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By James S. Browning

Heavy liquids have been used to separate minerals of different specific gravities for many years.4 5 6 7 8 9/ The method permits substantially quantitative evaluation of a variety of minerals and requires much less time than the usual methods of chemical analysis. This Bureau of Mines investigation was conducted to determine the applicability of heavy liquid mineral separation to the evaluation of certain spodumene and kyanite ores, prepared mixtures, and plant products. After careful standardization of the particular mineral and associated gangue, estimates of chemical analyses could be obtained from results of heavy liquid separations.

Jan 1, 1960

By C. A. Frenzel

Extensive spectroscopic data are needed in making reliable vibrational assignments for use in calculating thermodynamic functions of polyatomic molecules. The fundamental vibrations of organic molecules may be observed at any wavelength from 2.5 to 200 microns (micron = µ = 10-4 centimeters), but most often in the region from 3µ to 50µ. Raman spectra generally cover the range in which fundamental vibrations occur, but equally important infrared spectra usually are not measured at wavelengths longer than 25µ. This limitation results because most infrared spectra are determined for analytical purposes, which seldom require information outside the region 2µ to 25µ. Measurements of infrared spectra in the range 15µ to 35µ recently were begun by the Bureau of Mines to obtain data needed in making vibrational assignments. This report presents the spectra of the following thirteen compounds: Tetrahydrofuran, 1-methylpyrrole, piperidine, 2-methylpyridine, 3-miuthylpyridine, 2-propanethiol, cyclopentanethiol, 2-methyl-2-butanethiol, 3,3-dimethyl-2-thiabutane, cyclohexanethiol, cyclopentyl-l-thiaethane, 2,4-dimethyl-3-thiapentane, and hexamethyldisiloxane.

Jan 1, 1960

By R. L. Montgomery

Heats of solution of yttrium chloride and oxide in hydrochloric acid were measured by Bureau of Mines researchers. Using the heat of combustion of yttrium mentioned in the literature, the Bureau calculated the heat of formation of yttrium chloride to be -239.16 + 0.50 kcal./mole. The Bureau experiments gave evidence that the heats of solution of yttrium chloride from the literature are mostly too low because of water and/or oxychloride impurities. Heat of combustion of yttrium (8)3/ and its heat of solution in hydrochloric acid (2, 14) have been measured. The earlier heat of solution measurement (2) is unreliable because of possible potassium contamination (4). Heat of solution of yttrium chloride has been measured by three researchers (3, 9, 15), who obtained widely different results. Spedding and Flynn (14) report the heat of formation of yttrium chloride as -232.69 kcal./mole from their solution studies. The present work was designed to check the reported heats of solution of yttrium chloride and to determine the heat of solution of yttrium oxide. The latter measurement would allow the results of solution and combustion data for yttrium to be intercompared.

Jan 1, 1960

By J. H. Field

Results of studies by the Federal Bureau of Mines on a pilot-plant scale for removing hydrogen sulfide and carbonyl sulfide from gas mixtures by the hot carbonate system are given in this publication. Gases containing up to 10 pet. hydrogen sulfide and 48 grains carbonyl sulfide per 100 cu.ft. were treated. In most tests carbon dioxide also was present and was removed simultaneously with the sulfur compounds. Because the rate of absorption of hydrogen sulfide is much more rapid than that of carbon dioxide over a wide temperature range, selective removal of hydrogen sulfide occurred in the bottom section of the absorber near the point of gas entry. Hydrogen sulfide was removed to pipeline specifications with carbonate solutions by using split-stream flows in the absorber and regenerator.

Jan 1, 1960

By T. A. Henrie

The Federal Bureau of Mines has investigated methods of sodium reduction of titanium chlorides to produce high purity titanium metal (14).4/ This investigation was made to obtain a better understanding of the reactions involved in sodium reduction of titanium chlorides and was part of the Bureau's activities toward improving the technology of titanium. Theoretical and experimental evidence show that sodium reduction of titanium tetrachloride occurs by stepwise reactions. The first stage reduction between sodium vapor and vapors of titanium chlorides produces titanium di-and trichlorides which subsequently condense with sodium chloride to form a salt mixture. The second stage reduction takes place in the condensed salt mixture between sodium and titanium subchlorides. Final reduction is a heterogeneous reaction between two separate phases, the a phase which consisted of sodium dissolved in sodium chloride and the ß phase titanium subchlorides dissolved in sodium chloride. The mechanism of the heterogeneous reaction between these phases is electrochemical in nature. The model proposed is a galvanic reaction at the interfacial region.

