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By R. Barany

This report contains the results of experimental work conducted by the Bureau of Mines to obtain the heats of formation at 298.15° K. of analcite, dehydrated analcite, lawsonite, anorthite, hexagonal anorthite, and leonhardite. Thermodynamic data for these minerals have applications in ceramics, extractive metallurgy, and particularly in geochemistry. Except for data on anorthite, no previous similar data existed. The present results will be a substantial aid in deriving the temperature-pressure-equilibrium relationships among these minerals. The heats of formation were determined by solution calorimetry, with hydrofluoric acid as the reaction medium. The results were expressed both in terms of the constituent oxides and in terms of the constituent elements. The heat of formation data were combined with related entropy values to obtain the free energies of formation at 298.15° K.

Jan 1, 1962

By Donna D. Harbuck

The Bureau of Mines has investigated a process to produce titanium powder directly from titanium salts. If successful, such a process could lower the cost and increase the use of titanium. In this study, K2TiF6, K2TiF3, and TiF3 were reduced with potassium in the temperature range of 650° to 750° C. Under certain conditions, titanium powder 1.6 to 3.3 microns in size was produced. After leaching the product with a 0.1M HCl solution, powder impurities as low as 0.04 pct potassium and 0.28 pct fluorine were obtained. However, oxygen levels of over 1 pct and the frequent formation of insoluble byproducts demonstrate the need for further research to make the powder suitable for powder metallurgy applications.

Jan 1, 2011

By W. W. Weller

This report provides low-temperature heat-capacity data and entropies at 298.15° K. for magnesium metavanadate (MgV206) and magnesium pyrovanadate (Mg2V207). The work completes low-temperature measurements planned for alkaline-earth vanadates; an earlier report dealt with calcium vanadates.4 No similar data for these compounds have been published previously. Free energy of formation values at 298.15° K. were derived by combination of the present entropy values with heat of formation data. MATERIALS The materials used in the measurements were portions of the samples described in a previous Bureau of Mines publication by King, Koehler and Adami.5 Methods of preparation, chemical analyses, and X-ray examinations are covered in this paper. The indicated purity of the samples was 99.9 pct.

Jan 1, 1962

By Seth C. Schaefer

As part of the Bureau of Mines, U.S. Department of the Interior, effort to provide thermodynamic data for the advancement of minerals technology, the Gibbs energy of formation of sphalerite (zinc sulfide) was investigated with a high-temperature galvanic cell employing stabilized zirconia as the electrolyte. In the temperature range 948 to 1,210 K, potential measurements were obtained for the cell Pt, ZnS + ZnO, S02 = 1 atm // Zr02 // Cu20 + Cu, Pt, with the overall cell reaction ZnS(c) + 3 Cu20(c) = ZnO(c) + 6 Cu(c) + S02(g). (1) These results, combined with the best available values of ?Gf° for ZnO, S02, and Cu20 from the literature, give the Gibbs energy of formation of zinc sulfide for the reaction Zn(l,v) + 1/2 S2(g) = ZnS© (2) ?Gf° = -64.223 + 24.02 X 10-3T ± 0.650 kcal/mole (3) (948-1,180 K; standard states - pure liquid zinc and S2 gas at 1 atm), and ?Gf° = -92.720 + 48.17 X 10-3 ± 0.650 kcal/mole (1,180-1,210 K; standard states - pure zinc vapor and S2 gas at 1 atm). A third law analysis yields for the formation reaction Zn(1) + 1/2 S2(g) = ZnS(c), (5) a standard enthalpy of formation as follows: ?Hf298.15 = -63.64 ± 0.700 kcal/mole.

Jan 1, 1978

By E. F. Foerster

The Bureau of Mines used a diphenyl ether calorimeter to determine the heat contents of natural and synthetic blast-furnace slags. For solid slags, enthalpy (HT-H298) at 1,448° to 1,680° K ranged from 282.1 to 348.5 cal/g (±3 percent); liquid slag values were 400.1 to 514 cal/g (±3 percent) in the temperature range between 1,626° and 1,890° K. Experimental results for liquid slags were 14.3 to 16.2 percent higher than the enthalpies calculated from thermodynamic tables; values for solid slags ranged from 5.3 percent lower to 3.9 percent higher than calculated values. Experimental results for liquid synthetic slags ranged from 14.9 to 24.3 percent higher than the calculated enthalpies; values for solid synthetic slags were from 1.0 to 3.4 percent higher.

