Search Documents

By Mary H. Brown

The heats of formation of oxalic acid and sodium, potassium oxalates, and lithium oxalates were related by solution calorimetry to the heat of formation of (COOH)2.2H20, a value believed to be reliable as reported in the literature. The following heats of formation were determined: (COOH)2(a), -198.1±0.1; (COOH)2(ß), -197.8±0.1; UAW,, -328.7±0.4; Na2C204 -316.2±0.1; K2C204, -321.9±0.2; and K2C204-H20, -393.5±0.2 kcal/mole. The heat of the crystalline transformation (COOH)2(a) ? (COOH)2(ß) was determined to be 0.30±0.02 kcal/mole at 298.15° K.

Jan 1, 1970

By Elizabeth A. Johnson

The vaporization thermodynamics of the aluminum-silicon carbides Al4SiC4 and Al8SiC7 were studied by the Bureau of Mines over the temperature range of approximately 1,500 to 1,700 K. Vapor pressures were measured by a Knudsen effusion-mass spectrometry technique in which powdered samples were effused from graphite crucibles through small orifices. For each compound, a total of six orifice diameters was tested to verify equilibrium within the cell. Aluminum, mass number 27, was the only vapor species detected over the range 4 to 200 amu. Experimental results are based on the following equations for incongruent decomposition: A14SiC4(cr) - 4A1(g) + SiC(a,hex) + 3C(gr); Al8SiC7(cr) - 8A1(g) + SiC(a,hex) + 6C(gr). The observed vapor pressure-temperature relationships determined with a cell orifice area of 2.0 x 10-3 cm2 for Al4SiC4 and 1.81 x 10-3 cm2 for A18SiC7 are the following: Log P - (-18,682/T) + 12.476, for Al4SiC4 (1,550 to 1,643 K) and Log P = (-19,308/T) + 12.421, for Al8SiC7 (1,526 to 1,784 K), with P in pascals and T in kelvins. Third-law analysis of the data provided the following heats of formation: A14SiC4 ?H at 298.15 K - -50.0 kcal/mol and A18SiC7 ?H at 298.15 K - -92.1 kcal/mol.

Jan 1, 2011

By L. B. Pankratz

High-temperature heat-content values of pure lutetium sesquioxide and dysprosium sesquioxide were measured over the temperature range from 298° to 1,800° K. Similar data for cerium sesquioxide were calculated from measurements of a mixture of cerium sesquioxide and dioxide and known values for cerium dioxide. The results for lutetium sesquioxide are regular. Dysprosium sesquioxide has a minor thermal anomaly near 1,590° K, the extra heat absorption being 220 cal/mole, Hexagonal cerium sesquioxide undergoes a transformation around 1,050° K, which is only slowly reversible; consequently results were obtained for both the low- and high-temperature varieties. The original heat-content data are reported, and smooth values of heat content and the corresponding entropy increments are tabulated. Equations were derived to represent the heat-content values.

Jan 1, 1963

By G. H. Keith

The Bureau of Mines determined the mechanism(s) involved in observed anomalous changes in mechanical properties of vanadium-base alloys. Tensile properties of electrorefined and commercial-purity vanadium-base alloys containing up to 5 atomic percent molybdenum or titanium were measured between 77° and 673° K. Snoek oxygen and nitrogen peak heights were measured to determine the changes in dissolved interstitial content caused by increasing quantities of solute. In addition, changes in lattice parameter were followed wit: precision X-ray techniques. Softening, observed in alloys containing titanium, is explained by the formation of a second-phase titanium compound with oxygen or nitrogen. However, because of partitioning of titanium between compound formation and solid solution formation, about five times the stoichiometric amount was required for complete reaction. Addition of 1 percent titanium drastically lowered the strengthening due to strain aging, at 673° K, and 2 percent titanium essentially eliminated it. All alloys were ductile at 77° K. Variations in the tensile properties of the molybdenum-containing alloys are explained by variations in the amounts of interstitial impurities present. The molybdenum did not react with these impurities and had no effect on strengthening due to strain aging. Commercial-purity vanadium alloys containing more than 2 percent molybdenum were brittle at 77° K.

Jan 1, 1969

By Larry A. Haas

The Bureau of Mines constructed a torsion effusion apparatus to measure the equilibrium vapor pressure of pure metals, alloys, and compounds at temperatures up to 1,500° K. The reliability of the apparatus was established by determining the vapor pressure of silver. The data obtained on solid and liquid silver in the temperature range 1,200° to 1,500° K can be expressed by the following equations:

Jan 1, 1965

By J. M. Stuve

Low-temperature adiabatic heat-capacity determinations were made by the Bureau of Mines in the temperature range from 5 to 300 K for the two crystalline modifications of zinc sulfide, sphalerite (ß) and wurtzite (a). The entropy at 298.15 K of sphalerite was evaluated as l4.02±0.04 cal/deg mole and wurtzite, l4.06±0.04 cal/deg mole.