Jan 1, 1960

By H. H. Heady

A naphtha obtained by destructive, recycle hydrogenation of crude shale oil, produced by gas-combustion retorting of Colorado oil shale, was found by the Bureau of Mines to contain 49.1 percent paraffins, 20.3 percent cycloparaffins, 7.8 percent olefins, and 22.8 percent aromatics. The naphtha contained only minor amounts of sulfur, nitrogen, and oxygen compounds. Compounds containing less than 5 carbon-atoms per molecule were removed by distillation before analysis. The paraffins where predominantly straight-chain compounds; n-Hexane was present in the largest quantity, and the other straight-chain paraffins decreased in amount as the molecular weight increased. The cycloparaffins, which contained both cyclopentanes and cyclohexanes, were evenly distributed throughout the boiling range. Although the naphtha had been produced by hydrogenation, it contained a small quantity of olefins. Straight-chain olefins with a terminal double bond comprised about two-thirds of these compounds. Among olefins with an internal double bond, those having trans configuration were present in three times the quantity of those in the cis form. In the aromatics all but one of the alkylbenzenes having nine or less carbon-atoms per molecule were identified; toluene was present in the greatest quantity. Only a few of the higher molecular-weight homologs were identified. The composition of the naphtha was computed from analyses of 105 narrow¬boiling distillation fractions. Volume, density, refractive indices, bromine number, and an ultraviolet spectrum were determined on each fraction. From these data the hydrocarbon-group composition of each fraction was estimated. A silica gel adsorption analysis was used to check the values of nearly one-third of the fraction calculated from physical-property data. Mass and infrared spectra were obtained on some fractions for identifying individual compounds or types of compounds, such as terminal olefins.

Jan 1, 1960

By G. L. Cook

The design of a dual-inlet system for a Consolidated model 21-103C mass spectrometer is described in detail. The system permits both high-mass and low-mass samples to be run by using a single instrument. The difficulties of using a single instrument for both purposes are given and a method of minimizing these difficulties through the use of the present design is discussed, After examining the experience of five years of use, the conclusions are that the bimodal operation is practical and the low-mass analyses had nearly the same precision as before the modifications to the instrument were made. In 1951, O'Neal and Wier.5/ published the first description of the modifications made to a mass spectrometer so that the spectra of hydrocarbons with molecular weights up to 600 could be obtained. Further discussion of the equipment of O'Neal appeared in 1953.6/ Also, Brown, Melpolder, and Young7/ described a parallel inlet system designed to reduce sorption effects at room temperature.

Jan 1, 1960

By E. G. King

Thermodynamic calculations involving the oxides of tungsten and molybdenum have been hampered by lack of accurate entropies and high temperature heat contents. This paper presents work by the Federal Bureau of Mines on new low-temperature heat-capacity data leading to the evaluation of the 298.15° K. entropies of tungsten dioxide and tungsten trioxide, as well as high-temperature heat contents (above 298.15° K.) of molybdenum dioxide, molybdenum tri-oxide, tungsten dioxide, and tungsten trioxide. Included are heats of fusion of the two trioxides. The heats of formation at 298.15° K. of these four oxides are tabulated as measured by Mah4 5/ of this laboratory. Included also are the 298.15° K. entropy of Mo02 measured by Kin 6/ of this laboratory, and that for Mo03 according to Kelley and King.7/ These basic data provide a consistent compilation from which to perform accurate thermodynamic calculations involving these compounds. No previous low-temperature- heat-capacity measurements have been reported for tungsten dioxide. Seltz, Dunkerley, and DeWitt8/ measured the low-temperature heat capacity of tungsten trioxide. The only previously-reported high-temperature heat-content measurements for any of the oxides were conducted by Cosgrove and Snyder,9/ who measured molybdenum trioxide to 1,300° K.

Jan 1, 1960

By W. M. Mark

This investigation was undertaken to develop methods to improve the quality of titanium sponge produced by the Bureau of Mines modification of the Kroll magnesium reduction process. Research revealed that by systematic elimination of detrimental impurities introduced with the raw materials and by improved handling and processing techniques, high-quality ductile titanium with a hardness of less than 110 B.h.n. (Brinell hardness number) can be produced consistently. This improvement was accomplished by helium (or argon) stripping of residual atmospheric and other dissolved gases from the titanic chloride, preliminary dehydration of crude titanium sponge, and careful regulation of the titanium tetrachloride (TiC14) feed rate to the reactors.

