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By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

By Charles Will Wright

Brief descriptions of the occurrence of the various deposits of strategic minerals then known in South America are published in "The Mineral Deposits of South America," by B. L. Miller and J. T. Singewald, 1919; in "Ores and Industry in South America," by H. F. Bain and T. T. Read, 1934; and in many publications on the individual countries. To give a gen.era1 idea of the situation today and possibilities for future output of strategic minerals in several of the countries, the following notes are offered. All tonnages are in metric units.

Jan 1, 1940

By L. E. Mannion

Sodium carbonate (soda ash) is one of two principal commercial alkalis. Its principal competitor is sodium hydroxide. The use of sodium carbonate is recorded in ancient Egypt, where naturally occurring brines and solid salts provided impure soda for early glassmaking. Until the 19th century, soda ash (as well as potash) was recovered mainly by leaching wood or other plant ashes. In 18th-century Europe, for example, leaching seaweed ash with hot water produced a brown laundry lye. One of the better grades of this material was a Spanish product, barilla, which analyzed 24 to 30% Na2CO3 (Hou, 1942). The modern chemical industry was born in 1691 with the LeBlanc process for making sodium carbonate from salt, sulfuric acid, and lime. English industry used this process extensively in the 17th and 18th centuries. The next major advance was in 1863, when Ernst Solvay devised the ammonia-soda, or Solvay process. The first of many Solvay plants was built in 1874. These supplanted the LeBlanc method and dominated worldwide soda ash production until 1974, when mined sodium carbonate became predominant. Although considerably less important until recently, natural sodium carbonate deposits historically have supported small soda ash operations throughout the world. Shortages during World War II stimulated production of "natural" soda ash from such deposits, particularly at Searles Lake, CA and Lake Magadi, Kenya. More spectacularly, increased production from the vast trona deposits in Wyoming has virtually supplanted the Solvay process in the US. Principal producers of natural soda ash as well as the character of the source deposits are listed in Table 1. [ ]

Jan 1, 1983

By J. S. Ross

Few Canadians realize the role of their domestic industrial minerals industry because it is over-shadowed in production value by a large metallic minerals industry. But since 1960, Canada has had a reasonably well balanced, mature industrial minerals industry; and although the nation's sparsely scattered population has not been able to support an industrial minerals industry in a manner comparable to the domestic and foreign support given the metal mining sector, Canada is, nevertheless, exporting large quantities of higher priced nonmetallic minerals. Production of many of the basic minerals had been firmly established long before 1960, but it was not until the late 1950's that the output of cement, salt, titanium dioxide pigment and slag, sulfur, gypsum and sodium sulfate reached relatively high levels. Shortly after 1960, the significant potash and lithium chemicals industries were established and their effect is just now being realized.

Jan 11, 1964

By Chester O. Ensign

Results of the application of geologic knowledge to grade control have been remarkable. Grade reduction from dilution has been diminished from greater than 9% at the time of the program's beginning to about 2% at present. This has resulted in an increase of about 1.8 lb of copper per ton of ore mined and has made a substantial contribution to earnings at White Pine during the past two years. Even more improvement is expected in the future. The White Pine orebody, situated in the southwestern portion of the Keweenaw peninsula of upper Michigan, is a gently dipping stratiform or bedded deposit. Copper distribution is stratigraphically controlled with higher values being confined to specific beds in the ore column. Room-and-pillar mining is practiced. Mining technique and geologic characteristics present a special array of problems in controlling the grade of ore.

