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By R. G. Dressler

The design and operation of the Koppers powdered-coal gasifier and its auxiliaries at Louisiana, Mo., are described. This unit was designed to convert 1 ton of coal per hour with oxygen and superheated steam into synthesis gas - primarily carbon monoxide and hydrogen. The first run was made on May 4, 1949. After this, 44 short runs (less than 8 hours each) and 1 long run (lasting 11 days) were made. Total gasification time was 420 hours. The gasifier was not cooled down during the year when these runs were made. After an initial period of test operations and equipment proving, during which 12 runs were made, the effect of numerous variables on gasifier performance was studied. The long run was made primarily to check the equipment in sustained operation. Detailed data from these runs are presented.

Jan 1, 1954

By Katherine Mather

This paper is an attempt to put together petrographic, physical, and chemical data about the large and varied group of rocks generally called limestones. Results of the properties of these rocks on their performance as concrete aggregates are discussed. CRUSHED stone classified as limestone comprises about 70 pct of the crushed concrete aggregate and roadstone produced in this country, and the product has amounted in the recent past to about 97 million tons per year, valued at more than $123,-000,000.' Therefore an evaluation of the properties of rocks classified in these statistics as limestones and an ability to predict their behavior as aggregate in portland cement concrete are matters of considerable economic consequence to producers and consumers of aggregate. This paper is an attempt to put together petrographic, physical, and chemical data about the large and varied group of rocks generally called limestones. It also points out certain results of the properties of these rocks on their performance as concrete aggregates. The problems encountered in efforts to explain the behavior of limestones, dolomites, and related rocks as concrete aggregate lie on the frontiers between the ignorance of the geologists and the ignorance of the engineers. The mineral composition and textures of the rocks have not been adequately explored and described, and the effects of mineral composition and texture on the performance of aggregates have been worked out in only a few cases. There are instances of unsatisfactory performance and some generalizations of those experiences. There are many more examples of satisfactory performance than of unsatisfactory, but there is practically no published information as to why a particular aggregate was satisfactory in a specific use. There are all too few investigations of undeteriorated concrete; more is known about the pathology of concrete than about its normal structure and aspect. As part of the investigation of aggregates, the classification of rocks is not an end in itself, but is a step toward recognition of properties expected to influence the behavior of aggregates in their intended use. Rock of any type may perform well or poorly as concrete aggregate, depending on the physical condition of the rock, its physical and chemical properties as compared to those of the matrix in which it is placed, and the circumstances under which the concrete is exposed. Some classification and descrip- tion of the limestones is necessary to distinguish subgroups whose members will probably behave in similar ways and to evaluate the group as a whole. The group name, limestone, includes and tends to conceal the identity of rocks that have a very great range in chemical and mineralogical composition, structure and texture, conditions of deposition, subsequent history, and suitability for use as concrete aggregate. All the rocks classified as limestones include one or both of the most abundant rock-form-ing carbonate minerals, calcite and dolomite, as major constituents. Carbonate rocks is a more descriptive and more accurate group name than limestone, which has generally been used to include dol-omitic or magnesian limestones and dolomites as well as calcitic limestones. Classification and Description of the Carbonate Rocks The question of names to be applied to the carbonate rocks may appear academic, but it is of practical importance as long as there are specifications for aggregate that result in acceptance or rejection of rocks by name and as long as failure to make distinctions among the carbonate rocks leads to misunderstandings of their properties and of what may be expected of them in performance. Materials included in production statistics as limestone and tested for concrete aggregate as limestone range in fact from calcareous shale and calcareous or dolomitic sandstone and argillaceous limestone and dolomite to calcitic limestone and pure dolomite and to rocks close to calcitic and dolomitic marble. To take a simple example: consider two manufactured coarse aggregates, both dense and unweathered, one composed principally of crystalline calcite and the other of crystalline dolomite, but both known as limestone. If each is used as coarse aggregate in a standardized concrete mixture with the same fine aggregate used in both cases, made into concrete specimens, and tested in accelerated freezing-and-thaw-ing, the test results will probably be quite different, because of the differences in internal bond and thermal properties between the two aggregates. As long as both aggregates are called limestone, the test results cannot be explained, or used except in a very limited way; if the aggregates are distinguished as limestone and dolomite and the consequent differences in texture and thermal properties are recognized, the results are reasonable. Classification of the carbonate rocks used as aggregate should be based on structure and on composi-

