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By L. B. Pankratz

Heat content measurements were conducted for GaPo.996 and InPo.986 over the temperature range from 298° to 1,100° K, and for In2S2.897 over the range from 298° to 1,200° K. Both the actual experimental data and values adjusted to conform with the stoichiometric compositions (GaP, InP, and In2S3) were reported. Entropy increments above 298.15° K were calculated for the stoichiometric compounds, and heat content and heat capacity equations were derived.

Jan 1, 1965

By J. N. Sicking, F. H. Brinkman

A new method for obtaining equilibrium vaporization ratios (K-values) for reservoir fluids has been developed and tested. By application of the method, complex experimental measurements of liquid and vapor phase compositions are eliminated. This simplified technique reduces the cost of experimental equilibrium-ratio data for reservoir studies of condensates and volatile crude-oil systems. The method is designed for systems of constant composition and, therefore, is best suited for depletion studies where compositional changes at high pressures are minor. The basic data required, in addition to the composition of the initial reservoir fluid, are the relative vapor-liquid volumes and densities at reservoir temperature and variom reservoir pressures. Tests demonstrated that the method predicts equilibrium ratios accurately for condensates. A single test on a crude oil was not conclusive; further testing will be necessary before the accuracy of the method can be determined for crude-oil systems. In addition to determining equilibrium ratios, the calculation method provides information on the physical properties of the "plus" component in the vapor and liquid phases. The "plus" component is that mixture of components heavier than the least volatile fraction analyzed. This information is useful in studies of both natural depletion and cycling operations for condensate reservoirs where the heptanes-plus component in the gas phase is produced from the reservoir. INTRODUCTION As more volatile oil and condensate reservoirs are found, the use of phase behavior techniques to predict their performance is increasing in importance. These techniques have long been used for condensate fields and have more recently been applied to crude-oil fields containing oils of medium-to-high volatility. In these phase behavior methods, equilibrium ratios (K-values) are used to predict compositional changes in the reservoir fluids—thereby accounting for the recoverable oil that exists in the gas phase. The reliability of the predictions depends to a large extent on the equilibrium ratios used. These values must be obtained for each component for the entire pressure range being investigated. Unfortunately, because of the complex nature of hydrocarbon mixtures, accurate K-values are hard to obtain. The equilibrium ratios for a particular component will vary not only with the temperature and pressure, but also with over-all composition of the system. The importance of composition is quite critical at elevated pressures, but becomes negligible at pressures below about 300 psia. Therefore, because most phase behavior problems involve the high-pressure region, each fluid system becomes a special case. Experimental programs to determine characteristic K-values are quite difficult and time-consuming. Thus, it is often necessary to resort to approximations of the K-value data. Charts giving K-values for various mixtures and classes of mixtures are available in the literature. However, there are two major difficulties in using them: (1) the K-values of the "plus" component (that mixture of components heavier than the last one analyzed) must be obtained by extrapolation from the K-values of the other components; and (2) the K-values obtained must finally be adjusted by trial and error to agree with observed volumetric data. To eliminate these difficulties, a new method of determining equilibrium ratios was developed. Briefly, after the composition of the system as a whole has been analyzed, the method uses empirical correlations and the gross fluid properties of the system (relative vapor-liquid volumes and densities) to calculate K-values. Because the calculative procedure is long, it is best solved on a digital computer. About one hour of machine time on an IBM 650 computer is required to develop a K-chart for the fluid being examined. DEVELOPMENT OF THE METHOD OF OBTAINING K-VALUES Equilibrium ratios are defined as the ratio of the mole fraction of a component in the vapor phase to its mole fraction in the liquid phase. This statement is expressed in Eq. 1. A typical plot of equilibrium ratios for a particular system is shown in Fig. 1. It should be noted that, at pressures near the saturation pressure, the K-values appear to converge to a common point. This apparent convergence point is called the convergence pressure and is a characteristic of the system involved. Various empirical correlations of K-values have been noted. It has been observed that an isothermal plot of

By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.' Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.' The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965