Jan 1, 1960

By J. P. Capp

This experiment, one of a series on underground gasification of coal, was an investigation by the Federal Bureau of Mines of hydraulic fracturing as a means of increasing the air acceptance of a coalbed to permit introducing combustion air and removing product gases. Specific objectives of the investigation included: (1) Fracturing a coalbed; (2) determining the distance the coal was physically affected; (3) ascertaining the effect of the fracture on air acceptance of the coalbed; and (4) gasifying the coal. The coal was fractured with a fluid consisting of 15,000 lb. of sand mixed with 10,000 gal. of fuel oil and 5,000 gal. of kerosine, injected at pressures up to 900 p.s.i.g. and rates up to 425 g.p.m. The oil served as the fracturing medium, and the sand as a propping agent to hold the fracture open. From the fracture point, (the place in the bed where the fluid was injected), the fracture extended 200 ft. or more along the face cleats, somewhat less along the butt. cleats, and was confined to the coalbed. At the fracture point, the bed accepted about 500 std. c.f.m. of air, which was an etghtyfold increase. Fracture effects were extensive, as airflow was noted from old mine workings and outcrops 600 to 800 ft. from the fracture point. It is probable the actual fracture was much less than 600 ft. and that normal coalbed permeability beyond the fracture limits was responsible for this flow. This indicated that effects of the fracture extended beyond the area of coal physically affected. Although no attempt was made to gasify coal more than 200 ft. away, these effects plus the natural permeability of the bed likely would permit combustion beyond the outer limit of the fracture. As these experiments continued for more than 2 years, and greater air acceptance due to the fracture was observed at the beginning of each test, it is apparent that the effects of the fracturing persist for a considerable time.

Jan 1, 1960

By Robert W. Smith

Computation of the thermodynamic properties of the reaction products in the deflagration of explosive gas mixtures has been a most valuable guide regarding the possible kinetic mechanisms of homogeneous combustion processes. Knowledge of the physically possible end states is indispensable for understanding observed deviations from equilibrium in heterogeneous combustion. However such information on dust flames is entirely lacking. To complement a Federal Bureau of Mines study of stationary graphite dust flames burning in pure oxygen,6/ this report gives examples, at atmospheric pressure and room temperature, of composition profiles in an idealized oxygen-dust flame, with both mass and enthalpy being preserved. Similar profiles can be obtained from the data of the paper for elevated temperature and pressure.

Jan 1, 1960

By R. M. Becker

THIS IS a progress report on a study of the application of statistical practice to mine and mineral sampling undertaken by the Federal Bureau of Mines to provide sound theoretical and practical data for use of the mineral engineering professions. One of the problems in mine sampling is determining the reliability of the results. For certain types of sampling data (random data) the reliability of the results can be stated mathematically. For other types of data there is no known means of quantitatively expressing reliability. In applying measures of reliability to a set of random data, some knowledge or assumption of the characteristics of the particular data is necessary. In many fields these characteristics are well known. However, in mining, where the data are in assays, these characteristics are not well known.

Jan 1, 1961

By R. L. Marovelli

ANTICIPATING the eventual use of the huge tonnages of nonmagnetic taconites of the Mesabi range of the United States, the Federal Bureau of Mines is classifying and evaluating these deposits in detail. This introductory report describes work begun in 1954 as part of a long-range program to sample, classify, and evaluate important occurrences of nonmagnetic taconite on the Mesabi, range. Included in this report are brief discussions of the geology, history, and potential of the Mesabi range district and mining industry, together with a more detailed presentation of the sampling and metallurgical evaluation of these nonmagnetic taconite deposits. A total of 898 field samples was collected. Most of these were taken in the region between Grand Rapids and Chisholm, Minn., but a few came from the area between Chisholm and Buhl, Minn. Of the total samples, 865 were from open pit bank faces where the greater vertical distances presented by the cherty members facilitated the taking of a large number of samples. Conversely, the narrow face presented by the slaty members confined and limited the areas from which samples were taken. In addition, 33 of the field samples were taken from rock dumps in order to determine, in a preliminary way, the characteristics of these materials.

