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By J. E. Murphy

The Bureau of Mines developed a hydrometallurgical method for recovering mercury metal from mercury sulfide concentrates. Sulfide flotation concentrate from the McDermitt Mine was leached in a cupric chloride solution at 80° C. The redox potential of the solution was maintained at 850 mV during leaching by chlorine sparging. Mercury extractions exceeded 99 pct in 3 h of leaching. After leaching, the pH of the solu-tion was increased from 1 to 4.5 to precipitate copper as atacamite. The pregnant solution typically containing 100 giL Hg was sent to elec-trolysis to produce high-purity mercury metal and chlorine for recycle. In a 200-A electrolytic cell operated for 24 h, current efficiency was 99 pct and the energy requirement was 0.9 kW·h/lb of mercury produced. Mercury removal from the waste stream was also investigated. Iron or zinc cementation, sulfide precipitation with H2S, and activated carbon adsorption all decreased the mercury concentration from 10 giL to 0.01 mglL, which is less than the Environmental Protection Agency limit on wastewater of 0.02 mg/L.

Jan 1, 1987

By Nicholas Kyriazi, John P. Shubilla

The National Institute for Occupational Safety and Health, National Personal Protective Technology Laboratory, has undertaken a study to determine how well self-contained self-rescuers (SCSRs), deployed in accordance with Federal regulations (30 CFR 75.1714), hold up in the underground environment with regard to both physical damage and aging. This report presents findings regarding laboratory-tested SCSRs in the seventh phase of testing from May 1999 to August 2000. The SCSRs were tested on human subjects and on a breathing and metabolic simulator. The results indicate that most of the apparatus, if they pass their approved inspection criteria, perform satisfactorily. The deployed CSE SR-100s, however, exhibited significantly higher inhaled carbon dioxide (CO2) levels than new units, as they did in the previous two phases. Several Draeger OXY K-Pluses that rattled when shaken were found to have potassium superoxide (KO2) particles throughout the breathing circuit, including the mouthpiece. Draeger investigated the problem and developed a shake test to detect damaged units. The durations of new Ocenco M-20s were statistically significantly longer than those of deployed units, although only by 2 min.

Jan 3, 2002

By Richard J. Mainiero, Michael J. Sapko, James H. Rowland III, Marcia L. Harris

All explosive materials produce a cloud of reaction products, the most toxic of which is nitrogen dioxide (NO2). In the study reported here, 4.5-kg (10-lb) charges of blasting agent confined in either thin-wall 10-cm (4-in) diameter galvanized pipe or 10-cm (4-in) schedule 80 seamless steel pipe were detonated in a closed chamber. The detonation gases were analyzed for NO2, nitric oxide (NO), ammonia (NH3), hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), nitrogen (N2), oxygen (O2), and methane (CH4). Data were evaluated to determine the kinetics of the oxidation of NO to NO2. Analysis revealed that the only mechanism for NO loss for the conditions existing in the chamber was the reaction 2NO + O2 6 2 NO2. The rate constant was 2.08 @ 10-38 cm6 molecules-2 sec-1 for the rate equation -½d [NO]/dt = K @ [NO]2 @ [O2] for NO concentrations up to 100 ppm. The rate constant is in agreement with that recommended by Baulch, Drysdale, and Horne (1973).

By C. A. Komar

The Bureau of Mines conducted oil-displacement tests in the laboratory with three water-in-oil and five oil-in-water emulsions that were created with ultrasonic energy at a frequency of 20 kHz and an acoustic intensity of approximately 100 watts per cm2. Emulsions of either crude oil or kerosine, brine, and 112 to 2 percent emulsifier were formed during 30 seconds of acoustic irradiation. Results indicate that ultrasonic energy induces greater and more uniform dispersion of one liquid in another in the presence of small amounts of chemi¬cal emulsifiers. When the emulsions were injected as a buffer slug before waterflooding, recovery of the oil-in-place was 8 to 22 percent greater than with conventional waterflooding in the test specimens, regardless of the con¬tinuous phase (oil or brine). The emulsions do not appear to be applicable to the Appalachian area; however, because the oilfields are too "tight," the clays in the formation remove the emulsifier from the displacing fluid, and not enough additional oil is produced, compared with recovery using conventional waterflooding, to warrant the increased operating costs.

