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By James R. Welty

Heat content values were experimentally determined for yttrium metal between temperatures of 400° and 1,300° K and for iron pentacarbonyl between 301° and 380° K. The drop technique was used; that is, a sample of material sealed in a protective capsule was heated to 3 desired temperature in a furnace and then dropped into an ice calorimeter. A revised technique for determining heat content values from calorimetric data is described. Heat content and corresponding entropy-increment data above a reference temperature of 298.15° K are presented in tabular form. Equations for heat content and heat capacity as functions of temperature were derived for each substance. These equations are [Y (c): HT-H298.15 = 1.2041T 1 3.393 x 10-3T2- 0.4176 x 10' T"1 + 739.9 cal/mole Cp = 1.2041 + 6.786 x 10-3T + 0.4176 x 106-T-2 cal/deg mole Fe (CO) E, (1) : HT - H298.15 = 55.636T - 16,588 cal/mole Cp = 55.636 cal/deg mole]

Jan 1, 1963

By A. R. Taylor

Low-temperature heat capacities of cesium chloride (7° - 300° K) and cesium iodide (13° - 300°K) were measured with an adiabatic calorimeter. The heat-capacity measurements were analyzed graphically to determine smooth values of heat capacity, entropy, enthalpy function, and free-energy function at 10° K intervals and at 273.15° and 298.15° K.

Jan 1, 1963

By Charles Prasky

This report describes and appraises recent progress in the development of a differential sulfatizing process for recovering a ferrograde manganese oxide from low-grade manganiferous ferruginous materials in the Cuyuna range. Individual process steps were carried out successfully using a 20-inch-diameter shaft for continuous countercurrent sulfatization of the manganese, a multiple-compartment rotary drum for leaching the water-soluble manganese sulfate, a submerged-combustion evaporator for the recovery of monohydrate crystals of manganese sulfate, and a shaft furnace for the thermal decomposition of sulfate crystals for production of a ferrograde manganese oxide and a sulfur dioxide gas suitable for sulfatization of fresh are. Of the two general kinds of Cuyuna manganiferous materials--the carbonate slates and the oxidized ores--only the slates were studied at pilot scale.

Jan 1, 1963

By M. M. Wong

Electrolysis of titanium carbide and a material consisting of titanium, carbon, nitrogen, and oxygen as soluble anodes in Used electrolytes was investigated by the Bureau of Mines for the preparation of crude titanium metal. Tests made in all-chloride electrolytes showed only a low recovery of titanium as well as a substantial volatilization of titanium trichloride (TiC13) when present in the electrolyte. Electrolysis at 750° to 850° C in a mixture containing 85 percent NaC1-15 percent potassium floutitanate (K2TiF6) yielded as high as 91 percent recovery of titanium from titanium carbide and 62 percent recovery of titanium from the titanium-carbon-nitrogen-oxygen material. Problems associated with the preparation of crude metal by fused-salt electrolysis are discussed. The crude metals produced from both anode materials were electrorefined in a sodium chloride-titanium chloride (NaCl-TiC12) electrolyte, and ductile titanium metal was obtained.

Jan 1, 1963

By T. A. Henrie

A technique was devised for measuring the rate of chemical reactions between reactive metals and molten-salt mixtures at high temperatures. The rate of the heterogeneous reaction between high-purity titanium metal and titanium trichloride in molten sodium chloride was determined. The reaction is surface-controlled, and the heat of activation is 8.29 kilocalories per mole TiC13. An active site or reaction nuclei is created by adsorbing a TiC13 molecule at the metal surface. Reaction of the second TiC13 species forms an activated complex that decomposes into three TiC12 molecules.

Jan 1, 1963

By James H. Gary

Data regarding the composition and physical properties of Florida land-pebble phosphate-waste slime are presented, and the feasibility of dewatering and beneficiating the slime by several different methods is discussed. Chemical analyses, electron micrographs, and X-ray diffraction data showed that principal constituents of the slime included quartz, attapulgite, and flaorapatite. Viscosity of the slime changed with pH; thixotropic, Newtonian, and rheopectic states were observed as the pH increased. Use of various flocculating agents was not effective in improving thickening properties of the slime. Dewatering tests using pressure filtration showed that temperature influenced the filtration rate more than pressure; the filtration rate at 165° C was tenfold that at room temperature. Selective flotation of the slime, using two different processes, gave promising results. About 25 pct of the phosphate was recovered in a concentrate assaying 31 pct P205, Other tests demonstrated that the slime could be successfully fractionated at 20-microns using a hydrocyclone. In hydrometallurgical tests about 80 pct of the phosphorus and alumina were chemically extracted from the slime using sulfuric acid. Limited bacteriological studies made of the slime showed that several types of microorganisms were present and grew in the material despite the presence of fluorine-bearing minerals.