Jan 1, 1961

By E. L. Litchfield

This report of work by the Federal Bureau of Mines has two primary objectives: A survey of the present status and usefulness of the minimum ignition-energy concept, and the presentation of recent data that are believed to bear on the safety problem associated with the ignition of combustible gases by electric discharges. The minimum ignition-energy concept has widespread applicability, especially to safety. The primary obstacle in making theoretical calculations of the requisite ignition energy is the lack of data on chemical kinetics and flame hydrodynamics. The new data on electrical ignition are representative of the great increase in knowledge that can be achieved by proper utilization of geometrical and electrical characteristics associated with the ignition source. CONCEPT OF MINIMUM IGNITION ENERGY The basic concept of a minimum ignition energy (the minimum amount of energy required to cause ignition) follows quite naturally from general physical principles and from the stability (lack of chemical reaction) of the gaseous mixture under the initial conditions. It also follows that if, as a first condition, lossless, instantaneous, and spatially localized energy can be injected and, as a second condition, the relaxation time for conversion of this type of energy to the type required for the reaction is short compared to some characteristic time scale of the ignition phenomenon, the energy requirements will be essentially independent of the type of energy source. Even if condition one cannot be fulfilled, it is sometimes possible to estimate the energy content of the gas required for ignition, and under these circumstances, condition one is fulfilled in effect. There are several instances where results can be interpreted for circumstances that effectively satisfy conditions one and two; these will be discussed later.

Jan 1, 1960

By L. J. Kane

Chemical processes using coal often require economical removal of dust from high-temperature gases. Laboratory-scale investigations by the Federal Bureau of Mines have shown that an aluminum silicate fiber is suitable for filtering dust from gases at 1,800° F. The effects of the bulk density of the filter, rate of gas-flow, concentration of dust in the filter, fiber diameter, depth of filter, and concentration of dust in the feed gas on removal efficiency, pressure drop, and capacity of the filter to hold dust were studied. The laboratory filters were difficult to construct because the fibers were longer than the tube diameter. This caused irregular distribution of fiber that permitted dust-laden gases to leak through channels developed in the filter. Leaks also formed between the filter and the tube wall, but this was minimized by improved filter design. However, edge leaks and leaks through channels in the filter probably would be insignificant in properly constructed filters of industrial size. As the concentration of dust in the filter increased, the efficiency of the low-density filters decreased, contrary to expectations, probably because a higher percentage of the dust passed through channels that developed in the filter. The efficiency of high-density filters, however, increased with the concentration of dust in the filter. Results indicate that loosely packed filters would have a longer life than tightly packed filters at the expense of efficiency. As regeneration or replacement of stationary filters is difficult and expensive, loose filters would be best for filtering gases containing much dust. Gases containing little dust may be cleaned with tightly packed filters to obtain higher efficiency. For either type of filter, precleaning with cyclone separators or other means is advisable.

Jan 1, 1960

By Henry H. Ginsberg

The effectiveness of 0.01 pct. molybdenum, as ammonium molybdate impregnated on coal, on the hydrogenation of a high-volatile bituminous C coal at 8,000 p.s.i.g. and 460° to 480° C. has been studied in a pilot plant by the Federal Bureau of Mines. Under these conditions, the Bureau obtained 98 to 99 pct. conversion5/ of coal to liquids and gases at throughputs of 29 to 101 lb. of m.a.f. coal per cubic foot of reaction space per hour. At 460° C. the indicated yield of oil ranged from 63 pct. (based on m.a.f. coal) at a throughput of 35 lb./c.f.h. (pounds per cubic foot per hour) to 68.5 pct. at a throughput of 58 lb./c.f.h., and the yield of gaseous hydro-carbons ranged from 25.5 to 19 pct. at the same throughputs. The maximum measured yield of oil boiling under 325° C. was 47 pct.