Jan 1, 1969

By K. K. Kelley, L. B. Pankratz, W. W. Weller

The heat capacity of columbium (niobium) carbide (CbC ) was measured over the temperature range from 51 ° to 298 ° K, and the entropy at 298.15° K was evaluated . Also , the heat content above 298.15 ° K of columbium carbide was measured to 1,800 ° K. The results were combined with the known heat of formation at 298.15 ° K to obtain values of the heat and free energy of formation over the temperature range from 298.15 ° K to 2,000 ° K.

Jan 1, 1964

By Stanley C. Rhoads

The Bureau of Mines investigated the complete ternary system K2 HfF6¬K2ZrF6-l.25 weight-percent HF at 40° C. In addition, solubility curves have been established at 25°, 30°, 500, 60°, and 70° C. These solubility data implemented a study of hafnium enrichment in feed solutions for liquid-liquid extraction processes.. Selected K2HfF6-K2 ZrF6-1.25 weight-percent HF mixtures were equilibrated in a constant temperature bath. Compositions of the equilibrated solutions and wet residues were established from combined hafnium and zirconium oxide and total fluorine analyses. All solubility curves were essentially parallel on triangular coordinates. At 40° C, the solid phase of the K2HfF6-K2ZrF6-1.25 percent HF system is a series of solid solution hydrates with K2HfF6-H20 and K2ZrF6.3H2O segments existing at the respective extremes. Since this system contains K2HfF6-H20 and K2ZrF6.3H20 segments, it is not ideal for simple separation of high-purity K2HfF6 from K2HfF6-K2ZrF6 mixtures by recrystallization. However, it would be useful for producing hafnium-enriched feed solutions from zircon concentrates for liquid-liquid extraction of hafnium from zirconium.

Jan 1, 1973

By L. B. Pankratzt

The heat capacity of dimo1ybdenum carbide (Mo2C) was measured from 51° to 298° K, and the entropy at 298.15° K was evaluated. Heat content measurements above 298.15° It were conducted for dimolybdenum carbide (M0caY) and monotantalum carbide (TaC). The results were combined with known heats of formation and the 298.15° K entropy for TaC to obtain values of the heat and free energy of formation from 298.15° K to 1,400° K for MoaC and from 298.15°K to 1,800° K for TaC.

Jan 1, 1966

By Robert L. Lagace

[Suuple Iheorctrccil models are I'M lllolalcd to cltaraclerl/c medium frequency (MF) radio vase pi opaiation in undcrgiounli room arid pillar coal mines fur the purpose of predleiln the most lavolable operating fIegtucncics,md nr,ixunum communic;IIIoil ranges for pottahIe rldu)s with I top antennas. I or conductul IrCC areas, at hree layer propaeaIion IltodcI wit II a Iiallsmissloil IIIIi- lhlllllIIal'u11 lot the plupa!edti ii unlstallt Iris been dcvcloped ;md verified experimentally. 1 lie mode u1 propaCaUetl lakes Ills form of i parallel plane (0,t)) TIM lransnussu)nhne 1% PC of mode with the electric held vertical and the magnetic held hoti/cntal t itliin a planar coal scam in which the tunnels Can he ignored and which 1s hounded above and below hp richer conductivity rock. 1lie model lilt the data best river the 200 io 1000 kH/ frequency hand and exhibits a rc;;lon of optlnrul1l Pelffelntance, with respect Io maxnluiulg radio Communication range, between 300 and 100 klf/. Maximum cunununlcatrorl ranges are sliongls dependent oil the sigiial alleilliatroil sale, ant) Illelclulc on the electrical conductivltles of the coal seam and surrounding ruck. These ranges v;ny tutu about ,,5 Io 100 nleleis Ill a high Iuss scam such as the Ilelllit No. fl to about .100 to 400 meters in a low loss seam such as the Pittsburgh foil portable intrinsically safe radios. The ieslllls die haled on the comparison oftheorc' and experiment for eleven n n. ill sesen coal seams. V OT ate is dice: a conductor such as a power Cable, is present a model has been developed for the coupling of loop antennas to a low loss Coaxial TEM ti;u?smisslon line mode in which the cable acts as the inner conducl,lr and the rock above and below acts as the outer conductor. The electuc and md' nctic Itelds for till` (node are apprlixitllatcly transverse to the cahlC and fall oil expontially with distance in the transverse plane. The principle of reciprocity is used to simplify the analysis. More expelitnental data arc needed to help resolve discrepancies between the theory and the limited data available to date.]