Jan 1, 1954

By J. L. Taylor, P. Duwez

The phase boundaries in the ternary system Ti-Cr-Al have been established at 1800° and 1400°F for alloys containing more than 60 pct Ti. The martensite transformation temperature has been measured for the titanium-rich alloys. THE studies of binary alloys of titanium with the transition elements which have been published so far1-0 ndicate clearly that the solubility of these elements is always much greater in the high temperature body-centered cubic form of titanium (ß phase) than in the low temperature hexagonal form. In this category of alloying elements are iron, nickel, chromium, manganese, vanadium, molybdenum, tungsten, columbium, and tantalum. Although studies of the nontransition elements have been rather limited, early work on titanium binary alloys'" has shown that most of them were not very soluble in the a form, with the exception of aluminum, for which the solubility in a is about 25 pct.13, 12 In addition to this large solubility in a, aluminum is also soluble in ß titanium to the extent of about 35 pct and the transformation temperature from ß to a is raised with aluminum content. This effect is also typical of aluminum, in contrast with that found for the transition elements which lower the ß to a transformation temperature. Therefore, it may be anticipated that tprnarv titanium alloys with aluminum and any one of the transition elements will constitute a class of ternary alloys having characteristic features absent in alloys involving two transition elements. Chromium was chosen as a typical transition element for the present study because ternary alloys of Ti-Al-Cr commercially produced have been found to possess very interesting physical properties (MST-3 pct A1-5 pct Cr of Mallory-Sharon).'" Binary Systems The binary systems Ti-A1 and Ti-Cr have been established recently by several investigators. The data used in this investigation were taken from the complete diagram of Bumps, Kessler, and Hansen." This diagram agrees quite well with earlier investigations." For the Ti-Cr system, the phase boundaries at 1800" and 1400°F were taken from refs. 6 and 7. The binary system Cr-A1 has been studied recently by Bradley." This system is rather complex and contains not less than seven intermediate phases. The present study was limited to the titanium corner of the ternary system (less than a total of 40 pct Cr plus Al) and none of the phases present in the Cr-A1 binary alloys were found in the ternary alloys investigated. Experimental Technique Microscopic observation and X-ray diffraction measurements were used to identify phases and de-

Jan 1, 1954

By C. W. Sill

[In the original Norris and Fay method for determining selenium, selenious acid is reduced by an excess of standard thicsulfate in accordance with the following reaction: H2Se03 + 4Na2S203 + 4HC1 = Na2SeS406 + Na2S406 + 4NaC1 + X20. (1) The excess thiosutfate is then back-titrated with standard iodine solution. The disadvantages of ouch a method are obvious. On an unknown sample, the quantity of thiosutfate required would be difficult to determine; a definite excess is required, but large back titrations would be undesirable. Inasmuch as thiosulfate is decomposed by acid, considerable error may be introduced in this method, the amount depending on the acidity, temperature, concentration of excess thiosulfate, duration of contact between thiosulfate and acid, and other factors, In a critical study of the Norris and Fay method, Coleman and McCrosky3/ show that the method is accurate to less than .1 part per thousand if the excess of this sulfate Is not greater than 5 ml. of 0.1 N solution (in 1.0 ml. of 0.x4 N sulfuric acid) whether the titration is made at 0° or 20°C. A greater excess produced unsatisfactory values at either temperature. Coleman and McCrosky regulated the excess thiosulfate by adding 5-ml. portions of thiosulfate solution followed by the addition of 1 to 3 drops of 2.5 percent potassium iodide in the presence of starch. If a starch-iodine blue color formed locally around the drops of potassium Iodide, the reduction of selenious acid was not complete. On stirring the solution, the local blue color fades and another 5-ml. portion of thiosulfate is added. When addition of potassium iodide fails to produce a local blue color, reduction of selenious acid is complete, and the excess thiosulfate is then back-titrated with standard Iodine solution. The number of equivalents involved in the reduction of selenious acid by either thiosulfate or iodide is the same, and therefore no correction need be made for the potassium iodide. This procedure is much better than the original Norris-Fay titration, but acidity and time would stilt be rather critical factors subject to variation with individual technique. Also, the method still requires the lose of two standard solutions, a rather undesirable factor from the standpoint of routine application.]

