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By M. J. Ferrante

Relative enthalpies of high-purity disodium hexatitanate (Na2Ti6013) were measured at the Bureau of Mines to provide new thermodynamic data needed to advance the technology of materials. Measurements from 298.15 to 1,478 K were made by drop calorimetry with a copper block. Tabulated values are listed for the standard relative enthalpy, heat capacity, en-tropy, and Gibbs energy function between 298.15 and 1,500 K. Enthalpy data are also given in equation form and are combined with thermodynamic data from the literature to derive values of standard enthalpies of formation, Gibbs energies of formation, and logarithms of the equilibrium constants of formation. Similar calculations were made for the reaction of Na20 with Ti02.

Jan 1, 1986

By D. A. Stanley

The Bureau of Mines is investigating a method of dewatering flocculated fine-particle waste that involves treating the waste with a high molecular-weight polymer such as polyethylene oxide (PED) followed by dewatering on a static screen and/or in a trommel. Dilution of the polymer solution used for dewatering and use of the ion-exchanged form of the montmorillonite clay were found to be major factors determining the amount of polymer required to dewater clay-containing slurries. The amount of polymer, A, required to dewater ion-exchanged montmorillonite can be described by the equation, An = kC + b where n, k, and b are empirical constants and C is the concentration of the polymer solution used for dewatering. Clays that require large amounts of polymer for dewatering also dewater to a lower solids content. The concentration of the polymer solution is important because it affects the radius of the polymer coil in solution and hence its ease of transfer to a bridging configuration by shear. The constant, n, a function of the charge to hydrated radius of the exchange ion, relates to the strength of the bond between the polymer and the surface of the clay through a water bridge. The constant k is related to the hydrated radi-us for sodium or to the unhydrated radius for the other exchange ions.

Jan 1, 1986

RI 9527. Effective Hazard Recognition Training Using a Latent-Image, Three-Dimensional Slide Simulation Exercise, by E.A. Barrett and K.M. Kowalski. Pittsburgh, PA: U.S. Department of the Interior, Bureau of Mines, 1995. NTIS stock number: PB95-170379. Rl 9531). Computer Modeling and Analysis of The Greens Creek Mine, Admiralty Island, AK, by MJ. Beus and T.J. Orr. Spokane. WA. -U.S. Department of the Interior, Bureau of Mines. 1995. NTIS stock number: PB95-176418. RI 9600. Application of Field Measurements and Computer Modeling to Evaluate Deep Mine Shaft Stability in Northern Idaho, by M, J. Beus, T. J. Orr and J. K Whyatt. Spokane, WA: U.S. Department of the Inferior. Bureau of Minus. 1996. NTIS stock number: PB96-140181. [ ]

Jan 1, 1995

By K. K. Kelley

Sodium-aluminum and potassium-aluminum silicates are among the more important rock-forming minerals of the earth's crust. They also appear as constituents of some metallurgical slags and of some refractory materials. Consequently, knowledge of their thermodynamic properties is interesting and valuable from several viewpoints. This paper reports experimental determinations of the low-temperature heat capacities and entropies at 298.16° K. of albite, jadeite, and nephelite it the sodium-aluminum silicate series and of adularia, ferriferous orthoclase, leucite and kaliophilite in the potassium-aluminum silicate series. Also high-temperature heat-content and entropy increments about 298.16° K. are reported for albite, jadeite, nephelite, and carnegieite in the sodium-aluminum silicate series. Except for a few high-temperature heat-content values for albite, all these data are available for the first time.

Jan 1, 1953

By Alla D. Mah

Titanium forms several compounds with oxygen and also is able to dissolve interstitially about 33 atomic percent of oxygen. Starting with titanium dioxide, reduction becomes increasingly difficult as oxygen is removed; and the final step, be reduction of the titanium-oxygen interstitial solutions, is by far the most difficult. The possibility of reducing titanium oxide, or of purifying titanium containing oxygen, by treatment with certain more volatile metals has been a subject of considerable interest. Theoretical appraisal of the limitations of this possibility, however, has been hampered by lack of adequate information on the thermodynamic properties of the titanium-oxygen solutions. The purpose of the present work was to remedy this difficulty by expanding the thermodynamic knowledge regarding these solutions. The experimental work involved three types of calorimetry and furnished the following information: (1) Heats of formation of 11 titanium-oxygen solutions, in the range of 0 to 10 wt.-percent oxygen, were determined at 298.15° K. As a byproduct, an improved value of the heat of formation of rutile was obtained, which, in turn, led to improved values of the heats of formation of the lower titanium-oxygen compounds. (2) Low-temperature heat-capacity data and entropies at 298.15°K in were determined for 2 representative titanium-oxygen interstitial solutions. (3) High-temperature heat-content data were obtained for 2 titanium-oxygen interstitial solutions to about 1,600° K.

Jan 1, 1957

By E. G. King

Thermodynamic data for the hydrated varieties of alumina are sparse, and those for the common clay minerals are virtually nil. This paper partly fills the vacuum by reporting low-temperature heat-capacity measurements and entropy evaluations of diaspore (A10(OH)) and three clay minerals of the composition A12Si207?2H20 - kaolinite, dickite, and halloysite. The heat-capacity measurements were made in the temperature range 510 to 298.15° K., and the entropies were evaluated at 298.15° K. Diaspore has an unusually low heat capacity and entropy compared with boehmite (another mineral of the same chemical composition). The entropies of the three clay minerals differ too little for entropy to be the important factor relating to differences in the thermal stability of these substances.