Jan 1, 1963

By G. T. Krempasky

In an attempt to develop a suitable precast concrete support for underground use, two different models (1955 and 1958) of a five-piece concrete set were designed, fabricated, and tested under adverse loading conditions. Model 1955 was designed to withstand an ultimate, uniformly distributed, vertical load equivalent to what a three-piece, 12- by 12-inch wood set of intermediate-grade Douglas fir would withstand. A design figure of 138,000 pounds for the vertical load was used on both the 1955 and 1958 models. In addition, the 1958 model was designed to withstand a uniform horizontal load of 7,000 pounds per foot and additional concentrated-point loading. The step- by-step design of each model is presented in the appendixes. A series of five destruction tests was conducted underground on the 1955 model, and results of the tests showed that the type and method of blocking were of major significance.

Jan 1, 1963

By William C. Miller

This report describes investigations by the Bureau of Mines designed to establish the noise level and spectrum of various types of pneumatic rock drills and to furnish information that would be useful in conducting sound measurements in mining environments and in reducing the noise generated in pneumatic drilling. These investigations show that (1) the noise generated by the drills in the frequencies below 100 cps is caused by the impact of the piston and drill steel, in the frequency range between 100 and 2,000 cps by the exhausting of air from the ports, and in the frequencies above 2,000 cps by the resonant frequencies of steel drill parts and of drill steel; (2) satisfactory instruments and instrumentation systems are available for field and laboratory measurements; (3) reliable sound measurements can be made in mining environments; and (4) devices can be developed that will abate the noise.

Jan 1, 1963

By W. E. Robinson

Samples of raw oil shale and kerogen concentrates were oxidized by alkaline potassium permanganate, air, nitric acid, oxygen, and ozone to obtain information about the chemical structure of organic kerogen in oil shale. In one test, oil shale and oil-shale products were oxidized exhaustively with alkaline potassium permanganate, and the distribution of the organic carbon in the final oxidation products was determined. Comparing results of this oxidation with those obtained from other carbonaceous materials and known compounds gave information about the structure of kerogen. Alkaline potassium permanganate oxidation also was used partly to degrade kerogen into soluble products for characterization purposes. Structures present in these degradation products were indicative of type structures originally present in the kerogen. Nitric acid, oxygen, and ozone were used also for partly degrading kerogen to soluble oxidation products. Carbon-balance oxidation tests using alkaline potassium permanganate showed that Colorado oil-shale kerogen differs from many other carbonaceous materials such as coal and kerogens from other areas. Composition of the degradation products indicated that Colorado oil-shale kerogen is predominantly cycloparaffinic and saturated heterocyclic structures with some long-chain paraffinic and aromatic structures present. The ring systems may be connected through short carbon chains or bridges containing oxygen, nitrogen, and sulfur.

Jan 1, 1963

By M. E. Hawkins

Mineral analyses and electrical resistivity measurements of 324 representative samples of oilfield brines from 24 oil-productive counties in Mississippi and Alabama are presented in tabular form. Results of the mineral analyses, which include calcium, magnesium, carbonates, bicarbonates, sulfates, chlorides, sodium, and barium (with strontium if present), are reported in milligrams per liter. Electrical resistivity measurements in ohm-meter2 per meter at 75° F are reported in ohm-meters in the tables. Chemical analyses of formation waters are helpful to operators having water problems associated with petroleum recovery; electrical resistivity values are helpful in making interpretations from electric logs.

Jan 1, 1963

By David J. Kusler

A gravimetric method for the determination of carbon dioxide, carbon monoxide, hydrogen, methane, and oxygen in blast furnace top gas is described. Nitrogen may be determined directly by volume measurement or by difference. The method is direct, permits continuous as sampling, and provides an averaged analysis over a selected range of sampling intervals from 1/2 to 24 hr or more. Neither expensive equipment nor specialized personnel are required. The method is suitable for routine analysis, and the results compare favorably with those obtained by established methods.