Jan 1, 1954

By R. F. Domagala, M. Hansen, D. J. McPherson

On the basis of metallographic analysis, incipient melting data, thermal analysis work, and X-ray diffraction, phase relationships in the 0 to 50 atomic pct alloy content were carefully resolved. Phase relationships in the higher alloy content regions were outlined. A single intermediate phase, peritectically formed, of the form ZrX2 was established in each system. A eutectic and a eutectoid were found in the zirconium-rich region of both systems. Appreciable solubility of molybdenum and wolfram was found in ß zirconium, but only a slight solubility in a zirconium. PREVIOUS work on these systems was limited to X-ray investigations of the intermediate phases1, 2 and preliminary surveys of the zirconium-rich alloys." The diagrams presented were determined principally by metallographic, thermal analysis, and incipient melting techniques. In accordance with the Atomic Energy Commission contract requirements, phase relationships up to 50 atomic pct molybdenum or wolfram were carefully resolved, while only a limited amount of work was done to outline the 50 to 100 atomic pct alloy region. A description and analysis of the metals used in the preparation of alloys for this study are included in Table I. A "low-hafnium" zirconium crystal bar, produced by the decomposition of a volatile iodide onto a hot filament, was employed for these studies. Westinghouse "Grade 3" crystal bar was used for all alloys. The zirconium, as received, was coated with corrosion product from a standard autoclave test by which its grade designation is determined. This was removed by a sand-blasting and HF-HNO, pickling technique developed by the Atomic Energy Commission. The bars were cold rolled to approximately 1/32 in. sheet, pickled for iron removal, sheared to 1/4 in. squares, washed with acetone, and stored for furnace charge. Molybdenum sheet. 0.003 in. thick, 0.001 to 0.005 in. wolfram wire, and M in. wolfram rod crushed to granular form, from Fansteel Metallurgical Corp., were used as alloying stock. Melting Procedure A nonconsumable electrode arc furnace identical to that described in detail by Hansen et al.4 was used. The source of power for melting Zr-Mo alloys was a 400 amp dc welding generator, while a 900 amp dc generator was used for preparing Zr-W alloys. Electrode tips of the same material as the alloy addition were employed in both systems, i.e., molybdenum tips were used for Zr-Mo alloys, and wolfram tips for Zr-W alloys. This precluded any possible electrode contamination during arc melting. Ingots of 20 to 30 g of Zr-Mo alloys were melted under high purity helium in the cavity of a copper block insert in a spun copper crucible. Homogeneity was insured by remelting all ingots four to six times without opening the furnace. Due to the large difference between the melting points of wolfram and zirconium, direct melting of the charged metals as above generally yielded ingots containing unmelted wolfram particles. This was overcome, after many variations in technique, by melting a pure wolfram charge at high power levels (700 to 900 amp) and slowly adding zirconium to form a master alloy. Such master alloys were sectioned and remelted several times, then crushed to serve as melting stock for alloys of lower wolfram content. Master alloys containing 26, 50, 52, 70, and

