oil in the ground rather than to produce it at a loss or on a small profit basis. The principal oil wells completed, by counties, are: Calhoun, 16; Clay, 10; Pleasants, 17; Ritchie, 42; Roane, 16; Tyler, 13; Wetzel, 11; Wirt, 14; Wood, 13. The leading counties in gas, with the number of successful wells in each, are: Boone, 54; Braxton, 31; Cabell, 48; Calhoun, 46; Gilmer, 82; Kanawha, 134; Lincoln, 44; Ritchie, 56; and Wayne, 26. General State of the Industry In Table 1 will be found an approximate summary of oil and gas territory and reserves, oil and gas production and number of oil and gas wells. The amount of land under lease is an approximation, because the exact figures are not available through any public or private agency. The proved land and reserves represent the opinion of the writer. The oil production for 1937 is subject to revision, and the gas production for the same year is only an estimate, based on demand and supply. The number of oil and gas wells now active is also an approximation, based on previous studies, and revised for completions and abandonments. Principal, Areas of Activity In Boone County, 62 wells were drilled in various localities, resulting in 4 oil wells and 54 gas wells with 18,170,000 cu. ft. of new production.

Jan 1, 1938

By Julius Pohlman

The history of Niagara Falls, as currently told, is simple, and by that very simplicity it has been rendered plausible. AS the story runs, the Falls were once situated at Lewiston, 7 miles to the north of their present site; and, since all the rocks in this section are alternate hard and soft strata, the waters acting readily upon the soft shales caused their removal, and the overlying hard lagers, deprived of support, broke down under the weight of the large volume of water that rushed over them; and this erosive action has sent the edge of the fall more and more southward, until it now has excavated the seven-mile gorge between Lewiston and the village of Niagara Falls. (See Fig. 1.) As early as 1790" we find this theory advanced in a description of this region; and it has been practically endorsed by subsequent observers, the most prominent of whom was Prof. James Hall, the State Geologist of New York, who surveyed the Falls in 1841, and gave the most exact description of their surroundings in the publications of the State Survey.? Not until 1883 was the correctness of the accepted theory of the Falls questioned.‡ The geology of the basins of the Great. Lakes, as elucidated by Newberry,§ Speneer,ll and others, has added largely to a clearer understanding of the life-history of the Falls. The investigators have shown us that Lake Erie, as a lake, is, geologically speaking, quite young; that its valley was excavated in pre-glacial times by a series of rivers; and that the Maumee, Sandusky, Cuyaboga, Alleghany and other rivers carried the drainage of the surrounding

Jan 1, 1889

By Frederick K. Allgaier

As part of an ongoing research program, the Bureau of Mines, U.S. Department of the Interior, is monitoring surface subsidence over six longwall panels at three Utah coal mines. These sites are characterized by mining depths of 244 to 610 meters (800 to 2,000 ft .), thick and massive sandstone layers in the overburden strata, multiple seam mining, extraction heights of approximately 1.8 to 3 meters (6 to 10 ft.), and rugged surface topography. Maximum subsidence, angle of draw, timing relative to mining, horizontal strain, and rate of subsidence development are being determined and correlated with mining and geologic variables. Results to date indicate the maximum vertical subsidence over the monitored panels ranges from 0.6 to 0.9 meters (2 to 3 ft.). The major factors controlling the amount of subsidence are the panel dimensions and the status of adjacent panel mining. Only minor surface cracking at the panel ends was evident at any of the sites. In all cases, there was a time lag of several months between the start of mining and subsidence at the surface. As subsequent panels are monitored and additional data become available, better estimates of the effect of various site characteristics on the subsidence will be possible. Ultimately, improved prediction capabilities will allow mine operators in the West to evaluate the potential for subsidence-related damage which could affect the current or future land use above the mine.