Jan 1, 1974

By K. K. Kelley, W. W. Weller

This report contains experimentally determined heat capacity data for four crystalline sulfides -- AsS , GeS , NiS , and Ni3 S₂ -- over the temperature range from 50 ° to 298.15 ° K. The heat capacity data were used to evaluate the entropies of the sulfides at 298.15 ° K. Entropies of formation from the metals and rhombic sulfur and from the metals and diatomic sulfur gas are also included .

Jan 1, 1964

By G. L. Humphrey

Although silicon carbide has been an important manufacture refractory for many years, knowledge of its thermodynamic values has been seriously lacking. In fact, some of the very properties that make it a useful substance, particularly chemical inertness, obstruct determination of its heats of formation and reaction. This paper reports the results of new measurements of the heats of combustion and formation, low-temperature heat capacity, entropy at 298.16°K., and heat-content and entropy increments between 298° and l,800°K. Two varieties of silicon carbide were studied -the common, hexagonal (type II) and cubic. The data are combined to obtain heat and free-energy-of-formation functions, which are given in tabular form. It is shown that the cubic variety is the more stable at temperatures to at least 1,800°K but, because of the inherent difficulties and errors in the heat-of-formation determinations at 298°K, it was not found possible to specify the free-energy difference accurately. The mechanism of silicon carbide formation from silica and carbon is not known and is not ascertainable from thermodynamic data. It appears improbable, however, that it can be a single-step reaction. Some reactions involving silicon monoxide gas and metallic Silicon, as possible intermediates in silicon carbide formation, are considered and shown to be thermodynamically feasible.

Jan 1, 1952

By E. G. King

Existing thermodynamic data for compounds of the rare-earth metals are few in number and often inaccurate because, in the past, it was difficult to obtain samples that were pure enough and reasonable in cost--a situation that is rapidly improving. This paper reports the results of low-temperature heat-capacity and high-temperature heat-content measurements for cerous fluoride (CeF3) and supplies the first such published data for a rare-earth fluoride. The low-temperature heat-capacity data cover the temperature range 51°-298° K. and serve to evaluate the entropy at 298.15° K. The high-temperature heat-content data cover the temperature range 298°-1,799° K., including the temperature and heat of fusion. The results are assembled for ready use in thermodynamic calculations. Cerous fluoride is one of the important intermediate compounds in the production of cerium metal.

Jan 1, 1959

By E. G. King

Cerium and thorium sulfides have found use as crucible materials for melting certain radioactive metals. However, thermodynamic treatment of these sulfides has been hampered by lack of experimentally derived entropy values. This Bureau of Mines report describes heat-capacity measurements between 51° and 298° K, and entropy evaluations at 298.15° K, for cerium monosulfide (CeS), cerium sesquisulfide (Ce2S3), and thorium disulfide (THS2). The entropy values, with Literature results for the heats of formation, are used to obtain free energies of formation at 298.15°K. MATERIALS The samples used in this work were supplied by Prof, Leo Brewer of the Department of Chemistry, University of California. The methods of preparation and some of the physical and chemical properties of these sulfides were given by Eastman and coworkers.3 4/ Chemical analyses, conducted in our laboratory, gave the following results:

Jan 1, 1959

By W. W. Weller

Heat-capacity measurements of sodium dimolybdate (Na2Mo207) and sodium ditungstate (Na2W207) were conducted over the temperature range from 51° to 298° K. The entropies of the two compounds at 298.15° K were calculated from the heat-capacity values and were used, in conjunction with other entropy data, to evaluate the entropies of formation of the compounds from their constituent elements and oxides.

Jan 1, 1963

By W. W. Weller

Low-temperature heat capacity measurements were conducted, and entropies at 298.15° K were evaluated for sodium monomolybdate (Na2Mo04), magnesium monomolybdate (MgMo04), and calcium monomolybdate (CaMo04). The 298.15° K entropy values were sodium monomolybdate, 38.1±0.3 cal/deg mole, magnesium monomolybdate, 28.4±0.2 cal/deg mole, and calcium monomolybdate, 29.3±0.2 cal/deg mole.