Jan 1, 1954

By A. J. Barry

An apparatus and procedure have been developed for testing the anchorage effectiveness of slotted-type bolts. The apparatus consists of: (1) A hydrualic Jack assembly for loading the bolt and (2) a device (extensometer or cathetometer) for measuring displacement of the bolt as it is loaded. This apparatus and procedure permit measurment of anchor slip for loads up to the yield load of the bolt. Two representative makes of slotted-type bolts (a total of 94 bolts) were tested in typical sandstone and shale mine roof. Analysis of the test results showed that (1) anchorage capacities up to the yield load of the bolts can be developed in either rock type; (2) the shape of the slotted end of the bolt affects the ease with which the bolt can be driven; (3) all bolts for which the driving distance was more than 1.25 inches produced satisfactory anchorage in both rock types (thus, driving distance can be used as a criterion for satisfactory anchorage); (4) for the group of bolts that was satisfactorily anchored the anchor slip was unaffected by the type of bolt but was considerably larger in shale than in sandstone; and (5) the bolt expansion, that is, the amount the wedge expands the prongs in excess of the diameter of the hole, can also be employed as a criterion for satisfactory anchorage. Although the bolt-expansion and driving-distance results do not differ appreciably, the latter is recommended because it is easier to determine.

Jan 1, 1954

By B. M. Hamilton

"IntroductionTHE PROCEDURE and technique for drilling holes has probably undergone as great a change during the past ten years as any one of the other operations conducted in hard-rock mining. During this period, we have seen a change from the heavy leyners and drifters to the light jackleg type of drill machine; from steels that were forged and hardened on the bit end to the inserted •carbide-tipped rod, from the necessity of providing special bit-end fabrication and beat treatment of shank steels to the simple grinding or turning of a plain section on a shank with no heat treatment required for bit attachment.When the steel maker was first called upon to manufacture a hollow drill rod, it was required that the steel must not only have sufficient strength and fatigue resistance to cope with the stresses of service, but also must be capable of being heat treated on the bit end to a high hardness for resistance to wear and abrasion . Little was known at that time about alloy steels and the beneficial effects to be gained from additions of chromium, nickel , and molybdenum. So it was that the plain 0.80 per cent carbon analysis was selected, since it had already proven to be a suitable grade for chisels, hammers, and other such shock tools. This grade has long endured the test of time and is still used in considerable tonnage today, particularly by the construction industry.As the metallurgist learned more about the influence of alloying elements, a new hollow drill analysis was placed on the market in the early 'thirties'."

Jan 1, 1954

By H. A. Johansen

Recent advances in the metallurgy of chromium have enabled this metal to begin to take its place among the refractory metals. Considerable work is being done on the development of high-temperature alloys containing high percentages of chromium.1/2/ In spite of the relatively large amount of work done on these alloys, little is known of the properties of the pure metal. Information in the literature concerning the tensile properties of pure chromium metal is quite scant. This deficiency maybe explained by the great difficulty of preparing test specimens from such a brittle material, resulting in many losses in each phase of the specimen preparation and testing procedure.

Jan 1, 1954

By J. M. Harrison

"The Nor-Acme gold mine is near the shore of Snow lake, northern Manitoba, about 75 miles east of Flin Flon. The claims that form the nucleus of the present property were staked in 1927 by C. R. Parres, but it was not until 1941 that diamond drilling disclosed the potentialities of the deposit. In that year a large-scale drilling programme was begun under the direction of F. Ebbutt, of the Howe Sound Exploration and Development Company. Two orebodies were outlined containing about 5,000,000 tons of ore assaying $5.25 in gold per ton. In August, 1945, construction of the mining plant was begun.All information and interpretations contained in the following brief description of the deposit were obtained from surface mapping.GEOLOGYThe ore lies at the contact between a coarse, basic, pyroclastic rock, which is the hanging-wall, and grey, acidic lavas and sediments, which form the footwall. These rocks are cut by irregular basic intrusions that vary in composition from diorite to hornblendite, and by small acidic dykes . Tourmaline is locally common in the hanging-wall rock near the ore.The ore occurs in brecciated, silicified, and ·slightly carbonatized rock. Arsenopyrite is the main sulphide and the gold is associated with it. Pyrrhotite is locally abundant and minor pyrite, chalcopyrite, sphalerite, galena, and cubanite have been noted. Two orebodies are known, the Dick and the Toots. The Toots, which is much the smaller of the two, is about 1,000 feet west of the Dick."