Jan 1, 1982

By C. R. Knopp

Gas-oil relative permeability ratio is an important relationship in oil reservoir predictive calculations. A correlation has been developed from 107 gas-flood k/k tests on Venezuelan core samples. The correlating parameter is based on restored-state water saturation tests and' is applicable to both consolidated and poorly consolidated sandstone reservoirs. Data of the correlation show that there are no distinguishah1e differences between the mass-data groupings for the two c1assifications A procedure is recommended for running .sufficient relative. permeability analyses to compute a geometric mean of the sample group. The geometric mean is more representative of the total core, and probably the entire reservoir. For example, while only one in four of the k,,/k,., test curves agreed closely with the resultant correlation of this report, the geometric mean curves of the 16 suites (three samples or more). showed good agreetment ill three cases out of four. INTRODUCTION The gas-oil relative permeability ratio is an important, fundamental relationship in most oil reservoir predictive calculations. Predictive calculations are made to estimate future reservoir production characteristics and ultimate oil recovery. The k1,/k2, relationship is specifically needed to relate the surface gas-oil ratio to the reservoir oil and gas saturation, and to calculate the relative movement of these phases within the reservoir whenever some of the more complex driving mechanisms are present. Laboratory k1/k2, tests are not generally run as a routine analysis. Consequently, k1/k2 data often are not available when needed because the cost of laboratory work could not be justified or the need for such data had not been properly anticipated. When laboratory k1/k2, data are available, they are often very difficult to interpret. For example, wide divergence is sometimes shown in a family of k1,/k1, tests representative of the producing horizon in a single well. With these considerations in mind, a study was made to determine if a relationship might exist between the k1,/k2, curve and some other simple laboratory test criteria. The most probable k1/k2, curve correlation for Venezuela described in this paper is the result of the investigation. The presented correlation defines the most probable gas-flood k,,/k,, curve through the medium of air-water capillary displacement and centrifuge water saturation tests. The laboratory procedures of these tests are. relatively simple, and inexpensive; test data should be. widely available- from routine analysis. DATA AVAILABLE, LABORATORY METHODS The report correlation utilized 107 gas-Hood k1/k2, tests run on sandstone cores of Venezuelan reservoirs. Table 1 is a general tabulation of data pertinent to the tests, while Table 2 summarizes the data. Thetests include 96 from Western Venezuela and 11 from Eastern Venezuela. Eighty-two- of the 107 test samples were sandstones that varied from poorly consolidated to-unconsolidated; 25 were consolidated. The average sample porosity was 26.7 per cent and the average permeability was 1,121 md; these values typify the better sandstone reservoirs of' Venezuela. The Welge gas-flood technique,' based on fundamental Buckley-Leverett frontal displacement theory, was introduced in about 1952 and is widely accepted in the industry. The laboratory procedure is relatively simple, rapid, and can be performed on small core samples. While there have been some minor variations in sample preparation and laboratory procedure in the tests used for the correlation, these tests can be generally summarized as follows. The core sample was first sol vent-extracted and dried. Connate-water saturation was restored by the oil-flushing or evaporation-blow down methods. At the beginning of gas flood the hydrocarbon pore volume was completeiy saturated with the test oil phase. Unsteady-state gas-oil displacement then began with the injection of nitrogen or helium. while the displaced oil and gas phases were incrementally metered at the out-flow face. From the test data, the k,,/k,, curve was calculated by the Welge method.' The individual oil and gas relative permeabilities were also calculated." CORRELATING PROCEDURES In attempting to establish a basis of correlation, we found that broad mid-range sections of 105 of the 107 k,,/k,, test curves could be closely duplicated by a straight line. Only two curves did not show a degree of linearity in this region. Correlation-curve definition parameters were subsequently developed from this observation of consistent mid-range linearity. Possible correlating variables were limited to the physical properties measured on core samples that (1) were widely available as common test data and (2) could be easily and cheaply obtained through future laboratory work. The more obvious possibilities were porosity, permeability and