Jan 4, 1964

By Wallace Ralston

The East Texas area includes the northeast 38 counties of the state of Texas. It covers all, and extends beyond, the borders of what is commonly described as the East Texas Basin. It is one of the most important oil and gas-producing areas of the Mid-Continent Province. It includes four important oil fields—Van, East Texas, Cayuga and Long Lake— and the recent extension of Rodessa field into Cass County, Texas, may prove to be of major size. Four commercial gas fields are in this area— Bethany, Waskom, Cayuga and Long Lake. Up to January, 1936, all of the oil has been produced from the Upper Cretaceous formations, and most of that from the basal member, the Woodbine sand. Gas is produced from both the Upper and Lower Cretaceous formations. Development in Fields East Texas Field.—This field continued to dominate the drilling and production situation throughout the United States. There were 4036 wells completed in this field during 1935; that is, 365 more wells than were completed during 1934. Drilling activity was due to close spacing of wells and the addition of 10,000 acres to the field. The field is now drilled to a density of one well to 6½ acres, which is certainly more wells than necessary for economic production of the field. The close spacing of wells is due mostly to the type of proration, which is per well allowable based on a potential test, and does not take acreage into consideration, and also to the numerous small acreage tracts such as town lots and excess strips. The field now has 19,519 producing wells. The allowable production for the field during 1935 was 161,118,659 bbl.; estimated production, including illegal or "hot oil," was 174,200,150. The illegal production of oil gradually decreased throughout the year, until an estimated low was reached of 20,500 bbl. daily during the months of November and December. The price of oil remained at $1.00 per barrel throughout the year. As stated, about 10,000 acres were added to the field during the year, making a total of 128,000 productive acres. There is a possibility that

Jan 1, 1936

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

By Dorsey A. Lyon, Robert M. Keeney

The utilization of hydro-electriic power in electro-metallurgical industries, aside from purely mechanical operations, may be of two kinds. The electric energy may be used to supply the heat necessary for the performance of the chemical reactions of a metallurgical process, or the electrolytic action of a direct current may be employed for extraction of metals, either in a reduction process or a refining process. In discussing this subject, it is well to distinguish between established industries, which are producing metals and alloys at a, profit by use of the electric current, and the many processes which are either still in the experimental stage or have not even passed the paper stage of development of a patent. That is, we consider electro-metallurgical industries as commercial operations which are now consuming large blocks of electric energy, while processes which are not in commercial operation are only prospective consumers. Also, owing to the difliculty and risk of any attempt to foresee the effect of the European war upon electro-metallurgical industries, we have felt obliged to disregard the war entirely, and state our opinions regardless of its existence. Application of Electric Energy to Metallurgy Disregarding electrolytic refining processes, the applications of electric energy to metallurgy, when considered from a commercial viewpoint, may be classified as follows: Industries Experimental Processes Manufacture of aluminum Electric-furnace smelting of: Electric-furnace manufacture of: Ferro-alloys Copper ore Pig iron Zinc ore Steel In this paper only the above industries and experimental processes will be considered as possible consumers of hydro-electric power in large quan-

Jan 1, 1916

By David E. Jones, Dean K. Hunt, C. Y. Chen

INTRODUCTION Of all the numerous geological hazards that threaten the well-being of urban areas in the United States, probably none is so widespread, persistent, and diversified as surface subsidence (HRB-Singer, Inc., 1977). Simply defined, subsidence is the vertical displacement or sinking of the ground surface caused by either natural phenomena or man's activities. The downward movement, however, can be accompanied by horizontal movement, strain, tilt and even by a locally upward movement. Damage to structures and the environment can result from any of these movements. Extracting subsurface materials, fluids and solids, accounts for most man-induced subsidence in the United States. Among all the mining-related subsidences, the collapse of voids created by underground coal mining has been the major cause in inflicting surface damage (Comptroller General of the United States, 1979). Subsidence from coal mining may occur within a few weeks or be delayed for years, depending upon the mineral layer's depth below the surface, the overlying rock strata's characteristics, the extent and methods of mining that were employed, and the time deterioration of pillar and mine structure. Unless underground resources are not mined or control measures are implemented to prevent or minimize damage, some degree of surface subsidence and its accompanied deleterious effects are often inevitable. The ways to control the subsidence and minimize surface damage may include: 1. Precautionary measures built into new structures or surface features. 2. Preventive works applied to existing structures or surface features. 3. Mine design incorporating special underground layouts. 4. Any combination of the above measures. Upon the enactment of Public Law 95-87, the Secretary of the Interior, through the recently created Office of Surface Mining (OSM), was authorized to promulgate rules to regulate mining reclamation including subsidence control. Proposed on September 18, 1978, these rules were finalized, following public comment and hearings, on March 13, 1979, as part of the permanent regulatory program for the regulation of surface mining and reclamation operations which include the surface effects of underground mining. On January 28, 1981, Secretary Watt of the Department of the Interior issued an order to re- quire all agencies to identify with recommendations all regulations which are believed to be excessive, burdensome or counterproductive. Also on February 17, 1981. President Reagan issued Executive Order No. 12291 requiring all Federal agencies to conduct a regulatory review to make a determination that each promulgation of a regulation is clearly within the authority delegated by law and consistent with Congressional intent (Federal Register, 1981). As a result, OSM initiated the regulatory reform to revise the permanent regulatory program. Following a brief discussion of the technical aspects and the effects of subsidence on man and his environment, this paper presents a historical overview of how rules and regulations are used to govern the subsidence related problems. The development of the regulation of subsidence under Public Law 95-87, the Surface Mining Control and Reclamation Act of 1977 (SMCRA or the Act) are also discussed, including the new regulations being developed under the regulatory reform program. SOME TECHNICAL ASPECTS Am EFFECTS OF FINE SUBSIDENCE An extensive historical review of mining subsidence is given by Zwartendyk (1971) and Shadbolt (1978). Comprehensive technical presentations have been given by Henry (1956), King and Whetton (1957), Hall and Orchard (1963). Muller, et al. (1968). Grard (1969), Voight and Pariseau (1970). Kapp and Williams (1972), Cummins and Given (1973), Brauner (1973) , and NCB (1975). A theory of surface subsidence due to underground mining was perhaps first fundamentally stated by a French engineer, Toillez, in 1838, and formulated by a Belgian engineer, Gonot, in 1839 (Goldreich, 1913, cited by Zwartendyk, 1971). Since that time,