Jan 1, 1963

By D. A. Paice, A. B. Shimp

Illegitimate loads on a mine dc power distribution system can be detected by measuring a superimposed ac current. To implement such a scheme, a 10-volt, 3-kHz voltage is applied at each dc power substation. By this means, the mine dc power distribution network, consisting of a feeder and trolley wires with a grounded rail return, is caused to serve also as a 3-kHz ac distribution network.

Jan 1, 1975

By L. W. Brandt

As part of its objective to expand the body of mineral information as a basis for new technology, the Bureau of Mines conducted research on the fundamental behavior exhibited by phosphate clay waste in settling ponds. A semiempirical equation used to describe the compaction of ceramic powders in a single-acting die was applied to aqueous phosphatic clay waste and attapulgite slurries. This equation, [*V = a1 e ?k1/P + a2e ? k2/P] was found to describe the compaction of an attapulgite gel and a phosphate slime gel by a moving screen. [*V] is the ratio of the compaction achieved at a given pressure, P, to the compaction achieved at a pres-sure sufficient to remove all space between particles. The constant al represents the fraction of compaction achieved at low pressure by rearrangement of floes to higher packing density, and a2 represents the fraction of compaction achieved at higher pressure resulting from removal of voids within floes. K1 and K2 are constants determined from the experimental data. Both the low-pressure and high-pressure compaction mechanisms were observed in the compaction of the clays. These two compaction mechanisms offer an explanation for the observation that impounded slimes initially dewater rapidly and then dewater at a much slower rate.

Jan 1, 1982

By Rollie P. Dobyns

The K.M.A. reservoir was discovered to be oil bearing at a depth of 3,719 feet on March 11, 1931. Extensive development, however, was not begun immediately, because the discovery well had a low initial daily oil production, and market conditions for oil were unfavorable. Development of the field progressed slowly for the next 6.5 years. In the latter part of 1937, a wildcat well approximately 2 miles southwest of the discovery well was drilled on a magnetometer high and completed with an initial flowing production of 2,018 barrels of 430 A.P.I.-gravity oil in 12 hours. Rapid development of the southwestern part of the K.M.A. field was begun immediately and continued until over 700 wells were drilled and approximately 12,500 acres proved oil productive. Because of the large size of the entire K.M.A. field, this report is limited in scope to the southwestern part only, and the discussion that follows pertains to this area only. The closing date for production statistics is August 1, 1949. The K.M.A.? structure is a complex anticline having a maximum closure of 250 feet, and the K.M.A. formation is composed of sediments that grade from limestone through sandy lime and limy sand to sandstone with thin streaks of shale. Two "distinct members of the K.M.A. formation, zone I and zone II, are oil productive. Core analyses indicate the average porosity to be 16.5 percent for zone I and 16.1 percent for zone II. A relationship was established from core data, which showed the correlative permeabilities to be 42.1 millidarcys for zone I and 39.5 millidarcys for zone II, whereas the arithmetical averages of the permeabilities were 84 millidarcys for zone I and 216 millidarcys for zone II. Connate-water saturations were 17.5 percent for zone I and 20.0 percent for zone II. The porosity-saturation method, using a thickness-correction factor, was employed to calculate the volume of 168.1 million barrels of stock-tank oil initially in place in the reservoir. Analyses of the reservoir oil indicate that, although the initial reservoir pressure was 1,750 p.s.i., the original reservoir oil was saturated to only 1,300 p.s.i., at which pressure 1 barrel of stock-tank oil contained 525 cubic feet of ea~ in solution.

Jan 1, 1952

By Arthur B. Johnson

The Bureau of Mines investigated the concentration characteristics of high-clay sylvinite ores from four potash companies operating in the Permian Basin near Carlsbad, N. Mex. These ores, containing 13 to 22 percent K20 and 3 to 7 percent clay slimes, cannot be effectively processed by current commercial flotation methods because of their high slime content. A solution to this problem was shown to be the use of two-stage moderate scrubbing conditions and washing of the ore as opposed to strenuous attritioning. Bench-scale physical beneficiation techniques for recovering potash minerals and the development of ore-dressing systems by flotation resulted in obtaining acceptable product grades and recoveries. By using a coarse grind, emphasis was placed on production of premium granular and coarse products. Flotation results showed that concentrates of 58.7 to 60.4 percent K20 with recoveries of 71.0 to 83.4 percent 0f the K20 values can be obtained.

Jan 1, 1971

By L. B. Pankratz

High-temperature heat-content values of gallium and scandium sesquioxides were measured over the temperature range from 298° to 1,800° K. The results fill gaps in the thermodynamic information for these compounds; no previous similar data existed. The heat-content values were combined with heats and entropies of formation to obtain free energies of formation of gallium and scandium sesquioxides to 2,000° K. The thermodynamic stabilities of the sesquioxides of aluminum, gallium, scandim, and yttrium were compared.

