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By A. R. Taylor

Using solution calorimetry, the following heats of reaction were determined: (1) NaCN(c) + 1/Cu20(c) + 129H20(l) ? CuCN(c) + NaOH?128.5H2O ?H = -13.44±0.10 kcal/mole, (2) HCN(2) + NaOH?128.5H20 ? NaCN(c) + 129.5H20(l) ? = -2.52±0.02 kcal/mole. From these reactions, the heats of formation for CuCN(c) and HCN(2) were calculated to be 22.7±0.4 kcal/mole and 24.9±0.4 kcal/mole, respectively. Reaction 2 was made to check the consistency of literature values for heats of formation of HCN and NaCN. Adiabatic calorimetric measurements between 10° and 400° K showed the entropy and heat capacity of CuCN(c) to be 21.51±0.06 eu and 14.58±0.04 cal/mole deg, respectively, at 298° K. A broad anomaly in the heat capacity was found in the temperature range 285°-320° K. The heat of transition associated with this anomaly was less than 1 cal/mole, the sensitivity of the measurements.

Jan 1, 1971

By Vance G. Leak

Leaching of manganese from low-grade Minnesota ores was studied over the temperature range 25° to 225° C at atmospheric and elevated pressures to demonstrate that good recoveries of manganese could be achieved from unroasted ores using reagents available nearby. Various combinations of ore, pyrite, lignite derivatives, and sulfuric acid were tested on a small scale. Pyrite alone required the highest temperature to effect a good extraction, but the combination of pyrite, lignite char, and sulfuric acid solubilized 99 percent of the manganese after 30 minutes of reaction at 75° C.

Jan 1, 1971

By H. E. Blake

An evaluation was made to determine the economics of utilizing waste fluosilicic acid for production of (1) calcium fluoride, and (2) anhydrous hydro-gen fluoride. Two versions of each process were considered and compared. The evaluation showed that both products could be produced and marketed competitively. Lowest estimated product sales prices required to yield a 25-percent return on investment before taxes (discounted cash flow basis) was $339.34 per ton of hydrogen fluoride and $48.64 per ton of calcium fluoride.

Jan 1, 1971

By David P. Lindroth

The heat content above 25.0° C up to 1,000° C was measured for six rock types: St. Cloud Gray Granodiorite, Holston Limestone, Sioux Quartzite, Rockville Quartz Monzonite, Salem Limestone, and the basalt at Dresser, Wis. The calorimetric data were obtained with an isothermal jacket-copper block calorimeter. The experimental heat content data for each rock type are presented, along with specific heat data obtained from the temperature derivative of the heat content. For the six rock types the maximum deviations of the specific heats at a given temperature were within 10 percent below 575° C and within 34 percent above 5750°C. The increase in the values of specific heat range from a minimum of 13 percent for the basalt at Dresser, Wis. (temperature range, 100° to 1,000° C) to a maximum of 46 percent for Holston Limestone (temperature range, 100° to 870° C).

Jan 1, 1971

By L. M. Adams

Experiments in reclaiming acidic surface-mined coal lands with raw fly ash from bituminous-coal-fired powerplants were conducted by the Bureau of Mines at two sites in northern West Virginia. Plots at both sites were treated with varying tonnages of fly ash from three area powerplants and were planted with a variety of grasses, legumes, trees, and shrubs. Eight grasses and seven legumes were investigated. Greatest promise for growth under harsh soil conditions was shown by Kentucky 31 fescue, rye and red top grasses, and birdsfoot trefoil, a legume. Survival of trees and shrubs was negligible. Addition of fly ash to the spoil increased the pH to a range tolerable to some types of plant growth, improved the texture of the soil, and increased the available water of the resulting mixture.

Jan 1, 1971

By Galen G. Waddell

This report describes a method of measuring and analyzing the initial deformation which occurs in the medium surrounding a mine accessway as the opening is created. Discussed are (1) the hypothesis upon which the research is based; (2) the in situ rock-deformation measuring equipment developed; (3) the field tests, consisting of measuring the deformation of the medium around two 4-foot-diameter raise bores as the boring progressed; and (4) a finite-element technique to correlate theoretical with experimental results, using elastic theory. Described also are the raise-bore operation and performance. The instrumentation developed proved to have the sensitivity and resolution necessary to measure rock deformation around a full-scale raise bore during excavation. Tests show the relationships of rock deformation to progress of the raise boring and to time. The initial deformation of the opening appeared to be elastic. Using the deformation records and an estimated field stress, the modulus of elasticity was determined for the rock mass. In addition, the importance of this type of measurement in assessing support-problem areas is discussed.