By D. G. Westlake

Levine has concluded that prismatic slip in titanium is controlled by two distinct thermally activated processes in the temperature ranges O° to 220°K and 220" to 300°K. We feel that his evidence is not convincing. He has drawn a curve through the plot of activation volume u* vs temperature T with a break at 22WK, Fig. 2. We believe that considering the possible experimental error apd the fact that there are only four points between 4° and 196°K, one could be justified to represent these points by the smooth curve we show as a solid line in Fig. 12. Levine believes that (8rf/aT)+ is discontinuous at 220°K, but he hints that he recognizes the possible doubt. We doubt seriously that the results shown in Fig. 1 indicate a discontinuity at 220°K. Certainly if he were justified in drawing a straight line through only four points on Fig. 2, we are even more justified in drawing straight lines through the seven points between 77" and 297°K on Figs. 1 and 3, because a straight line touches all seven of his circles. If his measurements of t were so precise that his decision to draw two curves in Fig. 3 is valid, then the experimental technique is deserving of further mention. We have drawn a smooth curve through the results in Fig. 3 and used this and the curve in Fig. 12 to obtain the values of shown in Fig. 13. Finding continuous is a contradiction of Fig. 4, which deserves comment itself. Levine obtained the solid circles in Fig. 4 using Fig. 2 and a smooth curve through the points shown in Fig. 3. We have replotted these solid circles in Fig. 14. We submit that there is no basis for his two straight lines (dashed in Fig. 14), and therefore have superimposed the curve that we believe is indicated. Certainly, there is reasonable doubt that a discontinuity in dH/dT exists at 220°K, even when one accepts Fig, 2. Furthermore, if one draws the straight lines indicated by least-squares treatments of the results presented as open circles in Fig. 4, their intersection is at about 196°K, not at 220°K as shown. Thus the alleged agreement between Figs. 3 and 4 with respect to "break" temperatures is not apparent. In Fig. 9, Levine has drawn a straight line very much different from the one indicated by a least-squares treatment. Obviously, he has done this because he recognized that H = 0 when T = 0. He is consistent in drawing the low-temperature curves in

Jan 1, 1968

By Zhigan Deng

Cooling crystallization was used to separate iron (III) and nickel (II) from acidic sulfate solution produced by leaching of molybdenum-nickel black shale. The effect of K2SO4 concentration, crystallization temperature, solution pH and crystallization time on recovery of nickel (II) and precipitation of iron (III) was investigated, in order to obtain effective separation of nickel and iron. The optimum parameters determined were as follows: 200 g/L K2SO4, 10 °C crystallization temperature, solution pH of 0.5 and 24 h crystallization. Under these conditions, 97.6% nickel (II) was recovered as K2Ni(SO4)2, 6H2O crystals and only 2.0% of the total iron (III) was precipitated. Recrystallization yielded K2Ni(SO4)2, 6H2O crystals with a purity of 98.4%.

By Nobuaki Sato

The electrical conductivity, k, of pure and sodium doped sulfur melts was measured with and without ultrasonic waves at temperatures ranging from 140 to 340'C by the two probe method using an ultra high resistance meter. The k value of the pure sulfur melt with irradiation jumped at around 170°C by an order of 102 after which it mouutuniocally increased from 10-5 to10-4 A' 1 cm-1 with an increase of the temperature. The addition of the sodium metal to the sulfur melt was found to cause a larger jumping in the K value. The k value increased with the increase of Na proportion in the melt. For a 10mol% Na doped sulfur melt it was as high as max ~30 A 1cm -1 above 180 C under the irradiation of of ultrasconics.

Jan 1, 2003

By A M. L Smith, W E. Dubbin, K A. Hudson-Edwards

Jarosites (KFe3(SO4)2(OH)6) are examples of minerals that are highly effective scavengers of toxic elements, and are abundant in acid rock drainage systems, acid sulfate soils, metallurgical wastes and other contaminated sites. The K, Fe and S sites can be filled by toxic elements such as Cd, Cu and Zn, but the mechanisms of this incorporation are not well understood.We have used atomistic simulation methods to model the jarosite (102) surface and its interactions with Cd, Zn and Cu, in order to understand the mechanisms by which these potentially toxic elements are incorporated into the K-jarosite structure. Our results suggest that incorporation via a defect complex consisting of an impurity cation at the K site charge balanced by a K vacancy stabilises the (102) surface in the order Cu>Zn>Cd.

