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By Howard W. Wainwright

The Bureau of Mines is engaged in a research program on the characterization of tars produced by low-temperature carbonization of coal and their economical upgrading to more valuable materials, Throughout the years, hydrogenation has played an important role in the treatment of these tars, mainly as a means of converting the whole crude tar or selected fractions to motor fuels; diesel oil, lubricating oil, or various solvents. In some instances, production of specialty chemicals has been the objective. The purpose of this report is to summarize, without critical review, the information of the past 25 years on the hydrogenation of low-temperature tars and related substances as presented in the literature or its English translation. Published articles and patents not abstracted in the main body of this report are included in a bibliography at the end. HYDROGENATION REACTIONS The hydrogenation of tar follows three general types of reactions; 1. The removal of oxygen, sulfur, and nitrogen in the tar to form water, hydrogen sulfide, and ammonia, respectively: [ ]

Jan 1, 1961

By Charles B. Kenaban

The possibility of using ultrasonic energy as a tool to improve the electrolytic deposition of copper and zinc from several electrolytes was investigated by the Federal Bureau of Mines. Sound with frequencies of 20, 26, 38, and 400 kilocycles per second and acoustical intensities of 0.25 to 1.5 watts per square centimeter was employed. Measurements of cell voltage, anode and cathode current efficiencies, and electrode potentials were made at various current densities. Effects of ultrasonics on the quality of the deposit and on anode corrosion also was noted. In the electrolytic recovery of copper from an acid copper sulfate solution at 50° C., adherent, well-consolidated deposits are normally obtained up to a current density of 30 amperes per square foot. As the current density is increased above this value, the deposits normally become progressively more spongy and less adherent. Ultrasonic irradiation resulted in adherent and well-consolidated deposits at current densities up to 300 amperes per square foot. Radiation also produced smaller grain size and preferred orientation of the copper crystals. In addition, radiation caused as much as 3-volt decreases in cell voltages at the higher current densities. These decreases were caused chiefly by depolarization of the anode, although small depolarization effects were also noted at the cathode. Radiation apparently did not greatly affect cathode-current efficiencies, but prevented excessive anode corrosion at the higher current densities and resulted in more uniform corrosion. Ultrasonic radiation at a frequency of 400 kilocycles per second was not as effective as radiation at the lower frequencies. Circulation of the electrolyte at rates up to 5 percent of the cell capacity per minute did not produce results comparable to those effected by ultrasonic radiation. Rapid rotation of the cathode up to 1,800 revolutions per minute gave results approaching those obtained with ultrasonics.

Jan 1, 1961

Solvent extraction has recently been introduced into Australian hydrometallurgical practice for the production of a high grade uranium concentrate from El Sherana ore by a sulphuric acid leach and solvent extraction process. The solvent is a 5 per cent solution of tri(iso-octyl)amine in kerosene modified with 4 per cent of a long chain alcohol. The stripping reagent is a molar solution of sodium chloride.Preliminary testing for the development of the process showed that the leach liquor was quite amenable to the solvent extraction process and that the equilibrium and rate considerations of both the extraction and stripping steps were very favourable.The industrial plant contains four stages of extraction, three stages of chloride stripping and one stage of secondary carbonate stripping. An internal type of mixer-settler is used for the stagewise contact, the design being based on tests with model equipment.The performance and control of the industrial plant is satisfactory; 99·7 per cent of the uranium is recovered for a loss of 0·3 gallons of kerosene and 0· 4 pounds of amine per 1,000 gallons of liquor treated.INTRODUCTIONThe processing of El Sherana uranium ore from the South Alligator River valley commenced in April, 1959, and thereby introduced into Australian hydrometallurgical practice the unit operation of solvent extraction on an industrial scale. Although there are now some twelve mineral processing plants in the United States and Canada using solvent extraction, its application to the field of primary hydrometallurgy is quite new. Prior to 1956 none of these twelve plants was operating and hydrometallurgical application waslimited to the refining of comparatively high grade uranium compounds and fission products from nitrate and nitric acid solutions.