Jan 1, 1954

By R. W. Smith

The Bureau of Mines has been engaged in a systematic evaluation of the thermodynamic properties of combustion gases. These studies were designed to provide basic thermodynamic information of high accuracy, facilitating the theoretical study of flame and combustion phenomena.4 This report is the fifth of a series5/ presenting results of the study for particular fuel-oxidant systems. These calculations have as their objective the constant pressure flame temperature of acetylene-air for a range of pressures.

Jan 1, 1954

By H. M. Thorne

The Union of South Africa has been interested in oil shale for a long time, and deposits of oil shales, torbanites, and similar rocks have been found in many parts of the country. (Fig. 1.) Samples differ markedly in oil yield and in the characteristics of the oil. The strata vary in thickness, and most of the deposits that have been found are in unfavorable locations because of remoteness from markets or absence of transportation facilities. This report deals mainly with the torbanite deposit near Ermelo, Transvaal, in the Union of South Africa, and the operations of the South African Torbanite Mining and Refining Co., Ltd. (hereafter referred to as Satmar), in mining the torbanite, retorting it, and refining the crude oil.

Jan 1, 1954

By Arthur B. Yates

"The nickel deposits of Sudbury, discovered in .1885, have probably commanded as much attention as any single group of orebodies in the world. They have been the major source of the world's nickel supply since 1903, when their production first surpassed that from the Pacific Island of New Caledonia. From 1903 to 1914 the production from New Caledonia remained essentially constant, whereas that from Sudbury increased from 13,000,000 to 50,000,000 pounds a year. After 1914 the production from New Caledonia gradually dropped to about 4,000,000 pounds in 1919, where it remained until 1923. During these years the Canadian production increased steadily and since 1923 has gone up at an amazing rate to a peak of over 280,000,000 pounds in 1941. Meanwhile the New Caledonia production increased to about 10,000,000 pounds until the pressure of war raised it to roughly 14,000,000 pounds a year.The Sudbury deposits, because they have been the source of 80 per cent of the world supply of nickel, because of their economic importance to the world of metals, and because they are geologically unique in their occurrence, structure, and genesis, have attracted foremost consideration and the literature relative to their geology is voluminous. This is particularly true in regard to genesis.There is a significant and interesting parallel in time between the advancement of the science of economic geology and the great expansion of the nickel industry. The controversies regarding the fundamental classification of orebodies into generalized types were in full swing during the height of the development and expansion of the great nickel mines, and the Sudbury deposits, being the most important and the only ones of the sulphide type extensively developed, have been the chief source of information in regard to this type. The observations and the conclusions drawn thereon from numerous studies of the various mines of the district have not only influenced, but are the essence of, this chapter of the science."

Jan 1, 1954

By J. J. Forbes

This publication is a revision of the first of a series of four Miners' Circulars originally prepared and issued in 19'29 for use in a course of training designed to prepare mine officials to organize men for rescue and recovery operations. These circulars were revised in 1937 and 1938 and again in 1948. This circular (Miners' Circular 33) discusses mine gases and methods for detecting them. The second of this series (Miners' Circular 34) gives instruction in Bureau of Mines methods of sampling and analysis of mine gases; the third (Miners' Circular 35) describes methods and equipment used for protection against mine gases; and the fourth (Miners' Circular 36) explains procedures used in sealing and unsealing mine fires and in recovery operations after mine fires or mine explosions.