Jan 1, 1963

By Albert J. Rambosek

The results obtained in a study of the stress conditions existing in a drill bit-point area and in the underlying rock, when the bit was in full but nonpenetrative contact with the rock, are presented. This investigation by the Bureau of Mines was the preliminary exploratory phase of a long-range program of research on rock drilling to establish criteria for the maximum economically feasible rate of rock penetration. The photoelastic technique of experimental stress analysis was the principal method used to obtain the data. Transparent models and transmitted light were employed to investigate patterns in drill-bit models and isotropic materials under the bit when subjected to a concentrated static load. Comparative stress data for anisotropic rock were obtained by the reflective photoelastic technique. Brittle lacquer and an extensometer were used obtain supplementary information wherever substantiating data were desired to check photoelastic results. The zone of maximum shear occurs along an arc near the contact face of the bit. The stress distribution pattern in an isotropic model rock near the area contacted by the bit was nearly a mirror image of that exhibited within a similar areal zone of the bit. The stress pattern in granodiorite specimens was similar, though not symmetric, to the pattern in the isotropic model rock. The asymmetry of the stress pattern in the granodiorite was attributed to the anisotropic characteristics of the constituent minerals of various sizes.

Jan 1, 1963

By R. L. Crosby

The effect of indium on the solid solubility of calcium and of silicon in magnesium was studied using metallographic, X-ray diffraction, and electrical resistivity techniques. The addition of 2 weight-percent or more of indium reduced the solid solubility of calcium in magnesium by forming a compound containing indium and calcium. Indium additions have no perceptible effect on the solid solubility of silicon in magnesium.

Jan 1, 1963

By Alla D. Mah

Combustion energies of barium and strontium were measured by means of the combustion bomb calorimeter. The heats of formation obtained for the oxides were ?H298.15 = -139,060 ± 700 cal/mole of barium oxide (BaO) and ?H298.15 = -144,440 ± 400 cal/mole of strontium oxide (SrO). Tables containing heats and free energies of formation from 298.15° to 2,000° K were prepared.

Jan 1, 1963

By Laird Crocker

This report describes a study of beryllium recovery from sulfate leach liquor by di-2-ethylhexyl phosphate (EHPA) solvent extraction in conjunction with caustic stripping. The work was one phase of Bureau of Mines research on process development for Spor Mountain, Utah, ores. Solution for the solvent extraction studies was prepared by sulfuric acid leaching of ore containing 0.6 pet BeO, Before solvent extraction of beryllium, the leach liquor was treated to prevent coextraetion of iron by either (1) removal of ferric iron by amine solvent extraction or (2) reduction of ferric iron to nonextractable ferrous iron by treatment with sulfur dioxide. Beryllim was extracted from the aqueous leach liquor by countercurrent multistage contacting with a kerosine solution of EHPA. The loaded organic solution was stripped with sodim hydroxide solution. Subsequently, beryllium hydroxide was precipitated by boiling the sodium beryllate strip solution and converted to beryllium oxide of 98 pct BeO-grade by calcining. Material of this grade can be directly processed into beryllium-copper alloy or be used as starting material for further refining to produce high-purity, nuclear-grade beryllium. Over 90 pct of the beryllium contained in the leach liquor was recovered as beryllia.

Jan 1, 1963

By Sara Jane Boles

The purpose of this Bureau of Mines investigation was primarily to isolate and examine the effect of liquid content upon the apparent porosity and bulk density of compacts pressed from high-purity, fused aluminum oxide, and, secondarily, to study the actual mechanism by which the liquid content affects the bulk density. No attempt was made to approach the theoretical maximum density of the oxide by introducing additives, particle packings, or similar variables; instead this study is an intercomparison of the bulk densities obtained as functions of the water contents of the compacting mixtures. Water content was varied from 7 percent to 25 percent, on a total-weight basis. The data gathered indicated a well-defined optimum water content for obtaining minimum apparent porosity and maximum bulk density, under the conditions of the experiment. During the course of this study, a number of additional variables in the forming process were discovered and are introduced in this report, although a thorough evaluation was found to be beyond the scope of this present investigation.