Jan 1, 1980

By L. B. Pankratz

Enthalpies above 298° K were determined for AgCl to 1,400° K and for AgBr to 1,200° K by copper-block calorimetry. Before melting, both compounds showed an anomalous increase in enthalpy, an effect associated with lattice defect formation. Melting points and heats of fusion were determined to be AgCl, 730° K and 2,945 cal/mole; AgBr, 700° K and 2,030 cal/mole. The heat capacity of both melted substances decreased with increasing temperature over the entire liquid ranges investigated. Enthalpies above 298° K were tabulated at even temperatures along with derived entropy increments and heat capacity values. The results were combined with the known heats of formation and entropies at 29.8.15° K to obtain values of the heats and free energies of formation over the range 298.15° to 1,400° K for AgC1 and 298.15° to 1,200° K for AgBr.

Jan 1, 1970

By L. B. Pankratz

Present-day interest in the rare-earth elements and their compounds, for both metallurgical and ceramic uses, makes it highly desirable to accumulate basic thermodynamic data that can be applied to theoretical considerations of the processing of these substances. Such data still are seriously lacking. This Bureau of Mines paper reports the results of high-temperature heat content measurements of the sesquioxides of four rare-earth elements--europium, gadolinium, neodymium, and samarium--and of the closely related element, yttrium. The temperature ranges covered by the measurements are as follows: Monoclinic Eu2O3, 298°-1,802° K. Cubic Eu203, 298°-1,350° K. Monoclinic Gd203, 298-1,802° K. Cubic Gd203, 298°-1,550° K. Hexagonal Nd203, 298°-1,795° K. Monoclinic Sm203 298°-1,798° K. Cubic Sm203, 298°-1,149° K. Cubic Y203, 298°-1,799° K.

Jan 1, 1962

By L. B. Pankratzt

The heat content above 298.15° K of ferroelectric lithium columbate (LiCbO3) was measured to 1,770° K. The Curie temperature was determined to be 1,450° K, the melting point 1,540° K, and the heat of fusion 16.94 kcal/mole. Heat content and entropy increments have been tabulated for the temperature range from i98.15° to 1,800° K. Heat contents are also given in equation form.

Jan 1, 1966

By J. M. Stuve

The present Bureau of Mines investigation measured low-temperature heat capacities of NiBr2 (8 to 302 K) and NiS04 (9 to 70 K) by adiabatic calorimetry. The standard entropies (S°, 298.15 K) of NiBr2 and NiS04 were calculated as 29.26 ± 0.06 cal/deg mole and 24.21 0.04 cal/deg mole, respectively. (1 cal = 4.1840 joules.) Heat-of-solution measurements of anhydrous NiBr2 were used to determine its enthalpy of formation (?Hf°, 298.15 K) as -50.64 ± 0.31 kcal/mole. High-temperature enthalpies of NiBr2 and NiS04 were measured by drop calorimetry to 1,150 K and 1,002 K, respectively. Enthalpies, heat capacities, and related formation functions are tabulated to 1,200 K.

Jan 1, 1978

By L. B. Pankratz

High-temperature heat contents were measured for two praseodymium oxides and three terbium oxides. There were: Pr2O3 (298° to 1,600° K), PrO1.833 (298° to 1,050° K), Tb2O3 (298° to 1,600° K), TbO1.719 (298° to 880° K), and TbO1.812 (298° to 850° K). With the exception of PrOl.833, all results were regular. PrO1.833 had a small thermal anomaly at 760° K with an extra absorption of 380 cal/mole. The measured heat content values, tabulated smooth heat contents, and entropy increments are reported. Heat content equations were derived.

Jan 1, 1966

By A. R. Taylor Jr.