Jan 1, 1954

By J. C. Gibson, C. H. Stockwell

"The San Antonio gold mine is at Bissett, Manitoba, on the north shore of Rice lake, 100 miles northeast of Winnipeg. Gold was discovered on the property in 1911, but intensive exploration was not undertaken until 1926. Milling commenced on May 1st, 1932. Total amount of ore milled from that time until the end of 1946 was 1,766,670 tons, having a value of $18,378,317.GENERAL GEOLOGYThe rocks in the vicinity of the mine are Precambrian and include three groups, namely, the Rice Lake series of volcanic and sedimentary rocks, basic and acidic intrusions, and a younger formation of sediments known as the San Antonio formation (Fig. 1). The lower part of the Rice Lake series, consisting of flows of rhyolite, trachyte, and andesite with interstratified beds of agglomerate, occupies an area extending southward from Rice lake. The lake itself and the country to both east and west of its northern end is underlain by the next succeeding beds of the series, which are chiefly tuffs, arkose, and conglomerate, but include a thin band of basalt. Northward from the lake, these are succeeded by the upper beds of the series, first a thin band of basalt and, overlying this, porphyritic andesite flows interlayered with beds of volcanic breccia or agglomerate.The Rice Lake series has been invaded on the east side of the lake by a body of basic rock ranging in composition from gabbro to diorite and quartz diorite, now much altered. This is cut by younger sills and dykes of basic rock, probably diabase, the original texture of which is largely destroyed by alteration. Numerous dykes of feldspar porphyry, quartzfeldspar porphyry, and a few of a rhyolite-like rock, occur south of the lake, but are uncommon to the north. They cut the diabase and older rocks.Extending westward from Rice lake and lying with marked angular unconformity against all of these rocks is the San Antonio formation, consisting of cross-bedded, arkosic quartzite."

Jan 1, 1954

By Geology Staff, C. H. Stockwell

"The Flin Flon base metal mine, owned and operated by the Hudson Bay Mining and Smelting Company, is on the Manitoba-Saskatchewan interprovincial boundary at a point 400 miles north of the International boundary. The deposit was discovered in 1914 by Thomas Creighton and the Mosher and Dion brothers. Since production commenced in 1930, 25,000,000 tons of ore have been mined. On January 1st, 1946, reserves were estimated to be 26,000,000 tons, averaging 2.99 per cent copper, 4.i4 per cent zinc, and 0.089 oz. gold and 1.25 oz. silver per ton. In addition to the four metals named, others recovered from the ore include- cadmium, selenium, and tellurium. The mine workings extend to the 3,750-foot level, but little development work has yet been carried on below 3,250 feet.The known ore occurs in six lenticular to irregular bodies within a zone 500 feet wide. These bodies average 900 feet long, 70 feet wide, 1,500 feet in vertical depth, and 2,500 feet in length along the plunge. They were formed by replacement of the country rock and include ore of two types, solid sulphides and disseminated sulphides. Seventy per cent of the total known ore is of the solid sulphide type. This consists essentially of metallic sulphides- chiefly pyrite- with included remnants of the host rock, and additional quartz and carbonate. In places, the ore exhibits banding, inherited from pre-existing structures. The disseminated ore occurs usually on the footwall side, and along the bottom of the plunge, of the solid sulphide bodies."

Jan 1, 1954

By H. W. St. Clair

This study was undertaken to provide a more adequate knowledge of the chemistry of the sulfide volatilization process for recovery of tin from low-grade Bolivian ores. The investigation was partly supported by the Department of State under its program for scientific cooperation with South American republics. The results of this investigation demonstrate the conditions under which cassiterite (Sn02) may be converted to stannous sulfide by reaction with pyrite or sulfur vapor, Quantitative data are given on the rate of sulfidization and on the vapor pressure of stannous sulfide.

Jan 1, 1954

The Black Hills Mineral Atlas briefly summarizes all pertinent date available on the mines and mineral deposits in the Black Hills that have been explored, developed, mined, or located. The purpose of the atlas is threefold: First, from available date the general potentialities of the Black Hills region can be determined, although it is not possible to calculate actual ore reserves; second, it will provide the necessary basic information regarding a given property or commodity for further detailed study; and third, the compilation is a comprehensive directory of Black Hills deposits.

Jan 1, 1954

By V. A. Nieberlein

The purpose of this investigation is to determine the reserves of columbium (niobium) minerals in Arkansas and to develop metallurgical methods for concentrating the minerals and extracting the metal. The columbium resources of central Arkansas were explored by drilling and trenching, and a number of samples were taken. On the basis of this exploration the known reserves of the metal were estimated to be over 78,000,000 pounds. The reserves could possibly be extended by additional exploration to 150,000,000 pounds.