Jan 1, 1971

By Murray Jacobson

A method for determining airborne trona dust concentrations using a midget impinger was developed. During sampling, the trona dust, composed of sodium carbonate and bicarbonate, dissolves in the collecting medium (water). Resulting solutions are then titrated using 0.1 [N] hydrochloric acid solution. The mass concentration of the trona sample is determined from a calibration curve relating the volume of acid required for neutralizing a collected sample to the mass of the dust. Test results obtained using this method are equivalent to those obtained using a gravimetric sampling method.

Jan 1, 1971

By John Nagy

Data from experiments and literature on gas and dust explosions in closed vessels are presented to show the effects of the vessel size and shape; the initial pressure, temperature, and turbulence; and the fuel-air ratio and the strength of ignition source on pressure and rate of pressure rise. An attempt is made to correlate some of these parameters with an elementary mathematical model. Analyses of data on 17 vessels--spherical, cubical, cylindrical, and rectilinear in shape--ranging from 0,018 to 905 cubic feet in volume were made. Although the study was initiated to provide information primarily on dust-explosion phenomena, some data were obtained for gas explosions so that the factor of initial turbulence caused by the pneumatic blast used to disperse dust could be evaluated. The mathematical interpretation of the explosion phenomena was in general accord with the experimental data, and correlation was obtained for several factors affecting explosion development. Neither vessel size nor shape affected maximum pressure (when heat loss was neglected). The rate of pres-sure rise decreased as vessel size increased, and the rate was proportional to the ratio of the surface area of the vessel to its volume. Induced initial turbulence markedly increased the rate of pressure rise and slightly increased the maximum pressure. Changes in initial pressure produced proportional changes in maximum pressure and rate of pressure rise. Initial temperature and maximum pressure were inversely related, but initial temperature had little effect on the maximum rate of pressure rise. Comparative experiments showed no appreciable difference in explosion development of gas and dust fuels. The vessels and experimental work are described, and all data are given in tables. The mathematical model will facilitate extrapolation from laboratory to industrial conditions and will allow comparison of results obtained in different laboratories.

Jan 1, 1971

By George S. Koch

Several methods of calculating ore grades by diamond-drill sampling in the Homestake mine, Lead, S. Dak., have been evaluated by statistical analyses of assay data. The natural distribution of gold particles, partly masked through sampling and assaying procedures, is probably lognormal. As a consequence of the gold particles being clustered rather than randomly distributed within the ore bodies, (1) more mine samples are needed to obtain a specified precision of mean grade than the number predicted by the standard-error-of-the-mean law; (2) the variance of gold values is not inversely proportional to sample volume, and, therefore, small-diameter drill core yields samples nearly as good as larger diameter core; and (3) sampling at 5-foot intervals provides nearly as good results as sampling at shorter intervals.

Jan 1, 1971

By Foster Fraas

Calculations based on data related to the electrostatic precipitator illustrate the variation in the electric forces on a particle with change in position in the ionized field. The feeble forces in some separators are explained by the low field intensity at midpoint locations between the electrodes. When the particles are in contact with the exterior surface of a rotating cylindrical electrode, a high field intensity at the electrode surface combined with the image charge results in large electric forces. The permissible feed velocity increases as the square root of the electrode diameter, providing high values in efficiency and feed rate capacity, particularly in surface-to-mass ratio separations such as are encountered in secondary materials recycling operations.

Jan 1, 1971

By Richard N. Spencer

This report describes investigations of the economic merits of multiple zone mining and beneficiation versus selective mining of altered Western phosphate rock. The same deposit was considered in both instances and it was assumed that the grade of selectively mined ore was comparable to the grade of the concentrate from beneficiation. The beneficiating scheme used for the investigation was one proved by small continuous circuit operation. All economic factors were found to favor multiple zone mining plus beneficiation. Capital requirements and production costs were lower, and production life of the deposit was extended 4.5 times. The concentrate from beneficiation would be a uniform high-quality feed for acidulation and would be low in stable metallic oxide (R203) content. Such a feed would permit improved plant operating control, and the low R203 would promote more rapid filtration and minimize sludge formation in the phosphoric acid. With the proposed treatment, the concentrate produced by flotation from this deposit would cost about 1.5 times as much per ton as the concentrate produced by classification sizing. Therefore, inclusion of a flotation step in treatment schemes requires an economic analysis for each ore deposit.

Jan 1, 1971

By Aarne Visnapuu

Dissociation and vaporization of gold chlorides and bromides were investigated by a static pressure method and by Knudsen cell mass spectrometer. Two distinct chlorine and three distinct bromine pressure-temperature relation-ships were observed for the respective salts. The chlorine pressures are attributed to the dissociation of Au2Cl6 and Au2C12, and the bromine pressures to the dissociation of Au2Br6, Au2Br4, and AU2Br2, These pressure-temperature relationships were used to calculate dissociation pressure equations, enthalpies, and entropies of dissociation for each salt. Mass analysis of the vapors over AU2Cls between 83° and 152° C confirmed the existence of gaseous AU2C16. Ionization potential of this molecule is 11.0±0.1 ev and enthalpy of vaporization is 28.l±2.0 kcal/mole. Mass analysis of the vapors over the gold bromides detected only Bra in the temperature range 15°-150° C.