Jan 1, 1966

By Michael Tenenbaum

Selected characteristics of nonmetallic phases were determined in low-carbon sheet steels which had been produced by various refining; deoxidizing, and casting procedures. The results showed little influence of the refining process on the quantity, distribution, size, and character of the nonmetallic phases. The quantity of inclusions was governed by the deoxidation procedures. While the mode of casting influenced the internal structure and the pattern of inclusion distribution, it had little effect on the quantity of nonmetallics. The vast majority of inclusions were under 30 µ in diam, and there was little change in size distribution during hot and cold rolling. The composition and structure of the inclusions were expained an the basis of known equilibrium phase diagrams for the appropriate systems. Additional work is needed to explain some of the observations of this paper. HENRY Marion Howe's contributions to the metallurgical profession include his many writings, the wisdom that he imparted to his students, and the inspiration that he gave to the many scholars, teachers, and industrialists who knew him personally. It was Professor Howe's intimate colleague, Albert Sauveur,1 who, in the first Howe Memorial Lecture, could have been speaking for the metallurgist of our generation as well as his own when he wrote, "...how many of us on the point of going astray were called back to the right path by Howe's guiding torch?" More than a quarter of a century later, Francis Foley,2 one of the last in the Howe Lecture series who worked directly with the great man, delivered the ultimate tribute, "...truth, in its time is so hard to identify." While Professor Howe strove to be right, "he was content if he provoked the reader to take the next step along the path to greater knowledge." Like so many of my predecessors, I sought guidance for this lecture by referring to Professor Howe's two classic texts, Metallurgy of steel,3 and Metallography of Steel and Cast Iron: the former book interpreting the facts as he saw them near the start of his career, and the latter—published 26 years later—pointing to many fertile fields for metallurgical investigation. Those of us who harvest the fruits of Henry Marion Howe's contributions to the metallurgical profession now look with wonder at the tremendous legacy he has provided. It is rewarding to study his writings and to recognize the anticipation of such aspects of modern ferrous metallurgy as: 1) Direct reduction 2) Steelmaking reactions 3) The approaches and benefits of degassing 4) Solidification mechanisms 5) Habits and behavior of nonmetallic inclusions 6) Recrystallization phenomena 7) Slip and slip propagation 8) Dislocations 9) Discontinuous deformation 10) Microscopic and macroscopic segregation

Jan 1, 1970

By NEWTON B. KNOX

IN Bolivia, mining is still the principal economic activity, as it was before and during the Spanish Colonial period. Tin, tungsten, antimony, copper, lead, zinc, gold, silver, sulphur, and a little bismuth are produced. The Andes mountains are divided into two main ranges in Bolivia; the Western range marks the border with Chile and the Eastern range forms the backbone of the country; in the North it drops rather abruptly eastward, to the plains of the Beni, whereas in the South it splits and is separated from the Chaco flatlands by a series of folded mountain ranges. In general the mineral deposits are found within the Eastern range or in the hills that rise from the high plateau between the ranges - really parts of the Eastern range partly submerged by recent sediments. The mineral belt is thus over 500 miles long and about 100 miles wide and includes most of the principal centers of population and the most important means of communication. The region is mountainous and the roads are bad; furthermore labor is a serious problem, for the land is poor and the agricultural population is never far from hunger. The floating supply of miners is limited and soon exhausted in any emergency like the present.

Jan 1, 1945

Although the 71 Minerals operation is now closed down and the operating data presented is almost five years old, it is well worth describing since it was the first heap leaching operation conducted on a primarily silver ore. Tombstone was discovered in 1877 by Ed Schieffelen; and it became one of the most famous mining towns in the West through the stories connected with Wyatt Earp, Doc Holliday, and the Clanton brothers. Like many silver deposits .in the western United States, the Tombstone ores were relatively shallow. Several million ounces of silver were recovered in the relatively few years the camp was active; but mining virtually ceased by the early 1900s and was only continued in a small way until the 19409, a history similar to that of Tuscarora. The 71 Minerals operation was started in May 1975 and continued until late 1978 within the city limits of Tombstone on waste dumps; one was the' Lucky Cuss, Schieffelen's discovery, which had accumulated from the old underground operations. This waste material was mostly less than 50 mm (2 in.) in size, although there was some larger lumps. The grade was about 34 g Ag and 0.5 g Au per mt (1.0 oz Ag and 0.015 oz Au per st). The Tombstone dumps contained approximately 1,000,000 tons. The dumps and patented claims were held by a single owner, Tombstone Development Company, thus sufficient leaching material could be acquired from one source rather than dealing with a number of individuals, as is usual in putting together leaching ventures in old mining camps. 71 Minerals Ltd. was formed and a lease of the properties obtained. A site was selected close to the major mine dumps not far from down- town Tombstone. Pads approximately 90 m (300 ft) wide and 180 m (600 ft) long with an 8-degree slope were prepared using compacted old mill tailings as a base sealant on the pads. Mining was done at a rate of about 2,000 tons per day with a dozer, two scrapers, a front-end loader, and 30 ton trucks. The ore was dumped by the scrapers as it came from the dumps with no screening or crushing in 460 mm (18 in. ) layers and trimmed with the loader. Based on bulk sampling and laboratory testing, the majority of thegold and silver values were recovered within 30 days of leaching.