Jan 1, 1967

By J. M. Stuve

In this Bureau of Mines investigation, the low-temperature heat capacities of polycrystalline phases corresponding to the sulfide compounds CoSO?89' CoS1?33, and CoS2 were measured by adiabatic calorimetry within the nominal temperature range 5 to 300 K. The derived absolute entropies S298 were 10.36±O.02, 12.96±O.03, and 16.31±O.03 cal?mol-1?K-l, respectively, assuming third-law behavior. In addition, the standard enthalpy of formation 8Hf298 of CoSO?89 was determined by bromine solution calorimetry. The derived value of 8Hf298 was -50.63±2.1 kcal?mol-1, based on the 8Hf298 of Co0. This result is considerably more negative than previously published formation values based on high-temperature gas equilibrium studies.

Jan 1, 1985

By Gerald V. Gibbs

As a part of the Bureau of Mines long-range program in asbestos, synthetic asbestiform compounds and minerals were prepared and described. Fundamental structural data on two such compounds are given in this report. Crystallographic data are provided for the synthetic isotypic compounds potassium-lead silicate, K2.Pb4 -Si8021 (I), and lead-aluminum silicate, Pb2. Pb4 .Al2Si6O21 (II). The space group symmetry 14/mmm was assigned provisionally to I and II on evidence of single crystal and piezoelectric measurements. A statistical evalua¬tion of indexed powder diffraction data revealed the cell edtes of I to be a 11.816 and c 7.932A and those of II to be a 11.723 and c 8.044A. The phases are uniaxial with observed refractive indices eD 1.790, an ?D,699 and eD 1.884, cusp 1,807, respectively. The atomic structure of I and II may be based on a complex of chains of silicon-oxygen tetrahedra lying along the c cell edge similar to the type of chain structure postulated by Pauling for scapolite. K2.Pb4.Si8021 and Pb2.Pb4 Al2Si6021 were first described by Geller and Bunting (5, 6)4 as fibrous compounds similar in crystal habit to asbestos. These authors gave powder diffraction data, although no attempt was made to find the cell edges or to index the powder diffraction patterns. Later, Shell and others (9) conducted a crystallochemical study of these fibrous silicates in search of a substitute for strategic asbestos. Their single crystal data revealed K2.Pb4 -Si8021 to be tetragonal body-centered with cell edges a 11.66, c 7.95 A. Pb2.Pb4 Al2Si6021 was concluded to be isotypic with K2.Pb4 -Si8021 on the basis of similar powder diffraction patterns, chemistry, and physical properties. No attempt was made, however, to index the powder diffraction record nor to determine the appropriate space group of either compound.

Jan 1, 1962

By R. A. Franks, G. F. Friel, J. C. Edwards, L. Yuan

Two mine-fire experiments were conducted in the National Institute for Occupational Safety and Health's (NIOSH) Safety Research Coal Mine (SRCM) at the Pittsburgh Research Laboratory (PRL) which demonstrated that smoke from diesel-fuel fires of 500 kW and 660 kW heat-release rates in a return airway can develop, without causing a complete air flow reversal, into a roof layer that can migrate upwind forming a counter flow to the primary airflow in a crosscut. Subsequently, smoke can penetrate into an intake airway and create a hazardous atmosphere in the intake airway upwind from the fire. Visibility conditions less than 13 m were created by the smoke in the intake airway downwind from the crosscut. Modeling of the event with a three-dimensional, time-dependent, computational fluid dynamics (CFD) program correctly represented the smoke movement.

By Arnold B. Hubbard

A thermal decomposition study of the kerogen in three Colorado oil shales was made at different temperatures by heating the shales in the absence of oxygen at atmospheric pressure and measuring the decomposition products (gas, oil, and bitumen) formed. From these data the specific reaction rates, "k", for the thermal decomposition of kerogen were determined for each temperature studied, making it possible to calculate the time required to accomplish a given amount of decomposition within the temperature range. The influence of temperature on reaction rates was presented by plotting the data according to the Arrhenius equation, thus providing a means of estimating the values of "k" for any temperature within the range of this study. It was found that the specific reaction rates for the thermal decomposition of the kerogen in the three sampler were comparatively equal at corresponding temperatures.

Jan 1, 1950

By F. K. Shelton, J. C. Stah, Ruth E. Churchward

A study of the hydrometallurgy and electrowinning of cobalt from various domestic ores has been in progress at the Boulder City, Nevada, Experiment Station since February 1940. Previous reports covering certain phases of this investigation have been published. This report covers the research and pilot-plant work on the production of cobalt metal from cobalt-copper ores from the initial experimental work on crude ore through continuous operation. The ore types were from the Blackbird District, Lemhi County, Idaho. The initial tests were made with concentrated ore which was received by air mail and these experiments were expanded both in size and scope. After the laboratory was continued, improved, and extended tests were reported. Sufficiently advanced, a continuously operated plant producing 250 pounds of electrolytic cobalt per day was operated from June 15 through July 15, 1944.