Jan 1, 1961

By L. E. Lynd

Ilmenite concentrates prepared from beach and dune sands of Florida, India, Australia, and other localities deviate to varying degrees from the theoretical composition of pure ilmenite, and generally contain more TiO2 than the formula FeTi03 would indicate, and some Fe2O3. This variation in composition is due to different amounts of altered ilmenite in the concentrates. (') The alteration has been shown to take place by oxidation and leaching of the iron in ilmenite, to yield residual products consisting of amaphous or very finely crystalline titanium dioxide and ferric oxide. Other studies(2) have stressed that ilmenite may alter first to an amorphous titanium-iron oxide, or to an amorphous mixture of titanium and iron oxides, with later alteration to crystalline titanium dioxide. There has been some speculation as to whether alteration of ilmenite is usually caused by weathering or by hydrothermal pr0cesses.(3,4,5 Three main methods of approach were used to study the mechanism and rate of ilmenite weathering. (1) Etch tests were used to learn the relationship between crystallographic orientation and the rate of chemical attack on ilmenite. (2) Altered ilmenites in New Jersey sands were compared with ilmenite in rocks of the area from which the sands were probably derived. (3) Experiments were carried out to determine at what rate, and by what agents, originally fresh ilmenite could be altered in the laboratory under simulated weathering conditions. ETCH FIGURES ON ILMENITE CRYSTAL PLANES A rather large ilmenite crystal from Sannidal, Norway, about 11/2 x 11/2 x 2 inches, bearing a few natural faces with imperfect surfaces, was prepared for etching by grinding and polishing crystal planes whose Bravais-Miller indices (referred to hexagonal axes) had been determined by X-ray methods to be 00.1, 10.0, and 10.2. Metallographic examination showed that the crystal was homogeneous, and uniform in orientation, except for the presence of twin lamellae which were oriented with their broadest surfaces parallel to the 00.1 planes of the large crystal. Since ilmenite is rather inert to standard etch reagents, strong solutions of hot sulfuric acid and cold hydrofluoric acid were used. Preliminary tests established that better etch figures were obtained using HF than with H2So4 solutions. The etch figures produced on 00.1 and 01.0 planes of ilmenite by etching 3 to 5 minutes in cold concentrated HF solution are shown in Figures 1, 2, and 3. The figures on 00.1 are "etch hillocks", rather than pits, and according to Honess(6), this phenomenon

Jan 1, 1961

By R. C. Ellman

Since successful industrial lignite-burning equipment was developed in 1925, the commercial use of lignite as a fuel for power plants has increased. It has proved an entirely satisfactory fuel for generating power and can be burned efficiently by various methods.4/ Equipment to fire pulverized lignite was installed and used successfully at the Trinidad Station of the Texas Power & Light Co. as early as 1926. The lignite was predried in steam-heated grid driers before pulverizing.5/ This method of firing was used later in the Comal Station of the San Antonio Public Service Commission.6/ Both stations, however, have since been converted to use other fuels. Units for pulverizing and drying lignite are relatively new in the lignite-consuming region of North Dakota. The air which sweeps the pulverizer and transports the pulverized product to the burners is preheated to dry the lignite during pulverization. The first unit was installed in 1948 in one of the two boiler units of the Crookston Station, Otter Tail Power Co., Crookston, Minn.7/ In 1951 the 30,000-kw. W. J. Neal Station, Central Power Electric Cooperative, Inc., Voltaire, N. Oak., was designed and constructed for firing pulverized lignite exclusively. It is the largest lignite-fired, power-generating station in North Dakota. The 44,000-kw. Lewis and Clark Station of the Montana-Dakota Utilities Co., Sidney, Mont., is fired by a similar pulverizing system. Operation of this plant was begun in October 1958. At Fergus Falls, Minn., the 53,500-kw. Hoot Lake Station of the Otter Tail Power Co., also using a pulverized lignite-firing system, began operating in September 1959.

Jan 1, 1961

By F. E. Brantley

Research was undertaken by the Bureau of Mines to assess the technical feasibility of smelting cement-copper precipitate in an electric furnace to produce commercial-grade copper. The blister-grade copper produced in smelting was refined by gaseous oxidation and reduction methods to rive a product equal in quality to fire-refined copper. The cement copper used in the study was typical of the material produced in commercial operations. The sample product was received in a partially oxidized state and analyzed 77.5 percent Cu, 3.4 percent Fe, 0.8 percent Pb, 0.05 percent Ni, 0.6 percent Sn, and 0.9 percent S. Smelting tests were made on the precipitate using laboratory-size induction and electric-arc furnaces. Three types of furnace linings were tested during, the investigation: Carbon, including graphite; clay-graphite; and silicon carbide. Although all proved satisfactory, either carbon or graphite was preferred because of their superior refractory properties and low permeability to molten copper. Copper recoveries in the induction and arc smelting tests averaged 92 percent in commercial-grade metal assaying 99.8 percent copper. Refining the molten copper by oxidation and gaseous reduction or by chlorine lancing increased the purity to plus 99.9 percent.

