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By K. O. Bennington

Enthalpies of formation of three sodium titanates were determined by hydrofluoric acid solution calorimetry, The values obtained for formation from the elements at 298.15° K are -370.9±0.5 kcal/mole for Na2TiO3, -832.1±0.9 kcal/mole for Na2Ti307, and -1,510.9±1.7 kcal/mole for Na2Ti6013. Tables of enthalpies of formation and Gibbs energies of formation are given as a function of temperature both from the elements and from the component oxides for Na2Ti03 and Na2Ti307.

Jan 1, 1973

By Dorothy M. Richardson

The Bureau of Mines has participated in the American Petroleum Institute Research Project 48A (API-RP48A) program on the Separation and Identification of Sulfur Compounds in Crude Petroleum. The lack of reference compounds or infrared spectral data has made difficult the identification of individual sulfur compounds boiling above 140° C. The recent acquisition of 24 alkylthiophnnes has made possible a limited study of this important class of sulfur compounds. The infrared spectra of 2-monoalkylthiophenes and 2,5-dialkylthiophenes for the 2 to 15p range are reported. Correlations for determining the 2-alkyl and 2,5-dialkyl substituted thiophenes are derived from this information. The 2-alkylthiophenes show a unique pattern in the 5.50 to 6.54 region, while the 2,5-dialkylthiophenes show a distinctive pattern in the 5.6µ to 6.7µ region. A skeletal vibration occurs in the 9.5 to 10.0µ region for all of the thiophenes investigated. These data will aid the infrared spectroscopist in the identification of compounds of the type reported.

Jan 1, 1961

By J. W. Town

The Bureau of Mines studied the effects of reducing gas composition, tem-perature, and superficial gas velocity on the regeneration rate of alkalized alumina. Regeneration was assumed to follow the simple first order reaction for removal of sorbed S02: dµ/dt = -Kµ. An Arrhenius relationship can be plotted, which shows an activation energy of about 75 kcal/mole for simulated reformed propane. The general effects of the individual gases can be described as follows: (1) CO and H2 produced rates proportional to their con-centrations, up to about 5 percent for each; (2) addition of CO2 had no effects on the regeneration rate by CO; (3) the regeneration rate by H2 was lowered by the addition of H2O while the regeneration rate by CO was increased by 0 addition; (4) H2S showed a positive effect up to concentration levels of about 2 percent and then produced a rapid negative effect; (5) carbonyl sulfate (COS) increased the sulfur content; and (6) propane was as effective in regenerating the loaded pellets as was simulated reformed propane.

Jan 1, 1971

By H. L. Retcofsky

Carbon-13 nuclear magnetic resonance (18CNMR) spectra of nine 2-substituted pyridines, seven 3 -substituted pyridines, and nine 4-substituted pyridines have been obtained and analyzed. Substituents included both electron-releasing groups and electron-with hawing groups. Substituent effects on the magnetic shieldings of the ring carbons, except for those in the 2-positions of 2-substituted pyridines, were found to be quite similar to the effects reported for the monosubstituted benzenes, Thus, at least to a first approximation, the two classes of compounds have similar shielding mechanisms. Shieldings of the carbon atoms in the 5-positions of 2-substituted pyridines and those in the 6-positions of 3-substituted pyridines were found to reflect electron release or withdrawal by substituent groups, The pyridinium cation and the compounds 2,2'-dipyridyl and benzonitrile were also investigated.