Jan 1, 1948

By K. J. Liles

The Federal Bureau of Mines conducts a comprehensive test program on clay and shale at the Tuscaloosa Metallurgy Research Center. All samples are subjected to standard preliminary ceramic tests, which include firing formed briquets at temperatures ranging from 1,000° to 1,250° C to identify firing range and colors, and quick-firing to determine bloating characteristics. Materials that shop potential as structural products are further tested after either extrusion or dry-pressing. If the quick-fire test is positive, bulk samples can be fired in a rotary kiln to evaluate their potential as light- weight aggregate A number of miscellaneous tests also can be conducted if requested. These tests determine properties such as refractoriness (pyrometric cone equivalency), oil-bleaching characteristics, oil absorbency, viscosity for drilling-mud applications, sand-bonding properties for foundry usage, and pelletizing characteristics.

Jan 1, 1977

By Henry E. Blake

The purpose of this Bureau of Mines investigation was twofold. The first phase of the work was to determine the technical and mechanical feasibility of defluorinating low-grade siliceous fluorspars on an intermediate scale by high-temperature pyrohydrolysis in a rotary kiln. The second phase was to react the liberated hydrogen fluoride (HF) offgas with alumina monohydrate to produce commercial-grade aluminum fluoride (85 percent AIF3). The two phases of the work were to be integrated into a single continuous process. Evaluation of the data shows that low-grade siliceous fluorspars can be successfully defluorinated, either in a solid or a molten state, in a gas-fired rotary kiln in the presence of water vapor at 1,250° to 1,350° C. The water produced by combustion of propane was sufficient to yield defluorinatians of 75 to 85 percent.

Jan 1, 1962

By R. E. Lindstrom

Effective separation of rare-earth mixtures is obtained using hydrogen as a retaining ion at 200° F with ethylenediaminetetraacetic acid (EDTA) eluant. Results obtained in Bureau of Mines bench-scale apparatus and large columns with hydrogen as a retaining ion closely parallel those obtained with copper as a retaining ion. The use of hydrogen as a retaining ion permits EDTA and water, collected before rare-earth breakthrough, to be recovered in a form that allows the material to be recycled without extensive processing. With the exception of yttrium and dysprosium, separation of rare-earth mixtures is improved and throughput is increased by elevated temperatures. Separation with 1,2-diaminocyclohexanetetraacetic acid (DCTA) eluant increases markedly on increasing temperature from ambient to 250° F; however, on the basis of separation efficiency, DCTA does not compare favorably with EDTA.

Jan 1, 1962

By Ann G. Kim, Thomas R. Justin, John F. Miller

The U.S. Bureau of Mines applied its mine fire diagnostic method to an abandoned anthracite mine fire site in Carbondale, Lackawanna County, PA. The technique to locate fires in abandoned coal mines and coal refuse piles includes the determination of hydrocarbon concentrations in mine gases, the imposition of an underground gas flow direction, and use of a surface mapping method, to define heated and cold zones in underground coal strata. The heated zones at Carbondale were characterized by elevated methane concentrations. The results of 25 communication tests were analyzed to define 2 large (approximately 100 by 250 ft) and 5 small, isolated heated zones. An approximate correlation existed between the location of the heated zones and areas of anomalous snow melt. The correlation between the results of the diagnostic test and subsurface temperatures was not significant.

Jan 1, 1992

By Ann G. Kim

The U.S. Bureau of Mines applied its mine fire diagnostic method to an abandoned anthracite mine fire site in Carbondale, Lackawanna County, P A. The technique to locate fires in abandoned coal mines and coal refuse piles includes the determination of hydrocarbon concentrations in mine gases, the imposition of an underground gas flow direction, and use of a surface mapping method, to define heated and cold zones in underground coal strata. The heated zones at Carbondale were characterized by elevated methane concentrations. The results of 25 communication tests were analyzed to define 2 large (approximately 100 by 250 ft) and 5 small, isolated heated zones. An approximate correlation existed between the location of the heated zones and areas of anomalous snow melt. The correlation between the results of the diagnostic? test and subsurface temperatures was not significant.