Jan 1, 1963

By L. B. Pankratz

The heat contents of the sesquioxides of erbium, holmium, thulium, and ytterbium (Er203, Ho203, Tm203, and Yb203) in the cubic crystalline form were measured over the temperature range from 298° to 1,800° K. The erbium and holmium sesquioxides gave regular heat content-temperature curves. Thulium sesquioxide had a minor thermal anomaly near 1,680° K, with a heat absorption of 310 cal/mole; similarly, ytterbium sesquioxide had a minor anomaly near 1,365° K, with a heat absorption of 150 cal/mole. The heat content results are presented in both tabular form (at 100° intervals) and in algebraic form. Entropy increments, corresponding to the tabulated heat content results, also are listed.

Jan 1, 1963

By Alla D. Mah

Energies of combustion of vanadium nitride (VN) and vanadium carbide (VC) were measured. Correcting to vanadium tetroxide (V204) as the final state, the heats of combustion were ?H298.15=-118,700±100 cal/mole of vanadium nitride and ?H298.15=-240,270±360 cal/mole of vanadium carbide. With vanadium pentoxide (V205) as the final state, the heats of combustion were ?H298.15= -133.440±100 cal/mole of vanadium nitride and ?H298.15=-255,020±360 cal/mole of vanadium carbide. Combining these results with vanadium oxide data, the heats of formation obtained were ?298.15=-51,880±200 cal/mole of vanadium nitride and ?H298.15=-24,350±400 cal/mole of vanadium carbide. Heats and free energies of formation of vanadium nitride and carbide were calculated to 2,000° K.

Jan 1, 1963

By W. J. Boone

Experimental determinations were made of vapor-liquid equilibria data for a helium-nitrogen-methane system. A mixture composition was chosen to approximate the crude helium to be produced Or conservation that will eventually be further refined to obtain pure helium. Although there are publications of studies of the vapor-liquid equilibria of helium-nitrogen, helium-methane, and nitrogen-methane binary systems, there is little indication of work done on the ternary system of helium-nitrogen-methane. The experimental data presented in this report supplement the information available for the binary systems. The equilibrium vapor-liquid data and equilibrium vaporization coefficients are presented in tabular form. Graphs are employed to show an extensive amount of the data.

Jan 1, 1963

By Walter Kawa

The hydrogenation of phenyl ether, benzyl ether, and phenyl sulfide in the presence of iron catalysts was studied by the Bureau of Mines to gain a better understanding of the role of iron catalysts in the hydrogenation of coal. The carbon-oxygen and carbon-sulfur bonds in these compounds may be similar to some of the carbon-oxygen and carbon-sulfur bonds in coal which react during the early stages of liquefaction by hydrogenation. Experiments were made in batch autoclaves for 4 hours; hydrogen was at a pressure of about 540 atmospheres. In the hydrogenation of phenyl ether at 400° C, metallic iron catalyzed both hydrogenolysis (splitting-hydrogenation) and nuclear hydrogenation (addition of hydrogen to aromatic rings) reactions, Products were principally benzene and cyclohexane. The activity of metallic iron was decreased by adding carbon monoxide or a reactive sulfur-containing organic compound. Ferrous sulfide catalyzed the conversion of phenyl ether to benzene, phenol, and small amounts of cyclohexane. Hydrogenolysis of benzyl ether was catalyzed by metallic iron and to a lesser extent, by ferrous sulfide at 250° C. No nuclear hydrogenation was observed with either catalyst. Conversion of phenyl sulfide to benzene was nearly quantitative in experiments made at 250° C with equimolar quantities of phenyl sulfide and metallic iron or iron as ferric oxide. Conversions of metallic iron and ferric oxide to ferrous sulfide were nearly stoichiometric. No reaction of phenyl sulfide occurred in the presence of ferric oxide and water, and very little occurred in the presence of metallic iron and water. Ferrous sulfide also catalyzed the hydrogenolysis of phenyl sulfide to benzene, but conversion was lower than in experiments with metallic iron or ferric oxide. The activity of ferrous sulfide was increased by adding water and decreased by adding hydrogen sulfide. The results of this study suggest that ferrous sulfide is an active form of iron when iron is used as a catalyst for the hydrogenation of coal.

Jan 1, 1963