Jan 1, 1961

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 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 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 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 Clifford B. Farris

The natural cementation strength of retorted oil shale is the focus of this investigation. The optimum retorting temperature and residence time to obtain natural cementation strength in retorted Green River oil shale from western Colorado were determined as follows: [Optimum Conditions for Natural Cementation Maximum Residence Obtained Retorting Time at Compressive Mode of Temperature Temperature Strength' Retorting °F °C hr psikg/cm-2 Direct 1,520 822 2.0 270 19.0 Indirect 1,530 832 2.9 325 22.8] 1 Scattered samples were tested at strengths as high as 463 psi (32.6 k /cm 2) (Run 8, indirect mode) and 406 psi (28.5 kg/cm2) (Run 48, direct mode), but these high strengths were not confirmed by nearby tests. Minus 0.5-inch (1.3-cm) Green River oil shale was heated in a differential retort under conditions simulating potential full-scale retorting processes. The variables investigated were retorting temperature, residence time, retorting mode, and shale grade. Samples of the retorted Green River oil shale were moistened to optimum plus 2% (25%) moisture, compacted to 95% Proctor density, sealed and cured at 100°F (38° C) for up to 40 days. Lower curing temperatures, which are likely in the field, would probably result in significantly slower development of cementation strength, and might lower the ultimate strength developed. However, these effects were not studied in this project. The cured samples were tested for compressive strength, and correlative equations were developed for the increase of compressive strength with curing time as a function of retorting temperatures and residence time. Petrographic analysis indicated that the cementing mechanisms may be the interlocking growth of acicular hydrated calcium aluminum sulfate crystals between the contacts of retorted shale fragments. Samples of the retorted shale were also tested for optimum Proctor density and moisture. Permeability and quality of the leachate of shale from typical runs were determined. The effect of use of retort rather than tap water on compressive strength and leachate after curing was determined. The retorted shale effectively filtered several mineral constituents from the retort water.

Jan 1, 1979

An examination of the Census of Fatal Occupational Injuries (CFOI) data for the period 1992-1995 shows that 659 fatalities occurred in the mining industry as defined by the SIC. Oil and gas accounted for slightly more than one-half of all fatalities (figure 1-1). The coal industry had the highest fatality rate for the 4-year period, with 35.6 deaths per 100,000 full-time workers, followed by metal (23.1 per 100,000), oil and gas (23.1 per 100,000), and nonmetal (20.1 per 100,000). The fatality rate for all U. S. industries during this same period was 5.1 per 100,000 full-time workers. Figure 1-2 compares the fatal injury rates by year for the four major industry sectors of mining to the fatality rate for all industries combined. Figure 1-3 compares age-specific fatality rates in the mining industry to those seen for U. S. industry as a whole. Fatality rates for all industries combined were lowest for young workers and steadily increased in relation to workers' ages. In the mining industry, fatality rates by age group show a U-shaped curve. Young workers under 20 years of age had the highest injury rate (54.6 per 100,000), followed by workers aged 20-24 (50.8 per 100,000) and workers over age 65 (37.7 per 100,000). Table 1-1 shows the distribution of injuries by type of injury event. The mining industry, in comparison with all industries, had a considerably larger proportion of fatalities classified as caught in or crushed by collapsing materials (9.1% and 1.9%, respectively) and fires and explosions (10.0% and 3.1%, respectively). Transportation events comprised the largest proportion of fatal injuries in both the mining industry and all industries. Within the mining industry only, transportation accounted for the largest proportion of fatalities in all mining sectors except coal. A more detailed examination of the transportation events within the mining industry showed that highway incidents (50.5%) were the most common, followed by nonhighway incidents (22.2%), pedestrian incidents (10.6%), and those incurred during rail, water, and air transport (15.7%). Incidents involving caught in or crushed by collapsing materials comprised a higher percentage of injuries in the coal and metal sectors, while fall-from-height incidents were more frequent in the oil and gas sector. The classification system used in CFOI for type of injury event is not compatible with any variables contained in the MSHA data; therefore, direct comparisons are not attempted. [ ]

Jan 5, 2000

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 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 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 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 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 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 R. V. Ramani, C. B. Manula, A. Owili-Eger

ANALYTICAL PRESSURE - VOLUME COMPUTATIONS FOR THE MINE PROTOTYPE A new coal mine is projected, with entrance by slope 1,500 feet long. Nine main entries will be standard for development, five as intake and four as return. One return shaft is planned near the slope bottom, and an intake shaft and portal are planned 5,000 feet north of the slope bottom. The slope will have an area of 150 square feet and a perimeter of 55 feet. A belt and supply track will be within the slope. The return shaft will be circular with a diameter of 18 feet and will be 500 feet deep with an escapeway. Two hundred feet of the shaft and 500 feet of the slope will be concrete lined. Select the fan to operate five units per shift and drive the 5,000 feet to a proposed new portal, using the slope for an intake. Two main splits are planned with the maximum of three units on any split. The amount of air desired at each unit is 25,000 c.f.m; a shop at the slope bottom will require 10,000 c.f.m. In the solution of this or any similar problem, the first step is to determine the resistance factors. CALCULATION OF R FACTORS Slope area = 150 sq. ft.; Perimeter = 55 feet; Length = 1,500 feet. The friction factor K must be established. Five hundred feet of the slope is smooth lined, moderately obstructed by belt; K = 35. The remaining 1000 feet is in sedimentary rock and moderately obstructed; K = 85.

Jan 1, 1975