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By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman' provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry's law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

By M. D. Banus, M. B. Bever, A. K. Jena

The heals of formation at 78", 195, and 273°K of the ternary compound h3SbTe2 based on the elements and based on the binary compounds In Sb and [inTe have been measured. The heats of formation at these temperatlcres of the binary compounds In Sb and In Te based on the elements have also been determined. Heal contents and free energies of the three compounds have been calculated from 0° lo 80I)°K. The free energies of joyrrzalion, heats of formations, and entropies of formation at 298°K have also been calculated. The results shown that the tertnary compound is metastable with vespecl to InSh and ln Te below 696 °K. bul is slable above that temperature. The weaker bonding of results in a positice entropy of formation which with incrensirzg temperature makes increasing negative conlvihtclions to the free energy and above 696°K renders the compound slable. THE ternary compound In3SbTez occurring in the quasi-binary system In Sb- In Te' forms on cooling at 829°K by a peritectic reaction.' Observations at 673" and 573 K have shown that this ternary compound decomposes slowly into the binary compounds InSb and1n~e.l'' It has not been possible to analyze the metastable behavior of the ternary compound because up to the present time data on its thermodynamic properties have been lacking. Some information on the binary compounds, however, is available. The heat of formation of InTe at 273°K and its free energy at 673°K are kn~wn.~'~ The heats of formation of InSb at 78", 273', 298", and 723°K have been measured5-' and its heat capacity between approximately 12" and 300"Kg9l0 is also known. In the investigation reported here the heats of formation at 78% 195% and 273°K of the ternary compound In3SbTez have been measured. The heats of formation of the binary compounds InSb and InTe at these temperatures have been obtained by combining new calorimetric results with previously published data. The heat contents and free energies of the three compounds at various temperatures from 0" to 800°K have been calculated. Against the background of this information, the metastability of the ternary compound will be discussed. 1) EXPERIMENTAL 1.l) Preparation of Specimens. The materials used consisted of the elements indium, antimony, and tellurium, the binary compounds InSb and InTe, and the ternary compound In3SbTez. The elements, obtained from American Smelting and Refining Co., had a nominal purity of 99.999+ pct. The compound InSb was Cominco semiconductor grade; the compound InTe was prepared from the elements by melting under a vacuum of 10-h m Hg followed by slow cooling. Three batches of specimens of the compound In3SbTez were used. One batch was prepared by melting appropriate amounts of the elements in an evacuated and sealed Vycor tube. The melt was held at approximately 100°K above the liquidus for about 8 hr, shaken repeatedly, and quenched into a mixture of ice and water. The specimen was annealed in vacuum at 760°K for 4 weeks. In preparing a second batch, a mixture of the component elements was melted and quenched in water. The resulting ingot was powdered. The powder was pressed into pellets, which were annealed in vacuum at 748" to 773°K for 4 weeks. A third batch was prepared in the same manner as the second, except that the starting materials were InSb and InTe rather than the elements. Metallographic examination of samples of the three batches and X-ray diffraction examination of a sample of the second batch did not reveal evidence of microsegregation or a second phase. The results obtained with the three batches showed no systematic differences. 1.2) Calorimetry. The calorimetric method has been described in detail." Samples of the compound In3SbTez, mechanical mixtures of InSb and InTe in the proportion of 1:2, and mechanical mixtures of indium, antimony, and tellurium in the proportion of 3:1:2 were added to a bismuth-rich bath at 623°K in a metal-solution calorimeter. These additions were made from 78°K (liquid nitrogen), 195°K (dry ice and acetone), and 273°K (ice and water). The heat effects of the additions were measured. The difference in the heat effects of the additions of a compound and the additions of the mixtures of its constituents, adjusted for differences in the concentration of the bath, is the heat of formation of the compound. In the concentration range not exceeding 1.5 at. pct solute, the heat effect of the additions was a linear function of concentration. The heat of formation refers to the temperature from which the additions were made, namely, 78", 195", or 273°K. Several calibrating additions were made in each calorimetric run. The calculated heat capacity of the calorimeter and hence the calculated heat effects of the additions of samples depend upon the values adopted for the heat contents of the calibrating substance. In this investigation bismuth at 273°K was used and a value of 4.96 kcal per g-atom was taken for (HGZ3"k . 2) RESULTS AND DISCUSSION 2.l) Heats of Formation. The heats of formation of the ternary compound In~SbTez from the component elements indium, antimony, and tellurium and from