Jan 1, 1981

By Gerhard Derge, Harold Markus

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Harold Markus, Gerhard Derge

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

No. 264. A long established company operating steel and iron foundries, machine and forge shops, whose varied products are sold to the Government, railroads, mining and contracting industries, etc., has, openings in both manufacturing and selling departments for men with technical education and experience who are not subject to military call. State full particulars, kind of position preferred and salary expected. No. 265. Young man wanted, technical graduate preferred, to superintend construction f a small charcoal blast furnace. Man with blast-furnace experience preferred. For the right kind of man this is, not only a permanent job but an opportunity. In writing, give full particulars as to age, education, experience, salary wanted, etc. No. 26.6. An important copper mining and smelting company in Arizona needs two or three metallurgical chemists, at salaries. ranging front $150 to $175 per month. No. 267. A consulting mining engineer needs two superintendents for developing chrome deposits near Philadelphia; and another technical man for other engineering work in the same vicinity. No. 268. An iron-mining company, in New York State needs a mining engineer with knowledge of geology and acquaintance with construction work; A married man, with about 10 years' engineering experience preferred.

Jan 2, 1918

By G. M. Crosby

Seven mines with important production records in the Coeur d'Alene lie adjacent to the Gem stocks —the Frisco (Gem), Hercules, Interstate, Rex (Sixteen to One), Success (Granite), Sunset, and Tamarack. Old records are incomplete, but available data given in Table I show these mines have produced 10.550,721 tons of ore containing more than 50 million oz of silver, more than 1.5 billion lb of lead, and about 1 billion lb of zinc (approximately 1.25 million tons of lead and zinc combined). Average ore grade is 4.8 oz of silver per ton, 7.2 pct Pb, and 4.6 pct Zn. This impressive production represents about 12 pct of the District's yield. At present metal prices, with modern beneficiation, the gross value would be more than $400 million. THE GEM STOCKS The Gem stocks, considered to be outliers of the Idaho batholith of Late Cretaceous age, are located in the northern half of the Mullan quadrangle, and extend from the town of Gem, Idaho, along a strike of N30°E for a distance of approximately five miles. They occur as two major masses of monzonitic rocks commonly referred to as the North stock, which covers an area of 1.1 sq miles, and the South stock, which covers 2.6 sq miles. The areal pattern is roughly club-shaped, the North stock representing the handle and the South stock the head of the club. Two and a half miles west and five miles northeast are two groups of smaller stocks, isolated from the main masses but of the same general rock type. This discussion is limited for the most part to the North and South stocks. At the north end, where the intrusion is about 3200 ft wide, the walls are about parallel and dip very steeply west. At the south end, where the mass is about 7000 ft wide at surface, the walls dip away from each other at moderately steep angles. An aeromagnetic survey' detects and outlines with surprising accuracy the two main stocks. as illustrated on the magnetic contour map (Fig. 2). Of particular interest is the location and shape of the magnetic anomaly representing the South stock. The anomaly is centered over the south end of the outcrop, and a westerly extension joins it with a smaller anomaly over the Dago Peak stocks. The latter anomaly, likewise, is located over the south end of the isolated stocks. This pattern suggests the intrusion has greater extent at depth to the south and west. Though correlation between the Dago Peak stocks and the larger masses is suggested, the controversial aspects of the Dobson Pass fault, which separates the two areas, casts doubt on a correlation. Topographically the monzonite stocks are ignored by the drainage pattern indicating these rocks, and the invaded rocks of the Lower Belt Series react similarly to erosion. The drainage patterns of Nine Mile and Canyon creeks cut indiscriminately across the monzonite-Belt contact, resulting in both valleys and ridges in the southern end of the intrusion. Nine Mile Creek traverses diagonally the entire five-mile length of the stocks. The monzonite rocks of the intrusion are referred to locally as granite, but granite is rare and the rocks comprise a wide variety of types. Their characteristics, described in detail by F. L. Ransome and F. C. Calkins,' are summarized by P. J. Shenon.' The principal rock type is coarse-grained, light gray, porphoritic monzonite containing black crystals of hornblende. Pyroxene, epidote, and titanite