Jan 1, 1969

By K. K. Kelley

"INTRODUCTION The Bureau of Mines nitrogen peroxide process (2) 3/ for extracting manganese from low-grade ores is essentially a two-stage process involving the reversible reactionMnO2 + 2NO2 + 6H2O = Mn (NO3)2 . 6H2O (1).At lower temperatures this reaction proceeds to the rigth and affords a means of dissolving manganece and separating it from unreacted ore. At higher temperatures the reaction proceeds to the left and manganese dioxide is recovered and nitrogen peroxide regenerated for recycling. Evidently, therefore, the energy required for decomposition of manganous nitrate is a matter of practical importance. Similar information for certain other nitrates also is desirable beceuse the nitration step of the process produces appreciable amounts of nitrates of other metals, such as iron, aluminum, magnesium, calcium, and barium, some of which are not broken down in the evaporation and decomposition steps. Thus, a portion of the nitrogen peroxide is not directly available for recycling. Whether or not it is feasible to recover nitrogen peroxide locked in the more-stable nitrates depends partly on the energy required and the conditions necessary for their decomposition.To supply information bearing directly on these subjects, several researches were undertaken at the Pacific Experiment Station: (a) Heats of formation (24, 25, 26) of nitrates of manganese, magnesium, calcium, barium, and aluminum were measured at 298.2° K:; (b) low-temperature specific heats (23), in the range 51° to 298.2° K,, and entropies of nitrates of magnesium, calcium, barium, and aluminumm were determined; and (c) heat contents (21) above 298.2° K. of the nitrates of manganese, magnesium, calcium., and barium were measured. The results of these studies, when correlated by thermodymamic methods, permit evaluation, at any temperature of interest, of the energies required to decomposethe nitrates and furnish information concerning the equilibrium pressure temperature relationships."

Sep 1, 1944

By R. F. Abernethy

Analytical results, including ash fusibility data, are presented by the Bureau of Mines for 10 major constituents in coal ash from 373 samples of commercial U.S. coals. Determinations of Si02, Al2O3, Fe2O3, and P2O5 were made by colorimetric methods, Na2O and K2O by flame photometry, Ti02, CaO, and MgO by a spectrochemical method, and SO3 by a gravimetric method. In bituminous coal ashes the silicon, aluminum, and iron calculated as oxides often make up about 90 percent of the ash.

Jan 1, 1969

By John E. Pahlman

The Bureau of Mines investigated the feasibility of removing heavy metals from mineral-process waste streams by precipitation with lignochemicals and humic acids. Lignochemicals are by products from the paper industry, while humic acids are obtained by caustic treatment of peat, subbituminous coal, and lignite. These high-molecular-weight organic materials have many functional groups, which can coordinate and form innercomplex salts with heavy metals that are crystalline precipitates. Filtering of a humic-acid-or lignochemical-treated solution or waste stream containing these precipitates removes the heavy metal sequstrates. Tests were conducted with two lignochemical samples, three humic acid samples, lime (CaO), and sodium hydroxide (NaOH) in which increasing amounts of these additives were reacted with 50 mL of solution containing Fe3+ , Al3+, Cr3+, Pb2+, Cu2+, Cd2+, Zn2+, Co2+, Ni2+, Mn2+, and Hg1+. At the appropriate pH, greater than 90-and 99-pct removal was achieved for these 11 heavy metal ions from the 10-and lOO-ppm solutions, respectively, using lignochemicals and humic acids. Removal efficienC)' with these organic materials is better than that with CaO, especially for the more toxic ions, Hg1+, Cd2+, and Pb2+. Unlike the precipitates formed with NaOH or CaO, those with lignochemicals and humic acids are compact and noncolloidal. The volume of their sludge is sharply lower than that of the finely dispersed lime or soda precipitates; thus, their removal in settling tanks or by simple filtration is enhanced.

Jan 1, 1988

By David J. MacDonald

Stability constants, that is, equilibrium constants for complex-formation reactions, have been determined by a titrimetric method for complexes formed by the transition metal ions Ni2+, Cu2+, Zn2+, and Cd2+ with the structurally analogous bidentate ligands N-ethylethylenediamine and 2-(ethylthio)-ethylamine. The sulfur containing ligand was found to be the weaker of the two chelating agents for each of the four metals. Absorption spectra of the individual complexes have been determined in order to calculate their crystal field stabilization energies. The combined results suggest a linear relation between free energy of chelation and ionic radius of the metal ion.