Jan 1, 1960

By Henry H. Ginsberg

The Federal Bureau of Mines made pilot plant investigations of the process requirements necessary to produce heavy fuel oil by the liquid-phase hydrogenation of bituminous coal. The investigation was carried out in three separate series of experiments. The first series studied the effect of temperature and contact time on product distribution at 3,500 p.s.i.g. and 420° to 480° C. in the presence of 0.1 wt.-pct../ stannous sulfide plus 0.05 wt.-pct. iodoform based on gross coal. As a result of increased contact times and temperatures, the conversion-6/ and yield of hydrocarbon gas increased, the viscosity of product oil decreased, and elimination of oxygen, nitrogen, and sulfur from coal increased. The yield of oil did not indicate any definite trend with changes in temperature and contact time. The yield of oil ranged from 76 to 85 pct. for Pittsburgh coal and from 60 to 85 pct. for Rock Springs coal. Asphaltenes in the product oil ranged from 17 to 38 pct. of the total oil for Pittsburgh coal and from 12 to 22 pct. for Rock Springs coal. Fuel oils meeting Bunker C or American Society for Testing Materials (ASTM) Grade 6 specifications were produced with Rock Springs coal at 0.2- to 1.0-hr. contact time and 440° to 480° C. and with Pittsburgh coal at 0.3- to 1.0-hr. contact time and 420° to 460° C. In the second series of experiments tin, nickel, iron, and zinc were evaluated as catalysts for the hydrogenation of Rock Springs coal to heavy fuel oil at 3,500 p.s.i.g. and 460° C. Using the apparent conversion of coal as criterion of catalyst activity, at a contact time of 0.45 hr. tin was the most effective catalyst; nickel and iron were nearly as effective, but the use of zinc resulted in much lower conversion. When the contact time was increased to 0.80 hr., the apparent conversion of coal was essentially the same for each of the catalysts. When the yield of oil boiling below 3550 C. was used as criterion of catalyst activity, at 0.45 hr. the order of activity was tin, iron, nickel, and zinc; at 0.80 hr. tin was far superior and the others were essentially equal. The product oils contained from 8 to 20 pct. asphaltenes.

Jan 1, 1960

By K. C. Dean

A semiquantitative test for the presence and identification of cesium and rubidium in rocks, clays, and mineral waters has been developed by the Bureau of Mines. The test can be used in the field, as a guide for the prospector, geologist, or mining engineer engaged in location or development [w]ork. It comprises two simple spot tests of a solution prepared from the [m]ineral sample. Phosphomolybdic acid, added to a drop of the test solution, [d]etects cesium, rubidium, and potassium in quantities as low as 60 parts per [m]illion. Silicomolybdic acid, added to a second drop of test solution, enables the operator to distinguish between cesium and/or rubidium and potassium. Test procedures, equipment requirements, and limitations of the method are described in this report. Cesium and rubidium were discovered in 1860 and 1861 by Bunsen and Kirchhoff with a spectroscope. The elements usually occur together, particularly in granite and granitic pegmatites. Rubidium does not occur as an essential constituent of any known mineral, yet it is found as a minor element in so many minerals that rubidium is 16th in abundance in the earth's crust. Cesium, which ranks as the 37th most abundant element, is the principal component of pollucite and a minor element in a wide variety of minerals.

Jan 1, 1960

By Alla D. Mah

No experimental heat-of-formation value has been reported in the literature for cerium sesquioxide. The heat of formation of bismuth sesquioxide has not been determined in recent years, and the older value was subject to large uncertainty. Accordingly, the heats of combustion of cerium sesquioxide and bismuth metal were measured by the Federal Bureau of Mines. The heats of formation were: ?H°298.15 = -427.01 ± 0.70 kcal. /mole for cerium sesquioxide and ?H°298.15 = -137.16 ± 0.30 kcal./mole for bismuth sesquioxide. The free energy of formation was estimated for cerium sesquioxide and accurately calculated for bismuth sesquioxide. The data were compared with values in the literature.

Jan 1, 1961

By E. C. Tarpley

The Federal Bureau of Mines has studied solvent extraction as a means of concentrating the mineral components in coal. Solubilities of a number of American coals were determined using abietic acid as a solvent. The effect of rank on solubility was investigated, and maximum solubility was found with coals of intermediate rank. Vitrinite is the most soluble petrographic component; fusinite, micrinitc, and exinite are nearly insoluble. Spore exines also have a low solubility. Abietic acid is a hydrogen donor and reduces pyrite to ferrous sulfide. Mild hydrogenation of high-molecular-weight fragments of the coal structure to those of lower molecular-weight probably contributes to the solvent action. Even where solubility of the coal substance exceeds 90 percent, contamination of the mineral matter with coal makes identification of the mineral components difficult. Further separation might be possible by the application of float and sink techniques to the residue. INTRODUCTION Work n the solvent extraction of coal is conducted to recover commercially useful products and to characterize coal;. and obtain information on their structure. Some coals, particularly those of low rank, contain waxes, resins, and humic acids which can be removed by solvent extraction and find varied industrial uses. In World War II, solvent extraction of coal was conducted on a commercial scale in Germany to obtain a low-ash feed material for hydrogenation and to produce electrodes carbon for the aluminum industry.4 5/

Jan 1, 1960