Jan 1, 2010

By G. A. Smyres

A GaC12--B2 l-eachtng procedure and meEal-recovery method for treating an arsenical Cu-Co sulfide concentrate was developed by the Bureau of Mines as an alternative to smelting, which is no longer considered an environmentally acceptable method for treating arsenic-containing ores. The procedure involved leaching in a CaC12 solution with CaC03 for 96 h at 26 pct solids (concentrate and CaC03), 1150 C, and a pressure of 50 psig (345 kPa) with oxygen. More than 98 pct of the cobalt and 97 pct of the copper were extracted, and 99.98 pct of the arsenic and 99.9 pct of the iron remained in the leached residue. A filtration rate of 2.9 gal/(ft2.h) [118 L/(m2.h)] and a cake formation rate of 36 Ib/(ft2.h) [172 kg/(m2.h)] were obtained by filtering reacted pulp at 1000 C. More than 99 pct of the copper in the pregnant solution was extracted as CuCl2 by golvent extraction with a new copper extractant. Copper was stripped from the loaded organic with a sulfate-chloride solution, which was used as the anolyte for electrowinning of copper in a membrane cell. Copper plate produced was more than 99.99 pct pure and requi.red 0.81 (kW'h)/lb Cu [1.78 (kW·h)/kg Cu]. Cobalt sulfide was precipitated at pH 3 with Ca(HS)2.

Jan 1, 1986

By F. Fraas, H. H. Storch

"In the second paper 4 of this series, data were presented concerning the decomposi¬tion of polyhalite by saturated salt solutions. It was found that uncalcined polyhalite upon leaching with boiling saturated sodium chloride solutions yielded a brine in which the (K2 Mg) /304 ratio was considerably higher than that obtained from the calcined material, and for this reason appeared more suitable for the production of potassium chloride. It was found, in fact, that the leach liquors from uncalcined polyhalite deposited a mixture of KC1 and NaC1 upon evaporation and subsequent cooling, whereas those from calcined polyhalite yielded mixtures which contained not only potassium and sodium chlorides but also large quantities of glaserite, K3Na (S04)2. Hence it was decided to study the evaporation of the uncalcined poly—halite leach liquor and postpone experiments on the calcined polyhalite liquors until such time as a process for further removal of sulphate was developed.A considerable body of equilibrium data is available in the literature on thesystem K+ Mg++ — Na+ Cl—S04 =,— H20 for temperatures up to 83º C. Owing, however, tothe lack of data other than that corresponding to the invariant points and the complete absence of data for temperatures of 100 to 115°C., and owing to the fact that supersaturation phenomena render unsafe the prediction of the behavior of such a system upon evaporation, it was considered essential to obtain the necessary data by actual evaporation and analysis of the brines thus obtained."

Feb 1, 1931

By D. G. Foot

The Bureau of Mines investigated two methods for recovering potash from carnallite ore in continuous 100-lb/h flotation units. In the insoluble-slimes flotation procedure, insoluble slimes were removed by flotation prior to potash flotation. In the direct flotation method, insoluble slimes were depressed and the potash floated directly without prior removal of the insoluble slimes. Seventy-three percent of the potash in the ore was recovered in a leached final KCl product contain-ing 59.1 pet K20 using the insoluble-slimes flotation method. The direct flotation method recovered 74.5 pct of the potash in a final product containing 60.2 pet K20. The rate of return on the investment was calculated at 13 pct for the insoluble-slimes flotation method and 15 pct for the direct flotation method, based on a Bureau economic evaluation.

Jan 1, 1984

By A. R. Taylor

This report describes the design, construction, and operation of a low temperature adiabatic calorimeter for measuring heat capacities of solids or liquids from 60° to 300° K. A brief discussion of the basic theory involved in chemical thermodynamics and the problems involved in obtaining accurate experimental data is presented. The operation of the calorimeter was tested by measuring the heat capacity of a sample of benzoic acid obtained from the National Bureau of Standards over a temperature range of 60° to 300° K. The measured heat capacity values of the benzoic acid compared favorably with similar values obtained by the Bureau of Standards, the maximum deviation being 0.5 percent. THEORY A brief discussion of the basic theory involved in chemical thermodynamics will illustrate the applications of heat capacity data and the problems involved in obtaining accurate experimental data.

Jan 1, 1962

By Vance G. Leak

A technique for recovering copper and steel from metallic scrap has been developed by the Bureau of Mines based on preferential melting in molten salt baths at 1,150° to 1,250° C, The molten salt, preferably barium chloride or calcium chloride, both minimizes oxidation of the metals and promotes heat transfer. Cleanest separations (0.01 percent copper remaining in iron) have been achieved by pretreatment (dipping or spraying) with sodium sulphate or sodium silicate, which alters and coats the surface of the iron to inhibit the alloying or brazing with copper. An economic evaluation of the process was carried out on six combinations of sweating media and inhibiting reagents. On the basis of the postulated model, a cost of about $0.20 per pound of copper recovered has been determined for the sweating treatment operation.

Jan 1, 1973