Jan 1, 1972

By J. W. Griffith, J. L. Stauffer, L. M. Demers, D. C. Kuhn, S. Riliog

"The relative activation of eicosanoid production which results from the exposure of the alveolar macrophage (AM) to mineral dusts is thought to be a key factor in the pathophysiology of occupational lung disease. We compared in vitro basal and silicastimulated production of prostaglandin E2 (PGE2) and thromboxane A2 (TXA2) by AM from normal humans and non-human primates (Macaca nemistrina). In addition, we instilled mineral dusts directly into one lung of the non-human primate and evaluated AM eicosanoid production at two week intervals following dust instillation. Unstimulated AM from humans produce more PGE2 and TXA2 than do AM from M. nemistrina. However, in vitro exposure of AM from both species to silica dust produced a qualitatively similar increase in TXA2 production accompanied by no change in PGE2 production. Sequential analysis of AM eicosanoid production following a single bolus exposure to bituminous or anthracite coal dusts, titanium dioxide (Ti()i) dust or crystalline silica showed marked variability among individual non-human primates in qualitative and quantitative aspects of dust-induced eicosanoid production. However, the rank order of potency of the different dusts (silica> anthracite> bituminous) correlated with epidemiological evidence relating the type of dust mined to the incidence of pneumoconiosis. These studies suggest that the non-human primate may serve as a model for the study of both the role of eicosanoids in the etiology of dust-induced occupational lung disease and the biochemical basis for individual variability in the response of lung cells to mineral dust exposure. IntroductionOccupational inhalation of mineral dust can lead to chronic debilitating lung disease ( 1,2). One of the key components of the disease process is thought to be the interaction of mineral dust with the alveolar macrophage (AM) and the subsequent release by the AM of inflammatory and fibrotic substances (3,4). Chronic inhalation of mineral dust, depending on the type and amount of dust, may then produce a situation in which ongoing inflammation, accompanied by the destruction of functional lung tissue by products of activated AM and polymorphonuclear neutrophils, stimulates the production of nonfunctional matrix by lung fibroblasts.The AM produces several oxygenated derivatives of arachidonic acid (AA) which may play important roles in dust-induced lung pathophysiology (5,6). In previous studies in the rat, we found that prostaglandin E2 (PGE2). thromboxane A2 (TXA2) and leukotriene 84 (L TB4) were the major AA metabolites produced by AM (7). PGE2 is associated with pro-inflammatory activity (8) as well as anti-fibrotic activity since it downregulates interleukin -1 (IL-1) and tumor necrosis factor (TNF) release by AM (9-11). TXA2 is known to stimulate platelet activity, cause bronchial and vascular smooth muscle contraction (12) and to possess chemotactic activity (13). LTB4 is chemotactic for neutrophils and monocytes (14) and has been suggested as an additional regulatory factor in the release of TNF by AM exposed to silica dust ( 15)."

Nov 1, 1995

By W. I. Nissen

This Bureau of Mines report presents the design for a commercial-sized flue gas desulfurization (FGD) demonstration plant that uses the citrate process. The goal of the Bureau's citrate process is to minimize the undesirable environmental impacts of industrial plants emitting SO2-bearing gas. The FGD plant is located at the George F. Weaton powerplant, Monaca, Pa. Construction was completed in April 1979 and will be followed by preliminary testing and a 1-year testing and evaluation program. Design capacity of the FGD plant is 156,000 scfm of 0.2-volume-percent-SO2 flue gas yielding about 16 tons of sulfur per day. The plant is intended to (1) clean fly ash, SO2, and Cl- from the gas while cooling the gas in a venturi scrubber, (2) absorb SO2 from the gas using 1,200 gpm of a countercurrent-flowing citric acid-sodium citrate-sodium thiosulfate solution, (3) react the absorbed SO2 in two 13,000-gal stirred closed vessels with added H2S, thus precipitating elemental sulfur and regenerating the citrate solution for recycle, and (4) recover the sulfur from the slurry by air flotation, followed by melting in a heat exchanger and separation from the occluded citrate solution in a sulfur decanter at 35 psi and 135° C.