Jan 1, 1961

By W. N. Poundstone, G. R. Spindler

A comprehensive report on extensive experimentation in degasification of the Pittsburgh Coal seam is presented. Detailed accounts of the procedures and results are given for permeability tests, vertical bore hole tests, measurement of gas flow from sealed drainage areas, horizontal rib hole tests, and water infusion tests. The removal of methane gas from coal seams in advance of mining is not a new idea with mining men—much attention has been given to the possibility for many years. In other parts of the world, a principal concern has been in the recovery and utilization of the gas and a number of successful projects have been developed in Europe and elsewhere. In this country, the principal motivation has been related to the safety aspect with some possible side benefits concerning costs and efficiency in mining as secondary objectives. To date, experimental work in this country has been largely or entirely exploratory to determine bed characteristics with respect to the liberation of combustible gases to investigate or establish the possibility of degasification in advance of mining and as an aid in projecting mine ventilation systems to provide for safe, effective and economical handling of combustible gases liberated during mining. With these objectives in mind, the School of Mines and Engineering Experiment Station at West Virginia University, in cooperation with the Christopher Coal Co. of Osage, W. Va., initiated some experimental work in May 1952 and the project has been more or less continuous since that time. The work has been centered entirely in mines of the cooperating company in Monongalia County, W. Va., and Greene County, Pa. LOCATION AND GENERAL CONDITIONS OF THE AREA The principal mining in the area involved is in the Pittsburgh coal seam which lies at the bottom of the Monongahela series of the Pennsylvanian. The Pittsburgh coal in the area is generally uniform in its structure and physical characteristics. The bed thickness averages about 7 to 8 ft and the coal has a characteristic blocky structure as the result of pronounced face cleats and definite, but somewhat less pronounced, butt cleavage. It is a medium volatile coal, averaging about 37 pct, and is marketed principally as a steam fuel and for metallurgical purposes. The Pittsburgh coal outcrops along the Monongahela River and dips gradually, but not uniformly, slightly north of west (about N75°W). The westward extensions of the bed, from the areas contiguous to the Monongahela River which have been heavily mined, constitute the principal reserves and are all well below drainage with the depth of cover increasing with the distance from the river. In general, with deeper cover, it may be expected that methane liberation will be more of a problem in future mining as compared to areas mined previously; therein lies the interest in possible de-gasification in advance of mining. Fig. 1 shows the Pittsburgh coal area in the vicinity of Morgantown in Monongalia County, W. Va., and Greene County, Pa., in which the experimental work discussed is located. Fig. 2 shows the contours on the Pittsburgh coal in the test area. It will be noted that the first two bore holes for the experiments were at the edge of a bench or terrace with considerable change in the gradient in the immediate vicinity of the test holes and that the same general condition applies to later test areas. Mining is intensively mechanized in the area and in the mines involved in the experimental work with corresponding rapid advance of working faces a typical characteristic. In the areas now mined the total methane liberation ranges from moderate to relatively heavy, but the actual face liberation is extremely variable and may range from practically

Jan 1, 1961

By J. L. Gillson

The word "other" in paragraph 4, line 11, column 1, page 205, should read "over;" the correct version of reason 2, this paragraph, is: 'L. . . 2) to evaluate the usefulness of certain geo-chemical techniques, V. C. Kennedy and S. W. Hobbs of the USGS had already studied the distribution of copper, lead, and zinc in the soils (both in background areas and over veins) and in the water and plants, providing a criterion for measuring the magnitude and effect of soil contamination; ...9 On page 206, in the top left hand corner of Fig. 1 (in the area bounded by 47°35' and 116°10), the reference to Fig. 3 is incorrect. The area of Pine Creek, South Fork Coeur d'Alene River, and portion of Big Creek (the area which includes, from left to right, Kingston, Pinehurst, Smelterville, and Kellogg) should be identified as that of Fig. 2A. The headings for columns 1, 3, and 4, Tables I and 11, page 209, column 2, were reversed when the paper was printed. The corrected tables are:

Jan 1, 1961

By E. P. Carman

In this report, the Federal Bureau of Mines presents a summary of the occurrence, properties, and uses of some natural bitumens, using the layman's or dictionary definition of bitumens - that is, naturally occurring hydro-carbons. Emphasis is on the less common solid and semisolid bitumens, particularly those occurring or used to some extent in the United States. This comprises data from many sources and references to these sources for more detail than is given in this summary. This paper was prepared primarily to answer questions about some of the less known bituminous materials. The word hydrocarbons could just as well have been substituted in the title for bitumens, but bitumens was used, since an abstract of the paper was presented at a meeting where the major emphasis was on bituminous materials. The reader will realize that coals, of which only the more unusual such as the cannel coals and torbanites are discussed in this paper, are primarily mixtures of bituminous materials and carbon. The amount of bituminous material, or volatile matter, in coals is greatest in the lower rank coals and the unusual types described in this paper, and decreases as coal rank increases. However, since no method other than destruction of the original coal substance by heat is known that will separate the volatile matter from the carbon, it appears reasonable to classify the coals with other bituminous materials, particularly since bituminous coal - the most widely used coal - by its name indicates the combination of bituminous materials and carbon.

Jan 1, 1961

By E. Hornbogen

The deformation mechanisms of a iron-phosphorus alloys were compared at 20oand —196°C. Alloying with phosphorus increases the resistance to slip, but has little effect on the resistance to twinning. The stress for onset of twinning is nearly independent of temperature, but there is an increasing tendency for cleavage along (112) twin boundaries with decreasing temperature and increasing phosphorus content. FIVE iron-phosphorus alloys and one high-purity iron (0.004 pct C, 0.004 pct N, 0.05 pct O) were vacuum melted and cast, then homogenized for 6 hr at 1100oC and water-quenched. Single crystals were cleaved from the coarse grains produced in this manner. The hardness was measured* on polished (100) surfaces of the crystals at 20" and -196°C. Laue back-reflection patterns indicated a deviation of not more than 3 deg from coincidence of the {100} plane with the surface. The deformation mechanisms were studied by relief effects on the polished surfaces. Yield points in compression (0.5 pct offset) were measured with polycrystalline material. At 20°C the addition of phosphorus to a iron leads to a change from slip to twinning as the main deformation mechanism, Figs. 1(a), (b). Between 2 and 4 at. pct P slip and twinning occur simultaneously. In alloys with more than 4 at. pct P twinning is the main deformation mechanism and slip was observed only in the neighborhood of twin intersections. All cracks at 20oC were on (100) planes, some initiated by twins.' From measurements made at-196oC, hardness and yield points of all the alloys were nearly constant and the same as the hardness of high phosphorus alloys that deformed by twinning at 20°C, Figs. 2 and 3. In the high-purity iron, plastic deformation at -196°C occurred by both slip and twinning, but deformation in the iron-phosphorus alloys appeared to be entirely by twinning. In the high phosphorus alloys a large number of cracks formed along the (112) twin boundaries and at intersections of twins, in addition to the (100) cleavage, Fig. 1(c). DISCUSSION In , iron, plastic deformation can occur either by slip or by twinning, depending upon composition,

Jan 1, 1961

By W. C. Peters, M. W. Pullen, C. A. Bays

During the past three and a half years considerable improvement in the techniques of solution extraction of salt has been made by the use of wells which are cross-connected by hydraulic fracture at the base of the salt. Fracture is initiated by the application of hydraulic pressure. Underreaming and perforating techniques are used to control initiation. The fracture is then extended by continuous pumping until a pressure communication is obtained. Pressure communication is followed by washing-through to obtain a low-pressure connection. Well construction using non-shrinking cements that will bond with the salt and with associated strata is essential to the process. The connecting procedure described permits solution to attack the salt deposit from its base upward, thereby permitting greater recovery, fewer well repairs, better saturation of brine, and overall economy of development and operation. The fracture method of cross-connection requires special pumping of the fluid and is limited by present experience to initial well spacings up to about 1200 feet. The method has been used in bedded salts and is applicable for wells in salt domes. Since spring of 1956, new developnents in salt extraction wells have followed procedures substantially different from those in prior use. Although multiple well systems, connected either by the natural consequence of the solution process or by undercutting under protective pads, have been used previously, the past three and a half years have brought about new designs and new operation procedures based on cross-connection of the wells using hydraulic fracture. To date these techniques have been applied largely in the bedded salt deposits of Michigan, Ontario, Ohio, West Virginia, and New York. To the writers' knowledge they have not been used in salt dome wells. The methods have not yet been in use for a sufficient period to permit any statistical comparison with the older methods. It is evident from experience to date that the methods result in higher recoveries, lower capital and operating costs, better saturation of produced brine, reduced well maintenance and repair, and in considerably fewer production units to insure