Jan 1, 1968

By S. Vivek

An atomic force microscope (AFM) was used to measure the surface forces between silica plate and glass sphere in sodium oleate solutions. Hydrophobic forces were observed when the two surfaces were activated by CaOH+ or MgOH+ ions. The force measurements conducted in the absence of the surfactant showed that the activated silica surfaces do not exhibit the primary hydration forces that have been observed between unactivated surfaces. The activation mechanism was studied by calculating the contributions from electrostatic and chemical interactions to the total free energy change. The results suggest that the adsorption of the hydroxo-complexes is controlled mainly by the lateral interactions between the adsorbed species on the silica surface.

Jan 1, 1999

By Wagner Viana Bielefeldt, Felipe Buboltz Ferreira, Antônio Cezar Faria Vilela

The continuous casting machine is one of the most important steel production steps in a melt shop. The tundish, a reservoir between the steelmaking ladle and the mold, has great influence over the steel cleanliness, along with the productivity bid. It must takes into account the quality of the metal and operational safety. Several different variables are related to the tundish process, of inclusionary cleanliness. Some of them are discussed in this paper: the free opening of ladle, tundish inertization, steel temperature in the reservoir and clogging formation, besides a brief topic about castability. Therefore, a critical analysis, with a review from some papers available in literature, is proposed in this study, with its focus on tundish.

Oct 1, 2019

By E. G. King

Strontium sulfide and barium sulfide occur as intermediates in commercial treatments of the impure natural sulfates to produce pure strontium and barium chemicals. Thermodynamic considerations involving these sulfides have been hampered by lack of basic data, such as the entropies at 298.15°K. This paper reports the results of heat capacity measurements of strontium sulfide and barium sulfide in the temperature range 50°-298°K. The entropies at 298.15°K. were derived from the heat capacity values. Free energies of formation at 298.15°k. were computed from the entropies and literature values of the heats of formation. Strontium sulfide and barium sulfide are thermo-dynamically less stable than calcium sulfide, but more stable than magnesium sulfide.

Jan 1, 1960

By G. W. Birge

Twenty-eight samples, representing the Pittsburgh, Lower Kittanning, Stockton-Lewiston, Coalburg, Winifrede, Cedar Grove, Peerless, No. 2 Gas, Powellton, and Eagle beds, were carbonized by the Bureau of Mines--American Gas Association (BM-AGA) method, and yields of products and physical properties of cokes were determined. Expanding characteristics of 22 of the samples were determined in the Bureau of Mines sole-heated oven. The Kanawha County coals tested were high-volatile A bituminous in rank, with dry, mineral-matter- free fixed- carbon contents ranging from 53.9 to 66.3 percent. With few exceptions, they were chemically satisfactory for metallurgical use, and most of the coke-strength indexes were within the industrially accepted range for high-volatile blending coals.

Jan 1, 1963

By R. L. Grayson

Compliance standards for respirable dust which are reduced because of high quartz concentrations have become an industry-wide problem. Research on the physical and chemical character of quartz-classified particles in respirable coal mine dusts indicates that they may exist in intermixed layers or may be coated by clay or coal material. The relative amount of intermixing varies with the coal seam being mined. If most of the quartz particles of a mine dust are "pure," then the dust may have a high fibrogenic risk potential because of truly free silica and the compliance standard should be lowered. If, however, the quartz is locked inside another material matrix, or coated, a reduced compliance standard may not be appropriate.