Jan 1, 1982

By R. M. Caves

High-purity dense tungsten coating is obtained by means of a modified de Boer-van Arkel iodide process using tungsten bromides. The all-glass reaction system is pumped, baked, and sealed (pinched-off) at about 10-7 mm Hg pressure. The bromides then formed in situ are decomposed, depositing tungsten on heated tungsten surfaces. Heating of the specimen is done inductively in a novel arrangement that avoids electrodes of glass-to-metal seals. The tungsten, deposited at specimen temperatures from 2000° to 2800°F and bulb (halide) temperatures of 225" to 725°F, was adherent and uniform, and ranged in thickness to 1/8-in. REFRACTORY metals are of interest at NASA for use in hypersonic aircraft, in rocket engines, and in other thrust devices where very high temperatures are encountered. Tungsten, with a melting point about 6100° F, is potentially very useful for some of these applications. Considerable research on tungsten and its alloys is currently being conducted at the NASA Lewis Research Center. In this tungsten research program, there is need for a method of depositing high-purity, nonporous tungsten coatirlgs. Metallurgical bonding of the coating both to itself and to the substrate is required. In addition, it is necessary to be able to deposit thin, uniform coatings on substrates of a variety of shapes and sizes for laboratory test purposes. A survey of the methods previously used for depositing tungsten coatings indicated that none would likely meet these requirements for high purity, good uniformity, and high density except thermal decomposition of the halides. The method for coating that was selected for investigation was the thermal decomposition of tungsten bromide. This is a variation of the van Arkel and de Boer iodide process established years ago and recently reviewed.1,2 This process is applicable to the transition metals in general. More recently, the application and techniques were extended with chlorine3 and fluorine,4 and included the coating of tungsten. This is believed to be the first report on the use of the bromide for tungsten coating. Bromine was chosen over the other halogens because it promised a lower temperature for tungsten

Jan 1, 1962

By W. A. Hustrulid, N. A. Ross

An analysis of the design of medium to hard rock tunneling machines is presented. The developed equations are used to compare performances and machine requirements using kerf and fixed pick cutters to bore a given rock. With the use of pick cutters, required thrusts can be greatly reduced and still achieve the same boring rate as with present day tooth or kerf cutters. It appears that the cutting coefficient, which for most boring machines is of the order of 0.1, should be increased to one or larger to facilitate rock removal by cutting rather than grinding. The depth of cut and the indexing distance should be greatly increased to make use of inherent rock weakness.