Jan 1, 1961

By J. M. W. Mackenzie, M. H. Buckenam

Flotation experiments using stearic, oleic, linoleic, linolenic, and ricinoleic acids and naturally occuring products rich in these acids as collectors for calcite are described. The results confirm the validity of the rule of Hukki and Vartiainen relating the collecting power and unsaturation of the C18 acids. Reasons for this relationship are discussed and a close relationship between mineral depression and critical micelle concentration is reported. It has long been recognized that the unsaturated fatty acids are in general superior flotation collectors to their saturated homologues. Whereas earlier workers concentrated on saturated and monoethe-noid acids, recent investigations have centered on oleic, linoleic, linolenic, and the substituted mono-ethenoid acid: ricinoleic. From studies of the collecting properties of palmitic, oleic, linoleic, and linolenic acids on ilmenite, rutile, hematite, and magnetite, Hukki and Vartiai-nenl concluded that the collecting power of fatty acids increased with unsaturation of the hydrocarbon chain. Sun, Snow, and Purcel12 investigated the collecting properties of unsaturated fatty acids as collectors for phosphate ores and concluded that the collecting power increased with increasing unsaturation of the hydrocarbon chain up to two double bonds and that further unsaturation decreased the collecting power. More recently Sun3 studied the collecting power of the C18 fatty acids stearic, oleic, linoleic, and linolenic on 37 minerals. The results of these experiments with a few exceptions showed that the collecting power of the acids increased in the order stearic, oleic, linoleic, and linolenic. The relative collecting powers of linoleic and linolenic acids were in many cases altered by the cleanliness of the mineral surface prior to flotation. Sun concluded that linolenic acid may become oxidized by atmospheric oxygen during flotation, a reaction which would reduce its effectiveness as a collector. This deduction is supported by Gaudin and Cole4 who concluded that oleic and linoleic acids do not undergo appreciable oxidation of the double bonds during flotation but that the linolenic acid double bonds are measurably affected. The most complete investigation on the influence of hydrocarbon chain unsaturation on the collecting properties of fatty acids is that of Kivalo and Lehm~svaara.~ These workers using linolenic acid of a higher purity than Hukki and Vartiainen showed that this acid was superior to oleic and linoleic acids as a collector for magnetite. They also found that ricinoleic acid was a more effective collector for this mineral than the other acids investigated, an observation particularly apparent at high collector concentrations. Seeking to explain the superiority of the unsaturated acids these authors considered the effects of critical micelle concentration, surface activity, hydrolysis, and cross sectional area of the hydrocarbon chain in relation to unsaturation. Using what, according to the results of Caviere are erroneous surface tensions of the soap solutions of these acids, they concluded that the surface activity decreases and the critical micelle concentration increases with increasing unsaturation. In view of the data of Cavier, whose results show that surface activity of these soaps increases with unsaturation, the deductions of Kivalo and Lehmusvaara are open to criticism. The degree of hydrolysis of the soap solutions as measured by Kivalo and Lehmusvaara decreases as the unsaturation of the fatty acid increases, a result which helps to explain the superiority of unsaturated acids as collectors. In view of the superiority of unsaturated acids as collectors for many minerals, attention has been directed towards the utilization of fatty acid raw materials such as tall oils and linseed oils which contain considerable quantities of these acids. This paper describes test work to determine the effect of unsaturation of the hydrocarbon chain on the collecting properties of fatty acids on calcite, and includes comparable test work using natural products rich in unsaturated acids. TEST WORK Reagents: The pure fatty acids used were oleic, linoleic, and linolenic. Of these, oleic was supplied by British Drug Houses Ltd. and the others were produced by the Hormel Inst. When not in use these

Jan 1, 1961

By Ronald W. Schaefer

This report describes operations at the Rosiclare Fluorspar Works of the Aluminum Co. of America at Rosiclare, Hardin County, Ill. The works include the Fairview mine, the fluorspar mill, and related facilities. The publication covers exploration, development, mining and milling practices, mine-drainage problems, and other activities and is presented as part of the Bureau of Mines series of publications on mining and milling practices in various parts of the United States. The Rosiclare fluorspar area, for its size, has been the largest producer of high-grade fluorspar in the United States and probably in the world. The vein system in this area is over 5 miles long and 1/2 mile wide, and ore has been found as deep as 900 ft.