Jan 1, 1990

By R. L. Soderberg

Large open stopes mined by vertical crater retreat or sublevel s are sometimes backfilled with uncemented sand to support the stope walls and alleviate rock bursts. The failure of bulkheads in two different mines prompted a research project at the Bureau of Mines to prevent a recurrence of these failures. A series of laboratory tests with drains and sand filters was conducted to measure the bulk-head pressures when adequate drainage was maintained. Results showed that bulkhead pressure was reduced to near zero while drains were in operation, as compared to full hydrostatic pressure when drains were blocked or drainage was restricted. A relatively simple, free-draining bulkhead was shown to be adequate.

Jan 1, 1985

By Alla D. Mah

No experimental heat-of-formation value has been reported in the literature for cerium sesquioxide. The heat of formation of bismuth sesquioxide has not been determined in recent years, and the older value was subject to large uncertainty. Accordingly, the heats of combustion of cerium sesquioxide and bismuth metal were measured by the Federal Bureau of Mines. The heats of formation were: ?H°298.15 = -427.01 ± 0.70 kcal. /mole for cerium sesquioxide and ?H°298.15 = -137.16 ± 0.30 kcal./mole for bismuth sesquioxide. The free energy of formation was estimated for cerium sesquioxide and accurately calculated for bismuth sesquioxide. The data were compared with values in the literature.

Jan 1, 1961

By P. R. Taylor

Titanium carbide and titanium diboride powders have been successfully synthesized by direct treatment of ilmenite concentrates in a non-transferred arc thermal plasma reactor. Methane gas was used as the reducing agent and boron oxide was used as the boron source in these processes. Free energy minimization plots were used to predict the behavior of each system under different molar ratios and operating conditions. Products were characterized by XRD, SEM and chemical analytical techniques. The average size of the ceramic product is in the submicron range. Metallic iron apparently is finely deposited on the surface of the titanium carbide or titanium diboride particles. Minor impurities such as silica, manganese and zircon were converted to the carbide form.

Jan 1, 1995

By Roy J. Helfinstine

One of the most urgent needs in the field of coal combustion is the ability to predict the performance of a coal from knowledge gained from small-scale tests. Numerous types of analyses and tests are conducted on coal, including the proximate and ultimate analyses, heating value, varieties of sulphur, ash analysis, ash fusion temperatures, free swelling index, petrographic analysis, and Gieseler plasticity. The Illinois Geological Survey has made an intensive study of the value of these tests for judging the performance characteristics of the coal as actually utilized. To date, three reports 1 2 3 have been is- sued, and another is being prepared. The present paper briefly summarizes some of the results found in the studies.

Jan 1, 1949

By M. R. Anderton

"A hierarchical four-character code designed for geological and allied data may be used to log exploration drill-holes and store the information on magnetic media. The code is intended for use in semi-free format and permits the collection of as much, or as little, data as the geologist may require for the purpose in hand. A method of data storage by variable length records is discussed.Information may be retrieved by means of a simple enquiry language. Optional output facilities could allow the retrieval of data in a form suitable for direct input to a contouring package. The enquiry parameters and interrogation program can thus provide the interface between the data bank and associated application systems."

Jan 1, 2014

By J. O?Shea

From the characteristics of the new (1976) electronic components and units that are being marketed, the author has tried to foresee the types and the performances of the near-future slope-monitoring equipment. Much-improved sensors, instruments and systems for pit use can now be developed - sun-powered telemetry remote stations are feasible, very sensitive as well as precise and drift-free liquid level inclinometers will be available, new techniques for distance measurement with lasers obviate the need for atmospheric corrections and the latest generation of desktop calculators have become easily programmed minicomputers. Thus, it is realistic to assume that fully automatic pit-slope monitoring systems will be operational in the foreseeable future.

Jan 1, 1978

By M. M. Botz

Cyanidation tailings which are disposed in a surface impoundment experience a loss of cyanide due to natural degradation, frequently reducing the cyanide concentration to very low levels. Quantifying cyanide losses in terms of pond geometry, local weather conditions and feed solution chemistry has been largely empirical though in many cases mining operations rely on surface impoundments to reduce cyanide to below an internally regulated concentration or an effluent limitation. To permit a more quantitative evaluation of cyanide losses in an impoundment, a computer simulation was developed to estimate the losses of free, WAD and total cyanide due to dissociation, photolysis and volatilization. Results of the model are compared against data collected for a North American tailings impoundment during 1998.