Jan 1, 1979

By S. Akhtar

Interstitial compounds of iron, cobalt, and nickel, and their binary and ternary mixtures with silver, gold, palladium, and platinum were prepared and tested as fuel cell catalysts. The first step in the preparation of the interstitial compounds consisted of preparing finely divided metals. This was done either by the Raney method or by reduction of precipitated hydroxides of the metals. The finely divided reduced metals were then treated with carbon-and/or nitrogen-containing gases to prepare their carbides, nitrides, and nitrocarbides. The materials were tested for cathodic activity towards O2 and for anodic activity towards H2, C3H8, NH3, CO, and N2H4 in acid and alkaline electrolytes at 25° to 90° C in half-cell assemblies. Samples of carbided and nitrocarbided INi-lAg-1Au were about one fifth as active as Pt-black in the reduction of O2 in 35 percent KOH solution, whereas the activities of several interstitial preparations exceeded the activity of Pt-black in the reduction of O2 in 12M KOH containing N2H4. Nitrocarbides of x-Fe2C, 3Ni-1Au, and 1Ni-3Au were effective catalysts for oxidizing N2H4 in liquid NH3 containing NH4SCN. Corrosion of the catalysts by electrolytes was severe in many cases.

Jan 1, 1970

By E. V. Cilento, K. A. DiGregorio, R. C. Lantz

Pulmonary inflammation is accompanied by increased microvascular permeability and leakage of plasma into alveolar spaces. Serum has been shown to affect superoxide (O2-) production from pulmonary alveolar macrophages (PAM) in vitro, and in some cases serum has been shown to be necessary for stimulation of PAM. An electro-optical method was used to measure O2- production from single PAM by measuring the reduction of nitroblue tetrazolium (NBT) to a diformazan precipitate (NBTH2) from videorecorded images of individual cells. PAM were stimulated by their initial attachment to culture dishes independent of serum. The addition of 2% serum to the culture medium increased NBTH2 production during attachment, whereas concentrations of 5 and 10% serum had no additional effect. In contrast, PAM incubated for 2 hrs could not be stimulated by phorbol myristate acetate (PMA) or zymosan particles to produce O2- unless serum was present during the incubation and/or stimulation; however, NBTH production was similar in all cases of serum addition. Also2, serum alone did not stimulate adherent PAM indicating that serum is necessary but not sufficient for stimulation of attached. PAM. These results suggest that changes in microcirculatory permeability may have a pronounced effect on superoxide production by PAM and that serum may help regulate or condition these cells during inflammation of the lung. (Supported by USBOM Gll35142.)

Jan 1, 1988

By Bernard Porter

The solubility of UO2 was determined at 1,250° C. in ternary melts of UF4 and BaF2 with CaF2, LiF, and SrF2. The solubility of Ce02 was measured at 800° and 850° C. in a solution of CeF3, BaF2, and LiF. The amount of La203 which dissolves at 950° C. in a binary mixture of LiF and LaF3 and a ternary of LiF, LaF3, and BaF2 was also measured. In each case, the amount of soluble oxide was mound to be less than 5 weight-percent. A procedure was developed for filtering fused, oxide-saturated fluoride melts in order to obtain a representative sample for chemical analysis. The oxide content of the samples was determined by an inert-gas fusion procedure.