Jan 1, 1961

By Edwin B. Cook

Studies of flame and combustion phenomena at the Bureau of Mines have been facilitated by computer evaluation of the thermodynamic properties of gases formed by constant-pressure burning.4 5 This report is the sixth of a series6-10 presenting results of such calculations; it deals also with constant-volume deuterium-air flames.

Jan 1, 1961

By D. W. Fuerstenau

In 1940 Schuhmann1 showed that the size distribution of a comminuted material can be expressed by the following empirical relationship: y = 100 (|f [i] where y is the cumulative percentage of material finer than size x, k is a size modulus, and a is a distribution modulus which is constant for a given material and machine. During the past few years, considerable emphasis has been given to the investigation of the extent of size reduction resulting from the expenditure of mechanical energy in crushing and grinding. Recently Schuhmann' presented a derivation of the energy-size reduction relationship by postulating that comminution in a device such as a ball mill can be considered to be the summation of many single comminution events, each of which yields a size distribution of particles following the Schuhmann size distribution equation. By grinding

Jan 1, 1961

By Gerald V. Gibbs

Quadratic functions, Q(hkl), are given to six places in increments of 0.01° for 2? from 0° to 90° for CuKa and from 25° to 180° for CuKa1. The wavelengths used for Cu in the computation are those agreed upon by the Editorial Commission of the International Tables for X-ray Crystallography (1950): CuKal 1.54051 A.; CuKa2 1.54433 A. INTRODUCTION At the Federal Bureau of Mines laboratory, Norris, Tenn., X-ray diffraction crystallography using tubes with copper targets revealed a need for a handy reference for the quadratic functions of copper radiation. The tables presented here were prepared to satisfy that need. The quadratic form Q(hkl) may be expressed in terms of the Bragg diffraction angle 2? and of the wavelength ? as

Jan 1, 1961

By Mary S. Esfandiary

This list of organizations that conduct research and development programs on coal has been compiled by the Bureau of Mines with the thought that such a directory may provide a useful guide to worldwide research efforts in the areas designated and may facilitate communication between organizations with similar interests. This list includes government, university, private, and commercial organizations. Many of these groups are conducting comparatively modest but often particularly interesting or specialized investigations. The areas of investigation have been defined in a broad manner--these include analysis and constitution, mining and geology, preparation, combustion, briquetting, high- and low-temperature carbonization, gasification, hydrogenation, Fischer-Tropsch, and health and safety. In some instances such information is not available, but the names of the organizations themselves often indicate immediate arias of interest. Special publications issued by and describing the work of each organization have been cited, when known; almost all of the organizations also publish results of their investigations in the technical press. Several foreign technical and trade publications that include such information and are not published directly by any of the organizations listed are cited in the pages following the list of organizations in each country. This list is not complete. Information that would improve coverage and/or accuracy will be welcomed by the Bureau of Mines.