The heat capacities of a-quartz form beryllium fluoride were measured at approximately 3° intervals from 8° to 300° K., using an adiabatic calorimeter. At 298.15° K the heat capacity and entropy were 12.39 cal/deg mole and 12.75 ±0.04 eu respectively. Enthalpy measurements were made with an ice calorimeter at approximately 30° intervals on the quartz and glassy forms of beryllium fluoride between 300° and 1,200° K. A melting point of 825° K and an 0,-8 type transition at 500° K with a heat effect of 75 ca1/mole were deter-mined from the enthalpy data for the quartz-type sample. Beryllium fluoride glass crystallized spontaneously into the quartz modification at 500° K. The heat of the reaction BeF2 (a-quartz) .... BeF2 (glass) was found to be 1,125 ±16 cal/mole at 298° K by solution calorimetry. This value, when corrected to 273° K, was used to correct for the heat absorbed by the formation of glassy BeF2 when the sample was dropped into the ice calorimeter from temperatures above the melting point. Using corrected enthalpy measurements, the heat of fusion was determined to be 1.13 kcal/mole at 825° K.

Jan 1, 1965

By L. B. Pankratz

The Bureau of Mines conducted heat-content measurements above 298.15° K for dehydrated analcite (NaAISi2O6) to 1,000°K, kaliophilite (KA1Si04) to 1,800° K, and leucite (KAlSi206) to 1,800° K. Heat content and entropy increments were tabulated, and the heat content data, were given in equation form. A first order transition was noted for kaliophilite near 810° K with a heat absorption of 160 cal/mole. Leucite had a second order transition which became complete near 955° K. In this transition a crystal change occurred from tetragonal (low-temperature form) to cubic (high-temperature form).

Jan 1, 1968

By T. Estelle Gardner, A. R. Taylor

Heat capacity measurements were made on sodium bromide ( NaBr ) and sodium iodide ( NaI) in the temperature ranges of 7 ° to 300 ° K and 56 ° to 300 ° K using an adiabatic calorimeter . Smooth values of heat capacity, entropy , enthalpy function , and free- energy function were calculated from the heat capacity data at 10° K intervals and at 273.15° and 298.15° K. Entropy and free energy of formation values at 298.15° K also were calculated for the two compounds using entropy values determined in this study and other data reported in the literature . The entropy values calculated at 298.15 ° K were 20.75 ± 0.06 entropy units (eu ) for sodium bromide and 23.55 ± 0.07 eu for sodium iodide .

Jan 1, 1964

By B. B. Letson, D. F. Smith, T. E. Gardner, A. R. Taylor

Low- temperature heat capacities of strontium chloride (7° - 300° K) and strontium fluoride ( 11 ° - 300 ° K) were measured with an adiabatic calorimeter . Smooth values of heat capacity , entropy , enthalpy function , and free - energy function were calculated from the heat - capacity data . The smooth values are reported at 10 ° K intervals and at 273.15 ° and 298.15 ° K.

Jan 1, 1963

By L. B. Pankratz

Enthalpies above 298° K were investigated for four crystalline sodium borates by copper-block drop calorimetry. Determinations were made to 1,200° K for NaB02, 1,003° K for Na2B407, 1,005° K for NaB305, and 1,046° K for Na2Be013. No phase transitions or other thermal anomalies were found. The enthalpy determinations, when combined with known heats of formation at 298° K and other supplementary data, enabled the calculation of the heats and free energies of formation of the compounds to their melting points. Values of relative enthalpies, entropies, heat capacities, free energy functions, enthalpies of formation, free energies of formation, and equilibrium constants of formation were tabulated at even temperatures.

Jan 1, 1971

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 L. B. Pankratz

The Bureau of Mines measured heat capacities of alpha and beta spodumene (LiAlSi2O5) and of beta eucryptite (LiAlSiO4) over the temperature range 51° to 298° K. The entropies at 298° K were found to be 30.9 ± 0.2 cal/deg mole for alpha spodumene, 36.9 ± 0.3 cal/deg mole for beta spodumene, and 24.8±0.2 cal/deg mole for beta eucryptite. High-temperature heat content measurements above 298° K were conducted for the same compounds. Measurements were made to 1,150° K for alpha spodumene, 1,600° K for beta spodumene, and 1,470° K for beta eucryptite. Tables of heats and free energies of formation are given from the elements and from the constituent oxides.

Jan 1, 1967