Jan 1, 1971

By D. S. Burgess

A commercially available Halon 1301 extinguisher has been evaluated as part of an explosion-suppression system for use in coal mines. Studies were made both of the dispersion pattern of the Halon 1301 at an initial pressure of 280 psig, and of the efficacy of this suppressant against 9.5 percent methane-air flames. These flames were quenched successfully only when the suppressant was applied before the fireball diameter exceeded 18 inches.

Jan 1, 1971

By E. G. Davis

This report summarizes an investigation to determine the occurrence and recoverability of heavy minerals in sand and gravel operations in the Southeastern United States. A total of 61 samples from 34 sand and gravel operations in Alabama, Georgia, South Carolina, and North Carolina were studied. Heavy minerals, in amounts ranging from 3 to 400 pounds per ton, were found in all of the samples. Eighty percent of the samples contained 20 to 40 pounds per ton of heavy min¬eral. Valuable heavy minerals, in order of decreasing amounts, were ilmenite, kyanite, zircon, rutile, and monazite. Large-scale concentration tests were made on five samples from four major producers. Gravity concentration by Humphreys spirals and tables resulted in bulk heavy mineral concentrates that graded from 82 to 98 percent total heavy minerals. Mineral recoveries ranged, in percent, as follows: Ilmenite 60 to 95; zircon 96 to 100; kyanite 37 to 77; rutile 89 to 100; and monazite 96 to 100. Separation studies on the gravity concentrates showed they would respond to high-tension and high-intensity magnetic separation techniques to produce individual mineral concentrates. The recovery of each individual mineral from fractionation of the heavy mineral gravity concentrates, in percent, was: Ilmenite 77 to 94; rutile 41 to 68; kyanite 62 to 79; zircon 49 to 83; and rare-earth products, monazite and xenotime, 42 to 96. The grade of each mineral concentrate was: Ilmenite 51.1 to 68.7 percent Ti02; rutile 93.7 to 94.3 percent Ti02; kyanite 55 percent A1203; zircon 58 to 61 percent Zr02; and rare-earth products containing 73.8 to 90.8 percent monazite and 4.8 to 12.7 percent xenotime.

Jan 1, 1971

By A. F. Baker

Laboratory flotation of synthetic coal-pyrite mixtures and high-pyritic-sulfur coal indicated that ferric chloride (FeCl3), aluminum chloride (AIC13), chromium chloride (CrCl3), and cupric sulfate (CuSO4) are potential pyrite depressants. For each metal salt there appeared to be a range of pH values and optimum concentration for selectively depressing pyrite in coal flotation. Pyrite was depressed in the pH range from 4.5 to 7.0 with ferric chloride, from 5.8 to 7.0 with aluminum chloride, from 6.4 to 7.1 with chromium chloride, and from 6.4 to 7.4 with cupric sulfate. Best separation of pyrite from coal was achieved in flotation solutions containing from 2 X 10-5 to 5 x 10-5 mole/ liter of each salt. In solutions containing excess salt concentrations, coal was also depressed. These Bureau of Mines tests demonstrated on a laboratory scale that, in solutions containing 4 X 10-5 mole/liter ferric chloride and from 1 x 10-4 to 2 x 10-4 mole/liter sodium hydroxide, the pyritic sulfur content of a Lower Freeport bed coal sample could be reduced from about 2.51 percent to less than 0.60 percent with recoveries of over 83 percent. The depression of pyrite appears to be due to the adsorption of positively charged colloidal metal hydroxide at the pyrite-solution interface. This hypothesis is supported by zeta potential determinations which showed that suspended coal and pyrite particles in solutions containing metal salts are positively charged in the pH range where depression occurs.

Jan 1, 1971

By W. K. Sawyer

Resistivity, porosity, permeability, and saturation data were obtained on core samples from the Big Injun, Clinton, Gordon, Bradford Second and Third, and Venango Second oil sands and formation factor-porosity relationships were derived using the general form of Archie's equation F = aø-m, where F is the formation factor, ø is the porosity, and a and m are constants that depend on characteristics of the rock. It was found that a and m varied significantly between sands, as did the exponent in the Archie relation I = Sw-n, where I is the resistivity index and S, is the water saturation. The average exponent, n, determined from all data was 50 percent greater at residual oil saturation than at residual water saturation. Samples from each sand exhibited differences in directional resistivity and/or permeability. The Bradford Third sand data showed correlation between resistivity and permeability anisotropy.