Jan 1, 1960

By J. Chipman, G. G. Hatch

T. ROSENQVIST*—It is a pleasure to see the excellent way in which the experimental part of this work has been handled. There seems to be little doubt that the distribution data obtained corresponds most closely to thermodynamic equilibrium under the prevailing reducing conditions, namely equilibrium with graphite and one atmosphere CO pressure. The desulphurization curves in Fig 10 show the same general feature as the curves given by Holbrook and Joseph, but the distribution ratios are from 20 to 40 times greater—undoubtedly due to a closer approach to true equilibrium. In the theoretical discussion, the authors calculate a theoretical distribution (S) ration -jg-. which they find to be about 50 times greater than the experimental. The deviation is so great that the basis for their calculation needs a more thorough examination. The authors base their thermodynamic calculation on free energy expressions where diluted solutions of FeS and CaS are used as standard states. (The activity coefficient in diluted solutions is taken to equal unity.) Such a standard state will change when the nature of the solvent is changed. Taking the free energy of the reaction [FeS] ? (FeS), Eq 2, which is derived from the distribution of sulphur between an iron and a FeO-melt, it is very unlikely that the free energy of this reaction will be the same for a distribution between pig iron and a calcium silicate slag. Therefore a more fundamental basis for the thermodyuamic calculations seems needed, where all thermodynamic equations are referred to unambiguously defined standard states. The most natural standard states for CaO and CaS are the pure solid substances at the same temperature. As standard state for sulphur in iron, pure liquid FeS can be used. This rules out Eq 2 [FeS] ;=s (FeS) because ?F° = 0. The standard equation will then be: FeS, + CaO6 + Cgraph ?Fei + CaS8 + CO. vFo1773 = 25,000 cal It would be more universal and also simpler to refer the escaping tendency of sulphur in liquid iron to the corresponding H2S/H2 ratio which can readily be determined experimentally. As standard state a gas mixture H2S/H2 = 1/1 can be used. (This corresponds at the temperature of liquid iron closely to one atmosphere S2 vapor.) Thus the standard equation for the sulphur reaction can be formulated as follows: H2S0 + CaO3 + Cgraph ?H2o + CaS8 + COg The standard free energy of this reaction has been calculated from the best available data to AF°m3 = —35,000 cal. This gives for the equilibrium constant at 1500°C Now, the solubility of CaS in blast furnace slags has been determined by McCafferey and Oesterle* and corresponds at 1500°C to about 10 pet S (varying somewhat with the composition of the slag.) If the activity of CaS is assumed linear between 0-10 pet as curve 1, (see Fig 11), then acaO = 0.1 (S); (S) being wt. pet sulphur in the slag. For a diluted solution of sulphur in an iron melt saturated with carbon, the ratio H2S/H2 is, according to Kitchener, Bockris and Liberman,f about 0.01 [S], [S] being wt. pet sulphur in iron. Substituting these values in the expression for Kp we find The value 2.103 is only 4 times greater than the experimental coefficient found by Hatch and Chipman, but the value is very sensitive to a small error in AF°. A better agreement with the experimental distribution coefficient can be obtained if one assumes the activity of CaS to run like curve 2 (Fig 11). This (S) will give a lower theoretical W, value, a value which varies with (S) exactly as Hatch and Chipman learned. Such a shape of the activity curve, which corresponds to a positive deviation from Raoult's law, is actually to be expected from the fact that liquid silicate and sulphide phases usually show incomplete miscibility. A closer agreement between experimental and theoretical data can not be expected before we have more complete data for the individual activities of CaS and CaO in the slag. The activities acaS and Ocao referred to the solid phases as standard states, are exact defined quantities contrary to the somewhat undefined expression "free lime," and they are independent of any theory for the constitution of liquid slag. J. CHIPMAN (authors' reply)—The authors wish to thank Mr. Rosenqvist for his very interesting and useful thermodynamic addition. Curve 2 of his figure offers the needed basis for explaining the increase in the ratio (S)/[S] with increasing sulphur content. Attention is called to an error in the printed paper: Fig 2 and 3 are reversed. M. TENENBAUM*—In the figures showing the relationship between excess base and sulphur distribution (Fig 6, 7 and 9) the slope of the curve tapers off in the negative basicity range. Somewhat the same thing is observed with open hearth slags. In that case, the fact that some sulphur distribution between slag and metal is obtained with negative basicity is interpreted as indicating some dissociation of the lime silicate compounds whose existence in oxidizing basic slags has been used to explain various observed phenomena with regard to other slag-metal reactions. In the case of the blast furnace slags, the reduced slope of the sulphur distribution curve with decreasing excess base is attributed to the amphoteric effect of alumina. Has the possibility of other explanations been investigated ?

Jan 1, 1950