Jan 1, 1971

By Charles M. Behre

Under the caption "fault," geologists intend to include all mass movements of solid rocks over adjacent rock masses. When these are studied long after their origin, however, circumstances make it possible to recognize as "fault" only formations showing clear evidence of actual movement of one side with respect to the other. Necessarily the chief evidence consists of the offset of a vein, bed, or other key structure. Planes of movement parallel to the bedding, or nearly so, are recognized with difficulty or are overlooked and hence many important faults are wholly unrecorded. Indeed, among standard American references on structural geology, one alone emphasizes the importance of bedding-plane movements and that one only briefly1. For some time the writer, cognizant of this difficulty, has paid special attention to such movements, both as observed in the field and as recorded in the literature. It is believed that enough data are now at hand to justify a short discussion. Its purposes are fivefold. It is desired first to briefly classify and describe at least the more common kinds of bedding-plane faults, and second, to examine the causes and manner of their formation, at least in instances where the subject has not yet been well covered by other investigators. Third, certain by-products of bedding-plane movements are of such conspicuous importance to the economic geologist and mining engineer as to merit mention. Fourth, concrete illustrations should be placed before the reader in order to lend reality and to furnish a basis of comparison with his experience; such illustrations will necessarily be scattered through the text of this paper. They are only in part from the writer's own field observations. The fifth and prime objective of this paper is to direct attention to the great importance of movements on the bedding planes, in the hope that the recognition of such movements and their significance may simplify mining problems.

Jan 1, 1937

By W. M. Peirce, R. K. Waring

Zinc of high purity offers definite advantages in certain fields. A process by which zinc of 99.99 + per cent purity is produced by pyro-metallurgical methods is described in this paper. The process consists of a fractional distillation following the primary reduction; this fractional distillation employs the principles of rectification for the separation of lead and other high-boiling impurities and cadmium and other low-boiling impurities. Theoretical Considerations Involved in Production of High-purity Zinc by Distillation Fractional distillation, fractional condensation, and rectification are recognized methods of separating mixtures of liquids. In the field of organic liquids these methods are widely used but not commonly to effect as complete a separation of liquids as is done in the problem under consideration. Zinc boils at 905" C., cadmium at 778" C. and lead at about 1620" C. Zinc may contain from several hundredths of one per cent to over one per cent each of cadmium and lead, and the problem is to reduce these impurities to a few thousandths of one per cent. For lead and zinc, the spread in boiling points is substantial, 715° C., while for zinc and cadmium it is only 127" C. The basic limitation of any separation by distillation may be found from the relation between the equilibrium composition of the vapor and the liquid for all mixtures of the two substances involved. If a mixture of constant boiling point is found, or if a stable compound that vaporizes without dissociation occurs, there is a definite theoretical limit to the degree of separation that is possible when operating at atmospheric pressure with respect to that mixture. Otherwise, any degree of separation is theoretically possible. The equilibrium composition of vapor in contact with liquid mixtures of zinc and cadmiurn at the boiling point has been determined experi-

Jan 1, 1937

By J. M. GLEDHILL

(Washington Meeting, May, 1905.) A Discussion of Mr. J. M. Gledhill's paper, read by title at the Lake Superior meeting, but presented first at the New Yolk meeting of the Iron and Steel Institute (October, 1904), and here published under a mutual agreement. Between the two Institutes. Discussion. MR. E: WINDSOR RICHARDS, Past-President, said that at a recent meeting of the Institution of Mechanical Engineers a paper was read on tool steel, and he called the attention of the members to the high-speed tool steel at the Bethlehem Works. They would have the pleasure of seeing those wonderful works and would see 60, 70, 80 and 100 tons oil lathe with half-a-dozen of these high-speed tools running. PROP. H. M. HOWE (Columbia University) said that they all looked upon these high-speed tool steels as of very great importance, particularly to the machine shop. One point occurred to hire : Had it really been shown that Swedish steel is necessary, or better than equally pure steel that is not Swedish; and is cemented steel really necessary, and is there any advantage in using that, rather than equally pure open-hearth steel'! It might be well if the author could indicate the kind of evidence on which lie bases his assertion that it is necessary to have cemented Swedish steel. Many were hoping for the development of high-speed steels from elements which exist in great quantities, such as silicon, manganese and chromium, rather than from rarer metals like molybdenum, vanadium and tungsten, the supply of which is likely to be soon exhausted. If the high-cutting speed was to last more than a generation, it. seemed to him that they would have to draw upon the common ele¬ments and not upon the rare ones. MR. Tom WESTGARTH (Middlesbrough) said he fully appreci¬ated what had been said about the advantages of using high-speed steel, because great benefit had been derived from the