Jan 1, 1971

By Martin H. Stanczyk

Freezing to dewater typical Florida phosphate rock slime as demonstrated in laboratory tests appeared to have potential commercial use because of indicated moderate energy requirements, good compaction of dewatered solids, and effective recovery of usable water. After freezing, thawing, decanting, and filtering, batch freezing of gallon-size 13.7 percent solids slime samples yielded 42 percent solids products. Cationic amine, used as a process additive, yielded 46.8 percent solids product with significant filter area reduction. Semicontinuous 8 stage freezing tests also produced thickened slimes. Cooling and freezing 13.7 percent solids slime from 30° to minus 10° C required removal of 183 Btu per pound of slime; Carnot cycle calculation indicated that the theoretical minimum energy to transfer this heat was 27.8 Btu per pound. To produce 1 ton of 44 percent solids slime from 13.7 percent sol-ids slime, the calculated theoretical energy required for cooling and freezing was 52.3 kilowatt-hours. During the research heat capacity and heat of fusion data were determined for the slime at various percent solids.

Jan 1, 1971

By Robert Blickensderfer

Tungsten alloys with high-temperature strength properties, comparable to the best of alloys recently developed by others, were produced by a new process called here the oxyreaction process. The process involved additions of a powder of a reactive metal compound, ZrN, ZrW2, or HfW2, to a base metal powder, tungsten, which contained some oxygen. The powders were blended, compacted, sintered, and extruded. During sintering, diffusion and internal oxidation occurred to produce reactive-metal oxide particles and solid solutions. A dispersion of oxide particles could be precipitated by heat treating. The oxyreaction process circumvents many of the agglomerating and coarsening problems encountered in the current methods for dispersing a stable oxide in a metal. Oxyreaction strengthening results from solid-solution strengthening and from dispersion strengthening produced by the reactive metal and its oxides. At a test temperature of 1,650° C, the alloys prepared from WW, had tensile strengths up to 70,000 psi and stress-rupture lives up to 142 hr at 10,000 psi stress; the alloys prepared from ZrN powders had tensile strengths up to 80,000 psi and stress-rupture lives up to 27 hr at 10,000 psi stress. Tensile strengthening in the alloys was attributed to Zr in solid solution or to Zr-O-W structures too small to be observed in an electron microscope replica. Stress-rupture life was attributed to a dispersion of submicron Zr02 particles which precipitated and grew to 0.05-to 0.2-micron size during the test. Tensile strengthening and stress-rupture life were dependent upon both the zirconium and oxygen contents with the maximum occurring at roughly 0.9 atomic pot Zr and 0.9 atomic pot 0. Studies of the details of the oxyreaction process were made on the W-ZrW2 alloys and three general steps were determined: (1) The reaction of 0 in tungsten powder with ZrW2 to form relatively large Zr02 particles; (2) the dissolution of remaining ZrW2 into the W matrix and partial internal oxidation to form ultrafine but sparse zirconium oxide particles and possibly to establish Zr-O-W structures; (3) the development of ultrafine Zr02 particles during high-temperature aging.

Jan 1, 1971

By R. E. Meaker

Electrical conductivities and densities of molten fluoride systems were measured as functions of the melt temperature and composition. For any given mixture, the two properties change linearly with temperature. Three alkali metal fluorides were selected as solvents for melts of the type LiF-, NaF-, and KF-MFx, where M is a metal selected from the alkali metal or alkaline earth groups, or from the lanthanide or actinide series of elements, and x = 1-4. Heats of activation for conductance were calculated from the experimental data and varied from 2.3 to 9.2 kcal/mole at 1,000° C. Some relation between position in the phase diagram and the conductivity changes was suggested.

Jan 1, 1971

By W. F. Marshall

This report describes exhaust-emission data from 10 diesel engines: six 4-cycle, direct-injection, naturally aspirated engines; two 4-cycle, direct-injection, turbocharged engines; one 4-cycle, precombustion-chamber, turbo-charged engine; and one 2-cycle, direct-injection engine. These engines were tested over a 3-year period (1968-70). Lowest emissions were obtained with a precombustion-chamber engine. Emissions from the 2-cycle, direct-injection engine fell within the range of emission rates for the 4-cycle, naturally aspirated, direct-injection engines. Excluding the precombustion-chamber engine and excepting one of the 4-cycle, naturally aspirated engines, carbon monoxide emission rates were about the same for all engines tested. Test data on smoke, odor, and emissions of hydrocarbons, oxides of nitro-gen, carbon monoxide, and aldehydes are given.

Jan 1, 1971