Jan 1, 1961

By Laurance L. Oden

The Bureau of Mines studied three processes for preparing NaAl(OH)2C03) the intermediate compound which is calcined to produce alkalized alumina: (1) Mixing of Na2 C03 and of A12 (S04)3 solutions, (2) digestion of aluminum hydroxide in solutions of Na2C03 and NaHC03 at 90° C, and (3) addition of CO2 at 25° C to caustic solutions of aluminum to precipitate aluminum hydroxide followed by digestion at 90° C. The first process had the highest raw material consumption and washing requirements, and successful application of process 2 depended upon the availability of active aluminum hydroxide. Process 3 was the most effective, considering both process technology and raw material requirements. Procedures were also investigated for washing, filtering, drying, and calcining precipitates. Analytical methods included X-ray diffraction, atomic absorption spectroscopy, differential thermal analysis, and thermogravimetric analysis.

Jan 1, 1969

By N. Fragen, H. H. Stroch

"INTRODUCTION A previous paper by H. H. Storch 4 described. three processes for the production of potassium sulphate from polyhalite (K2S01.MgSO1.2CaS04.2H2o), Since these processes depended upon calcination of polyhalite followed by leaching with water at 100°C., the fundamental reactions occurring in these steps were discussed in detail. This paper, which describes processes producing syngenite (K2S04.CaSO4.H2O) and potassium sulphate and gives data concerning the production of by-product magnesia, presents the results of work performed at the Non metallic Minerals Experiment Station of the U. S. Bureau of Mines, maintained at New Brunswick, N. J., in cooperation with Rutgers University.A study of the solubility relationships of the system 5 Ca++ -Mg++ -K+-SO4 = H20 at 25ºC. shows that syngenite is stable in the presence of a concentrated MgSO4 solution, the K2SO : equilibrium concentration being comparatively low (2.6 per cent), The processes described below, which involve the conversion of calcined polyhalite to syngenite, are based on the 25°C. equilibria. It has further been found that syngenite can be decomposed by water at 100ºC, yielding a 9 to 10 per cent K250 solution, the solid phase being potassium calcium pentasulphate (K2SO, 3CaSO.H2O, hereafter referred to as ""pentasulphate""). This latter compound is unstable in the presence of water at 25°C., its decomposition resulting in a solution containing about 3 per cent of K2SO4 and a solid phase consisting of gypsum. This behaviour of syngenite with water at 100°C. and of pentasulphate with water at 25ºC. constitutes the basis of processes for the production of K2SO4 by way of the conversion of calcined polyhalite to syngenite,Syngenite is a product which may be used as a fertilizer per se. As produced in the process to be described, it contains about 50 per cent of K2SO1, and will readily give up its potash content on treatment with water, although the limiting concentration at ordinary temperatures is approximately 3 per cent. This definite but limited solubility should make this product more desirable as a fertilizer then the more concentrated forms of potash salts which have higher solubilities and hence involve the danger or plant injury due to a high local concentration of potash."

Sep 1, 1931

By John E. Kelley

The Bureau of Mines conducted a study to determine the feasibility of joining refractory metal compounds to each other and to oxide ceramics by a vacuum hot press-diffusion bonding method. Very satisfactory joins were made of ZrC to ZrB2, ZrN to ZrB2, ZrC to ZrN, and of ZrC, ZrN, and ZrB2 to Al203. Each of these join assemblies contained a mixture layer comprising 50 weight-percent each of the two end compounds. The mixture layer, sandwiched between each end compound, enhanced bonding and smoothed out the thermal expansion gradient between the two end members. Strength and thermal shock tests showed that the join areas of the ZrC, ZrN, and ZrB2 joins were stronger and more shock resistant than the parent materials. Also included in the joining tests was one each of TiC to TiB2, TiC to TiN, TiB2 to TIN, and TiC to ZrB2 joins. Each of these was well bonded, showing that the vacuum-hot-press method can be used for a variety of systems.