Jan 1, 2008

By Verne S. Mutton, William A. Slivensky, Eric S. Weiss, Kenneth L. Cashdollar, Deepak R. Kohli

The National Institute for Occupational Safety and Health (NIOSH), Pittsburgh Research Laboratory, cooperated with Tecrete Industries Pty. Ltd. and BHP Australia Coal in a research program to evaluate the strength characteristics and air leakage of four seal and two stopping designs for use in underground coal mines. A fundamental safety research area for NIOSH is to eliminate the occurrence of coal mine explosions or to mitigate their effects. One approach to achieve this goal is to develop new and innovative seal designs that provide increased explosion isolation protection for the mining personnel against ignitions that originate from within the gob or. other worked-out areas of the mine Full-scale seals and stoppings were constructed in the Experimental Mine at Lake Lynn Laboratory near Fairchance, Fayette County, PA. They were ail--leakage tested, then subjected to a series of explosions with average pressure pulses ranging from 25 to 500 kPa (3.5 to 72 psi). Instrumentation measured seal displacement and acceleration as a function of time, providing data to assist in the development of numerical models 1'01- future seal design. All three seals designed with Meshblock wire forlnwo~-k ant1 a lnonolithic shotcrete core withstood the first explosion test, which generated an avcr-age rnaximu~n pressure of - 140 kPa (-20 psi) while maintaining acceptable air leakage rates. These seals I-anged from 175 to 325 mm thick. They included a 2.7-m-high by 325-mm-thick seal that was tesled 27 hr after completion against this - 140-kPa explosion pressure, a special requirement of the test program. This seal survived explosions with pressure pulses up to 300 kPa (43 psi). The 2.3-m-high by 325-mm-thick Meshblock seal survived three explosion tests with overpressures up to 455 kPa (66 psi) and satisfied the air leakage criteria. A I ,200-mm-thick plug seal was constructed of two Gunmesh formwork walls in-filled with shotcrete and a 3,450-kPa (500-psi) strength Aquablend core. This plug seal survived three explosions with pressure pulses ranging 11-om 150 lo 430 kPa (-22 to 62.5 psi) with no measurable postexplosion air leakage. Two Gunmesh stoppings with thicknesses 01' 40 and 75 inln withstood explosion overpressures of 23 and 115 kPa, respectively. Anchoring all seal and stopping designs into the roof, ribs, and floor with steel "rootbolts" provided very effective boundary constraint that is critical to the performanceofstructures subject to explosion overpressures.

Jan 8, 1999

By R. X. Li

The overall flow-sheet of producing chromium (III) sulfate is described in this paper. The suitable conditions of each process such as sintering, leaching, aluminum removal, reduction, and de-composition conditions were experimentally studied. The results show it is reasonable to produce chromium (III) sulfate with the flow-sheet pointed out in this research work. The final product is Cr2(SO4)3 solution contained 150~250g/L Cr.

Jan 1, 2014

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

The heat capacities of four crystalline silicates of barium ( BaSiO3 , BaSiO4 , Ba Si¸0 , and BaSi₂0 ) and two crystalline silicates of strontium (SrSio and Sr₂Sio ) were measured over the temperature range from 51 ° to 298° K. The results were used to evaluate the entropies at 298.15 ° K. The entropy values were joined with known heats of formation to obtain the free energies of formation of the silicates with respect to their constituent oxides at 298.15 ° K.

Jan 1, 1964

By Mingyang Li, Yan Lv, Xiaolong Ma, Xudong Gao, Jie Zhao, Yingyi Zhang

The reduction process of pre-oxidized ilmenite concentrate powder in 30%CO–70%N2 atmosphere was characterized by thermogravimetric and differential thermogravimetric (TG-DTG) analysis system at the temperature from 1073 to1223 K. The isothermal reduction results show that the reduction process is divided into three stages and the corresponding apparent activation energies are obtained by iso-conversional method and model-fitting method, respectively. For the first stage, the conversion degree increases sharply with increasing time, and the reduction process is controlled by the random nucleation and subsequent growth model (A2 model). For the second stage, the conversion degree increases slowly with increasing time, and the reduction process is controlled by the diffusion of carbon monoxide in the reduced layer (D1 model). For the third stage, the reduction processes at different temperatures are controlled by the diffusion of carbon monoxide in the reduced layer (1073 K and D1 model), phase boundary chemical reaction (1123 K and R2 model), random nucleation and subsequent growth (1173 to 1223 K, A2, and A3 models), respectively. For the whole reduction process, the apparent activation energies obtained by iso-conversional method and model-fitting method are 71.72 and 31.92 kJ mol−1 , respectively