Jan 1, 1961

By R. Greenwood

The advent of the space age and its promise of interplanetary flight has prompted new ideas for propulsion systems that will allow maximum energy with minimum fuel weight. The use of cesium as the source of energy for such rocket flights has been found desirable. Theoretical efficiency of a rocket fuel is measured in terms of specific impulse, defined as the number of pounds of thrust per pound of propellant consumed per second. Specific impulse is usually expressed in seconds (the number of seconds for which one pound of fuel would produce one pound of thrust) although it is really a measure of total energy, not of power. The most sophisticated chemical fuels have a specific impulse of 300 to 400 sec; liquid hydrogen heated by nuclear reactor has a specific impulse of 1000 to 1200 sec. Specific impulses as high as 20,000 sec, however, are theoretically attainable with the ion rocket, in which free cesium ions are accelerated across a voltage drop and ejected at high velocity.' Characteristics of the system have been sketched by Boden.2 The desirable properties of an ion propellant are: 1) low ionization potential, 2) low boiling point, and 3) high atomic weight. Alkali metals best fulfill these requirements, and Table I indicates the superiority of cesium. The use of heavy complex ions such as UCl3 is ruled out by their instability and other disadvantages.' Despite its enormous superiority in specific impulse, the ion rocket is inherently low-powered, capable of very small acceleration. Application of ion propulsion will be limited to large rockets and spaceships on missions requiring powered flight for weeks or months and employing a separate chemical propulsion system for escape from the earth's atmosphere where power requirements are large but of brief duration. For example, Kraemer and Larson3 considered the case of an unmanned 25,000-lb pay-load placed in a 300-mile orbit by chemical rockets, proceeding thence by ion propulsion to the vicinity of Mars, where it would go into orbit once again. Calculations provide for 8500 lb of cesium for such a voyage. The question of whether such quantities of cesium will be readily available to the space program does not appear to have been considered by geologists and mining engineers. Present Production and Uses Literature on industrial applications of cesium is scanty. The metal is used in scintillation counters, photocells, infra-red detection devices, and as a "getter" in low-voltage vacuum tubes. Production is sporadic and total figures are not published, but the annual consumption is measured in pounds rather than in tons. The few pollucite deposits known, small as they are, can easily supply the present limited demand for gram or pound lots of cesium. Until recently the price of cesium was $2 to $4 per gram, but according to Chemical Engineering, cesium salts are now available at $13 to $27.50 per lb. Geochemical Distribution As a large alkali ion, the cesium ion accompanies potassium in geological processes and tends to be concentrated in the latest crystallizing fractions of potassium minerals in much the same manner as rubidium. Most of the cesium in igneous rocks, therefore, is in the micas and potash feldspars of granites, and especially in granitic pegmatites. The cesium content rises markedly in the micas of the late by-drothermal replacement stage in complex pegmatite~.' Typically, cesium is only 0.5 to 0.01 times as abundant as rubidium in potassium minerals. Rb', with a radius of 1.47 A, is close enough in size to K' (1.33 A) so that rubidium forms no minerals of its own. Cs+ is so large (1.67 A) that only small concentrations can be taken up in potassium minerals; when cesium is present in solution in larger concentration it forms the mineral pollucite, Cs3-Na2A17Si17O48.3H2O, which is known only in pegmatites. In the weathering of igneous rocks, cesium is dissolved, carried to the ocean, and apparently in-

Jan 1, 1961

[NORTH AMERICA UNITED STATES ALABAMA AUBURN Sturm & O'Brien, Consult. Engrs. °Sturm, Rolland G. BESSEMER Granger, W. C. BIRMINGHAM Air Reduction Sales Crockett, John M. Amer. Cast Iron Pipe Co. Carter, Sam F., Jr. Donoho, C. K. Anderson Elec. Corp. Davis, Moss V. J. B. Clow & Sons Neptune, Maurice D. Connors Steel Div. °Sandelin, Robert W. Hayes Aircraft Corp. Ricketts, W. E., Jr. Willhelm, A. Clyde, Jr. McWaine Cast Iron King, O. H. Worthington, B. W. Shook & Fletcher Sup. Co. Gearhart, Thomas A. Southern Res. Inst. Dismukes, Edward B., Wheelahan, Edmund J. Thomas Foys Miller, Ralph M. Union Carbide Metals, Co. Brandler, Edgar A. U. S. Pipe & Fdry. Co. Clay, Donald H. Unaffiliated Berg, H. A. Caldwell, H. A. Gilmer, H. U. Harris, Thomas H. Templeton, J. B.]

Jan 1, 1961

By Dorothy M. Richardson

The Bureau of Mines has participated in the American Petroleum Institute Research Project 48A (API-RP48A) program on the Separation and Identification of Sulfur Compounds in Crude Petroleum. The lack of reference compounds or infrared spectral data has made difficult the identification of individual sulfur compounds boiling above 140° C. The recent acquisition of 24 alkylthiophnnes has made possible a limited study of this important class of sulfur compounds. The infrared spectra of 2-monoalkylthiophenes and 2,5-dialkylthiophenes for the 2 to 15p range are reported. Correlations for determining the 2-alkyl and 2,5-dialkyl substituted thiophenes are derived from this information. The 2-alkylthiophenes show a unique pattern in the 5.50 to 6.54 region, while the 2,5-dialkylthiophenes show a distinctive pattern in the 5.6µ to 6.7µ region. A skeletal vibration occurs in the 9.5 to 10.0µ region for all of the thiophenes investigated. These data will aid the infrared spectroscopist in the identification of compounds of the type reported.

Jan 1, 1961