Mar 1, 1905

By S. J. Green, R. D. Perkins

Little data exists on the high strain rate behavior of geologic materials. Uniaxial stress tests by Kumar1 and by Serdengecti and Boozer2 present some results to strain rates in the range 10 to 103 per sec. The two references cited are the only ones the authors found for high strain rates. Techniques for experiments at high strain rates are not well developed and, in general, leave questions with respect to interpretation of data when the material behaves in a brittle manner. The most reliable data at very high strain rates (104 to 106 per sec) are found in some recent flat-plate work3-5 where experimenters have impacted one plate into another, thereby creating a uniaxial strain loading. The standard uniaxial stress-strain curves cannot be obtained directly from these tests; however, yield (or fracture) may be studied by measuring the "elastic" wave magnitude. These data then may be compared to uniaxial stress data by resorting to some preassumed yield/fracture criteria. Even with the most liberal interpretation of existing data, little can be said of the effects of high strain rate on stiffness, yield/fracture, and post-fracture behavior of geologic materials. It is the purpose of this work to begin to add to the understanding. The data presented here are intended to provide material information for use in calculating the response of geologic materials to high rate deformations. These data can be applied directly to determine parameters such as the elastic modulus and Poisson ratio as a function of stress. Furthermore, these data can be used to derive an understanding of yield/fracture and the effect of rate on the yield/fracture surface. The work presented is a first step, and is

Jan 1, 1972

By Richard D. Call

Predicting the performance of a waste embankment requires an estimate of the properties of the waste and foundation materials. The performance characteristics and the associated material properties are: [ ] Methods for obtaining estimates of the material properties include: laboratory and field testing, back analysis, and indirect estimates from other material properties. The most critical technical need is the development of indirect methods for use in feasibility studies and mine planning, prior to production when actual samples of waste material are not available. Material properties are not unique, single values; they are probability distributions. There are two components to these distributions: the uncertainties in testing and the inherent variability of the material. The objectives of a material properties evaluation should be to obtain an unbiased estimate of the property distributions rather than the average or the minimum value. Whether the current trend to a probability design analysis is followed or a simple sensitivity analysis is conducted, the unbiased probability distribution is preferable to single values.

Jan 1, 1985

By William Phillips

THE earliest mention of the sulphur deposits in what is now Culberson County, Texas, seems to be contained in "Explorations and Surveys for a Railroad Route from the Mississippi River to the Pacific Ocean, United States War Department, 1853-54." Captain John Pope (he was not commissioned Captain until 1856) had charge of one of the divisions of the Survey. In his report on the geology of the route, William P. Blake noted the analysis of a greenish earthy powder from the bed of Delaware Creek, at the springs, which contained 18.28 per cent. of free sulphur. The report states: "From the chemical examination of the waters of the spring, by Dr. Booth, it appears that chloride of sodium is the principal solid ingredient, but considerable quantities of sulphide of sodium are present. * * * * * The waters from the springs examined by Dr. Booth were alkaline, but it is possible that some of the springs are acid; and in this case the precipitation of sulphur would ensue on the mixture of the acid waters with those charged with alkaline sulphurets and the origin of the deposits of sulphur would he thus explained." This is the first reference to the existence of sulphur in that region, the first mention of the character of the water found there and the first suggestion as to the' origin of the deposits. The possibility of the existence of acid waters was confirmed by E. M. Skeats, nearly 50 years later.1 In this publication, Skeats says that the water from the sulphur deposits in Section 11, Block 114,, Township 5, contains 79.08 grains of free sulphuric acid per gallon. This locality is about 13 miles (21 km.) south of Delaware Creek and about 35-miles (56 km.) east of the Delaware Springs. The next published reference to the existence of sulphur in Trans-Pecos Texas is in the First. Annual Report of the Geological Survey of Texas, 1889, page 226, where W. H. von Streeruwitz mentions that sulphur is found in that region, but gives no further information. In the