Jan 1, 1954

By Arthur Baker III

The orebodies are long bedding-plane lenses of chalcopyrite and sphalerite, associated with garnetite masses. Most of the orebodies are within a 50-ft thickness of Cambrian limestone; other Paleozoic limestones and dolomites are locally metamorphosed but only slightly mineralized. Pre-mineral faults are numerous, but shallow folds were the main ore-localizing structures. JOHNSON camp is in the northwestern part of Cochise County, Ariz., about 50 miles east of Tucson. The nearest major mining districts are Tombstone and Bisbee, respectively 27 and 50 miles to the south, and the Superior-Miami-Globe-Ray porphyry copper group, about 90 miles northwest. Like many mining camps of the Southwest, Johnson camp is said to have been worked by the Spaniards. The first production on record was in the early 1880's, when an unknown amount of oxidized copper-silver ore in the Peabody mine was mined from replacement orebodies in the Pennsyl-vanian Naco formation. From 1904 to 1911 outcropping oxidized ores in the Cambrian Abrigo formation were worked, and an estimated 100,000 tons of copper ore were shipped. In 1912 the first large sulphide orebody of the district, the Republic Manto orebody, was discovered, and in the following few years some 250,000 tons of predominantly sulphide ore were shipped. The average grade of this ore was approximately 4.5 pct Cu, 6 pct Zn, 0.8 oz. Ag, and 0.001 oz Au. The Republic, Copper Chief, and Mammoth mines were the principal producers during this period. Mining ceased in the district after 1920, and until 1943 only small-scale leasing operations were carried on. In 1943 all the mines that had been productive were acquired by the Coronado Copper and Zinc Co., the present operators, and in the 10 years since that time the district production has amounted to approximately 350,000 tons of milling ore averaging 2 pct Cu and 6 pct Zn. Most of this ore was produced from the Republic and Mammoth mines, but since 1950 a large part of the production has been from the new Moore mine. The total known production from the district, then, is about 3/4 million tons of copper and copper-zinc ore of low grade. All of this ore was produced from orebodies associated with garnetite in the middle member of the Cambrian Abrigo formation. In addition to this known production, an unknown tonnage of ore was extracted from the Peabody mine orebodies that lie in the Pennsylvanian Naco formation. Published information on the geology of the district is limited. Aside from brief references in various mining journals, only three papers on the district have been published.1-3 One of these is a U. S. Bureau of Mines report on a diamond drilling program, one is a brief paper on the general geology of the district, and the third is a report on geochemical experiments, with a section on the occurrence of the orebodies. The last two are by John Cooper, of the United States Geological Survey, who has done much detailed work in the area. Stratigraphy The rocks of the mineralized area are Paleozoic sediments ranging in age from Cambrian to Penn-sylvanian. Several disconformities are present in the stratigraphic column, the most important one being between the Cambrian Abrigo formation and the Devonian Martin formation. There are no angular unconformities. Within the district, the Paleozoic sediments lie in a fairly uniform monocline, striking northwest and dipping 30" to 50" northeast. This local monocline is part of a domal struc-ture centered in the Little Dragoon mountains to the southwest. The Texas Canyon stock, a quartz monzonite body intruded probably during the Laramide revolution, lies south of the mineralized area (Ref. 2, p. 33). The Paleozoic rocks dip away from the stock, and on the surface are separated from it by at least 1500 ft of Pre-Cambrian rocks. The outcrop pattern of the northeastern edge of the stock suggests that it may dip gently northeastward, passing below the mineralized area at moderate depth. No quartz monzonite has been found in mine workings or diamond drill holes, which reach to depths of 1000 ft. The only igneous rock found in the mineralized area is a lamprophyre dike cutting the Naco limestone in and near workings of the Peabody mine. With the exception of the lowermost beds—the Bolsa quartzite and the shaly lower member of the Abrigo formation—the Paleozoic sediments are predominantly carbonate rocks, Fig. 1. The middle member of the Abrigo formation, which contains the principal ore-bearing beds, is limestone, with thin shale partings throughout most of its 250-ft thick-ness. Near the top of this member is a sandy bed some 25 ft thick. The upper member of the Abrigo formation and the lower half of the overlying Devonian Martin formation are dolomitic, with num-

Jan 1, 1954

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954