Jan 1, 1999

By R. K. Mehta

Conventional triboelectrification based dry coal beneficiation methods require ground coal as a prerequisite feed material, energy intensive static-in-line mixer or cyclonic tribocharger configuration, and transport and/or improvement in the design of free-fall separators to improve the separation efficiency of [me pyrite/mineral matter from coal. The proposed paper illustrates the two concepts. First, the use of ceramic media in a polyurethane lined attitor in achieving simultaneous grinding and differential charging. Second, the use of an electrocentrifuge to selectively separate coal from mineral matter present in the triboelectrified mixture. It is of interest to note that some ceramic media can satisfy the requirements of both desired density and work function to achieve grinding and differential charging.

Jan 1, 1996

By T. D. Moore

The use of a partially slotted 6.5-inch-inside-diameter vertical pipe to remove methane from a longwall gob area at a depth of 2,260 feet in the Pocahontas No. 3 coalbed was investigated. The value of gas removed by such a pipe under free-flow conditions was found to equal the cost of the installation in this case. Approximately 25 percent of the available methane passed through the pipe without the use of an exhauster; an additional 10 percent was removed when an exhauster was employed. The diversion of methane through a vertical slotted pipe to the surface permitted the use of increased mining rates and decreased the ventilation air requirements.

Jan 1, 1972

By Stephen Gerard Sawyer

A Fortran IV computer program entitled WAVE, which employs an explicit finite difference scheme for solving the one-dimensional wave equation for a time-dependent inelastic rock has been developed. The viscoelastic properties of the rock are represented in terms of a generalized Voigt model. The theory on which the computer program is based is rederived and a short description of the program is given. The computer program input instructions, a listing of the computer program, and example problems with required input and subsequent printed output are presented in appendixes. In the example problems) calculated results are free of spurious oscillations which occur in certain other methods of numerical calculation) notably the extended Ritz method.

Jan 1, 1972

By Fun-Den, Wang

An open pit rock structure usually contains geological planes of weakness. They are formed by joints, faults, bedding planes, fractures, and cleavages. Rock slope failures often occur in the form of sliding of rock blocks along a plane or several planes. Such a rock block has three- dimensional geometry, and consequently a vector method of analysis has been found useful in evaluating its stability. Rock blocks of a tetrahedral shape with one free surface have been analyzed by Londe. Rock blocks formed by sets of parallel joints have been analyzed by Wittke. The present chapter presents the analysis of rock blocks formed by planes of weakness of arbitrary orientation, and of three-dimensional geometry.

Jan 1, 1972

By Tibor Zoltai

Asbestos is a generic term for industrially useful fibers recovered from exploitable deposits of the asbestiform varieties of five silicate minerals: chrysotile, anthophyllite, actinolite-tremolite, cummingtonite-grunerite, and riebeckite. Asbestos and asbestiformm fibers of some other minerals are known to be carcinogenic. Minerals crystallized in the asbestiform habit are characterized by unique properties (morphology, strength and flexibility, physical and chemical durability, and defect-free surface structures). The key to the unusual properties, and health effects, of asbestifarm fibers appears to be in their unusual surface structure. In contrast, non-asbestiform crystals of the same minerals, including the five so-called asbestos minerals do not have these properties and are not carcinogenic (1, 2).

Jan 1, 1989

By Hamid-Reza Manouchehri

"The triboelectric charge attributes of feldspar, quartz and wollastonite minerals, after contacting different triboecharging medium made of different materials, were considered. Their charge acquisitions by different size fractions of minerals were monitored and accordingly their energetic work function values were estimated. Moreover the separation behaviours of these minerals through the electric field of a laboratory free falling separator were determined and the effects of some chemical reagents on separation their separation characteristics were studied.Finally an attempt was made to translate the findings from single mineral systems to a complex silicate ore, containing quartz, feldspars, wollastonite and some other silicates. The results show favourable prospect to apply the triboelectric separation technique for beneficiation such a complex raw material."

Jan 1, 2003