Jan 9, 1917

By Gust Bitsianes, Joseph H. M. Beaty

Successful blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blastfurnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO - 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which CO2 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature corn bustion of carbon above the tuyeres. Assuming that 1000 Ib. of limestone is used per ton of pig iron, about 435 Ib. of CO2 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb, would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1943

By Joseph H. M. Beaty, Gust Bitsianes

Successful blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blastfurnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO - 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which CO2 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature corn bustion of carbon above the tuyeres. Assuming that 1000 Ib. of limestone is used per ton of pig iron, about 435 Ib. of CO2 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb, would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1943

By J. N. Sicking, F. H. Brinkman

A new method for obtaining equilibrium vaporization ratios (K-values) for reservoir fluids has been developed and tested. By application of the method, complex experimental measurements of liquid and vapor phase compositions are eliminated. This simplified technique reduces the cost of experimental equilibrium-ratio data for reservoir studies of condensates and volatile crude-oil systems. The method is designed for systems of constant composition and, therefore, is best suited for depletion studies where compositional changes at high pressures are minor. The basic data required, in addition to the composition of the initial reservoir fluid, are the relative vapor-liquid volumes and densities at reservoir temperature and variom reservoir pressures. Tests demonstrated that the method predicts equilibrium ratios accurately for condensates. A single test on a crude oil was not conclusive; further testing will be necessary before the accuracy of the method can be determined for crude-oil systems. In addition to determining equilibrium ratios, the calculation method provides information on the physical properties of the "plus" component in the vapor and liquid phases. The "plus" component is that mixture of components heavier than the least volatile fraction analyzed. This information is useful in studies of both natural depletion and cycling operations for condensate reservoirs where the heptanes-plus component in the gas phase is produced from the reservoir. INTRODUCTION As more volatile oil and condensate reservoirs are found, the use of phase behavior techniques to predict their performance is increasing in importance. These techniques have long been used for condensate fields and have more recently been applied to crude-oil fields containing oils of medium-to-high volatility. In these phase behavior methods, equilibrium ratios (K-values) are used to predict compositional changes in the reservoir fluids—thereby accounting for the recoverable oil that exists in the gas phase. The reliability of the predictions depends to a large extent on the equilibrium ratios used. These values must be obtained for each component for the entire pressure range being investigated. Unfortunately, because of the complex nature of hydrocarbon mixtures, accurate K-values are hard to obtain. The equilibrium ratios for a particular component will vary not only with the temperature and pressure, but also with over-all composition of the system. The importance of composition is quite critical at elevated pressures, but becomes negligible at pressures below about 300 psia. Therefore, because most phase behavior problems involve the high-pressure region, each fluid system becomes a special case. Experimental programs to determine characteristic K-values are quite difficult and time-consuming. Thus, it is often necessary to resort to approximations of the K-value data. Charts giving K-values for various mixtures and classes of mixtures are available in the literature. However, there are two major difficulties in using them: (1) the K-values of the "plus" component (that mixture of components heavier than the last one analyzed) must be obtained by extrapolation from the K-values of the other components; and (2) the K-values obtained must finally be adjusted by trial and error to agree with observed volumetric data. To eliminate these difficulties, a new method of determining equilibrium ratios was developed. Briefly, after the composition of the system as a whole has been analyzed, the method uses empirical correlations and the gross fluid properties of the system (relative vapor-liquid volumes and densities) to calculate K-values. Because the calculative procedure is long, it is best solved on a digital computer. About one hour of machine time on an IBM 650 computer is required to develop a K-chart for the fluid being examined. DEVELOPMENT OF THE METHOD OF OBTAINING K-VALUES Equilibrium ratios are defined as the ratio of the mole fraction of a component in the vapor phase to its mole fraction in the liquid phase. This statement is expressed in Eq. 1. A typical plot of equilibrium ratios for a particular system is shown in Fig. 1. It should be noted that, at pressures near the saturation pressure, the K-values appear to converge to a common point. This apparent convergence point is called the convergence pressure and is a characteristic of the system involved. Various empirical correlations of K-values have been noted. It has been observed that an isothermal plot of