Jan 1, 1969

By Charles E. Semler

The possible utility of selected compositions in the systems SrO-ZrO2-MgO and SrO-ZrO2-Dolomite for commercial refractory products was confirmed in this study. Specifically the compositions of interest are located in the sub-systems SrZrO3-ZrO2-MgO and SrZrO3-ZrO2-Dolomite. Both sub-systems have regions that are not affected by hydration, but the sub-system SrZrO3-ZrO2-MgO has a larger candidate compositional region. Solid state phase relations were determined for the subject systems over the temperature range 1600°C to 1300°C, with compatibility diagrams presented for each. The systems appear to show good refractory character with no apparent low melting compositions. As the compositions of commercial interest lie mostly in the higher ZrO2 portion of each system, information is presented regarding the firing treatment required to develop stabilized cubic ZrO2. A list of suggestions for further study of these systems, to further delineate the characteristics required for possible commercial utilization, is presented.

Jan 1, 1982

By T. E. Bernard

The CO2-absorbent canisters used in four approved rescue breathing apparatus were investigated. A breathing machine was used to simulate human expiration with gas flow rates of 26, 37, and 48 1/min of 3.5% CO2 in air. The exit gas CO2 concentration, the pressure drop across the canister, and the exit-gas temperature were monitored. The absorbent capacities of the packed-bed canister designs were found to be dependent on flow rate within the range studied, while the capacities of the other designs were less affected. The radial canister had the least resistance to breathing while the complex bed design proved to be the most effective in utilization of the chemical. The overall results indicated that LiOH (lithium hydroxide) has the highest capacity for CO2 absorption among the absorbents tested. It can be used in a simple packed-bed design while maintaining acceptable levels of resistance and exit-gas temperature. Examination of oxygen supply with respect to CO2-absorption capacity suggested that it is desirable to closely match CO2-absorption capacity with the avail-able O2 supply to minimize the size and weight of rescue breathing apparatus.

Jan 1, 1979

By Arden D. Fugate

The Federal Bureau of Mines conducted extensive studies on solid-state defluorination (laboratory scale) and tests on molten defluorination (intermediate scale) of siliceous fluorspars. The studies were made to develop a pyrohydrolytic process for liberating fluorine from offgrade fluorspars. Test results showed that more than 90 percent of the fluorine can be evolved by solid-state defluorination at 1,300° C., and more than 97 percent can be liberated by molten-state defluorination at 1,420° C. Solid-state defluorination conditions were established by conducting tests on mixtures of ceramic-grade fluorspars and high-purity silica flour. Pelletized mixtures were defluorinated under varying conditions of time, temperature, and relative concentrations of silica, calcium fluoride, and water. The effects of adding various amounts and combinations of aluminum oxide and iron oxide on defluorination were also studied. Investigations of solid-state defluorination indicates that the following two reactions are involved: 2CaF2 + 3SiO2 = 2CaSiO3 + SiF4, and CaF2 + Sio2 + H20 = CaSiO3 + 2HF, The second reaction is dominant, although significant defluorination can be achieved by the first reaction.

Jan 1, 1961

By Laurance L. Oden

The Bureau of Mines is developing melting data for binary combinations of the alkaline earth fluorides and yttria to facilitate the formulation of slag compositions. The present report deals with the SrF2-Y2O3 system for which liquidus and solidus temperatures and solid solubilities were determined. The information is presented as the phase diagram. The phase diagram was constructed from information obtained by ceramogra¬phy, X-ray diffraction, thermal analysis, and electron probe microanalysis of small specimens encapsulated in platinum-20 percent rhodium or molybdenum ampoules. The data indicate a simple eutectic system with limited terminal solid solubilities. The eutectic temperature is 1,457°±5° C, and the eutectic composition is 4±1 mole-pct Y203. Strontium fluoride containing up to 2 wt-pct 0 2 was studied to determine the effects of oxygen contamination. Oxygen levels in excess of 0.2 wt-pct resulted in eutectic formation between SrF2 and SrO. The eutectic composition is between 0.2 and 0.7 wt-pct 02, and the eutectic temperature is 1,447°±5° C. No intermediate oxyfluoride phases were detected.

Jan 1, 1974