Jan 1, 1963

By J. E. Urosek, K. L. Cashdollar, D. A. Beiter, G. J. Shemon

The National Institute for Occupational Safety and Health (NIOSH) and the Mine Safety and Health Administration (MSHA) conducted joint research to evaluate explosion blast effects on mine ventilation stoppings at the NIOSH Lake Lynn Experimental Mine (LLEM). After mine explosion accidents, MSHA conducts investigations to determine the cause(s) as a means to mitigate or eliminate future occurrences. As part of these post-explosion investigations, the condition of underground stoppings, including the debris from damaged stoppings, are documented as evidence of the strength and the direction of the explosion forces. The LLEM data showed that a total pressure of 52 kPa (7.6 psi) destroyed the solid concrete block stopping, ~36 kPa (~5.2 psi) destroyed the hollow-core concrete block stopping, and 9 kPa (1.3 psi) destroyed the steel panel stopping. These results will assist investigators in determining the explosion forces that destroy or damage stoppings during actual coal mine explosions.

By Seth C. Schaefer

The Bureau of Mines studied thermodynamic properties of Al-Ni alloys con¬taining 0.54 to 30.04 atomic percent nickel with the aid of the high-temperature galvanic cell Al(1) // Al+3 (AlCl3 in NaCI.KC1) // Al-Ni alloy (1 or s). Activities of aluminum and nickel (compared with pure liquid metals as the standard state) show pronounced negative deviation from Raoult's law at 1,273 K. The properties [?G, ?Gxs, ?G ideal, ?GA1, AGxs1, ?Gni , and ?GNixs] have been derived from the experimental data and are summarized in tables and illustrations. At 1,127 K, the thermodynamic stability for the invariant three-phase equilibrium consisting of a saturated liquid, A13Ni, and A13Ni2 has been uniquely defined by an activity for aluminum of 0.751. A free energy of formation at 1,127 K of -7,940 cal/g-atom was derived for the compound A13Ni.

Jan 1, 1975

"SUMMARYThe K.M.A. reservoir was discovered to be oil bearing at a depth of 3,719 feet on March 11, 1931. Extensive development, however, was not begun immediately, because the discovery well had a low initial daily oil production, and market conditions for oil were unfavorable. Development of the field progressed slowly for the next 6 1/2 years. In the latter part of 1937, a wildcat well approximately 2 miles southwest of the discovery well was drilled on a magnetometer high and completed with an initial flowing production of 2,016 barrels of 43° A.P.I.-gravity oil in 12 hours. Rapid development of the southwestern part of the K.M.A. field was begun immediately and continued until over 700 wells were drilled and approximately 12,500 acres proved oil productive.Because of the large size of the entire K.M.A. field, this report is limited in scope to the southwestern part only, and the discussion that follows pertains to this area only. The closing date for production statistics is August 1, 1949.The K.M.A. structure is a complex anticline having a maximum closure of 250 feet, and the K.M.A. formation is composed of sediments that grade from limestone through sandy lime and limy sand to sandstone with thin streaks of shale. Two distinct members of the K.M.A. formation, zone I and zone II, are oil productive. Core analyses indicate the average porosity to be 16.5 percent for zone I and 16.1 percent for zone II. A relationship was established from core data, which showed the correlative permeabilities to be 42.1 millidarcys for zone I and 39.5 millidarcys for zone II, whereas the arithmetical averages of the permeabilities were 84 millidarcys for zone I and 216 millidarcys for zone II. Connate water saturations were 17.5 percent for zone I and 20.0 percent for zone II. The porosity-saturation method, using a thickness-correction factor, was employed to calculate the volume c 168.1 million barrels of stock-tank oil initially in place in the reservoir. Analyses of the reservoir oilIn that, although the initial reservoir pressure was 1,750 p.s.i., the original reservoir oil was saturated to only 1,300 at which pressure 1 barrel of stock,tank oil contained 525 cubic feet of gas in solution.A serious decline in reservoir pressure during the 2 years of rapid development alarmed the operators and caused them to consider a cooperative pressure-maintenance program. In the latter part of 1939, the K.M.A. Pressure Maintenance Association was organized, and the gasoline plants in the field agreed to process the wet gas and return the dry gas to leases having gas-injection wells. Approximately 27 percent of the cumulative volume of produced gas had been returned to the reservoir by August 1, 1949."

Jun 1, 1952