By Mingyang Li, Yan Lv, Xiaolong Ma, Xudong Gao, Jie Zhao, Yingyi Zhang

The reduction process of pre-oxidized ilmenite concentrate powder in 30%CO–70%N2 atmosphere was characterized by thermogravimetric and differential thermogravimetric (TG-DTG) analysis system at the temperature from 1073 to1223 K. The isothermal reduction results show that the reduction process is divided into three stages and the corresponding apparent activation energies are obtained by iso-conversional method and model-fitting method, respectively. For the first stage, the conversion degree increases sharply with increasing time, and the reduction process is controlled by the random nucleation and subsequent growth model (A2 model). For the second stage, the conversion degree increases slowly with increasing time, and the reduction process is controlled by the diffusion of carbon monoxide in the reduced layer (D1 model). For the third stage, the reduction processes at different temperatures are controlled by the diffusion of carbon monoxide in the reduced layer (1073 K and D1 model), phase boundary chemical reaction (1123 K and R2 model), random nucleation and subsequent growth (1173 to 1223 K, A2, and A3 models), respectively. For the whole reduction process, the apparent activation energies obtained by iso-conversional method and model-fitting method are 71.72 and 31.92 kJ mol−1 , respectively

By E. G. King

This report contains experimentally determined heat-content values for cerium dioxide and Columbium (niobium) dioxide in the temperature range from 298° to 1,800° K. There are no previous similar data for Columbium dioxide, and those for cerium dioxide have an upper limit of 373° K. The heat-content and corresponding entropy-increment data are presented in tabular form. Equations were derived to represent the heat contents and heat capacities. The data for cerium dioxide are entirely regular, but those for columbium dioxide show two previously unreported anomalies at 1,090° and 1,200° K.

Jan 1, 1961

By K. K. Kelley

This report contains heat-content values for hexagonal crystalline germanium dioxide between 298.15° and 1,350° K., and for germanium dioxide glass between 298.15° and 1,800° K. experimentally determined by the Federal Bureau of Mines. No similar data for these substances are to be found in the literature. The heat-content and corresponding entropy-increment data are presented both in tabular form and by equations. Free energy of formation values are estimated for germanium dioxide glass at 298.15° and 1,800° K.

Jan 1, 1961

By R. V. Mrazek

The heat of formation of vanadium trichloride was determined at 298.15° K. Measurements were made in a solution calorimeter in which an aqueous hydrochloric acid-potassium dichromate solvent was employed. Data are presented for the heats of solution of vanadium trichloride and the vanadium trioxide "backup" compound, and for appropriate dilution reactions needed to preserve stoichiometry. The resulting heat of formation of vanadium trichioride (VCI3) at 298.15° K was found to be ?H°298.15° K = -138.89 ±0.37 kcal/g mole.

Jan 1, 1968

By B. Aydin, G. Erturk, G. Bulut

Coal is a complex material because of its structure consisting of carbon constituents and mineral matter. Flotation is readily carried out due to hydrophobic characteristic of coal. Therefore coal flotation is the most commonly used technique for fine coal beneficiation in order to acquire clean coal separating ash forming mineral matter from carbonaceous matter. In the coal flotation, floatability of coal both depends on characteristic of coal and used flotation reagent. Frothers as a flotation reagent are used to facilitate air dispersion into fine bubbles by prevention of bubble coalescence in the pulp phase, and stabilization of flotation froths. In this study, the effects of frother types and concentrations at different pH and particle size on the coal flotation were investigated. The representative sample was taken from Zonguldak, Turkey. It contains 9.1% ash and 7313 (kcal/kg) calorific value. Pine oil, Dowfroth 250, MIBC and Isooctanol were tested as frother types. It is determined that 1.92 ppm frother concentration is sufficient to float coal, except pine oil. In mixed frother tests, it is seen that Dowfroth 250 is more effective than others. No significant difference in coal recovery was observed for flotation tests at the different pH values. The best results are obtained in size of coal (-0.1 mm) with all frothers.

Jan 1, 2014

By G M. Evans, C M. Phan

This paper presents an analysis on the dynamic adsorption of frothers and collectors onto air bubbles in flotation. The analysis was carried out using the theory on the surfactant transfer by diffusion and adsorption. The bubble size was considered when solving the diffusion equation for the dynamic surface excess. The adsorption kinetics was modelled employing the Langmuir adsorption isotherm and its extension with the inclusion of the lateral interaction of the adsorbed molecules (the Frumkin adsorption isotherm). The numerical computation was applied to solve the governing equations. The dynamic adsorption of the surfactants was measured in terms of the dynamic surface tension for sodium dodecylbenzene sulfonate (SDBS) and Dowfroth 250, using pendant bubble tensiometry. The results show that for air bubbles with diameter of the order of 1 mm, the bubble size effect on the dynamic surface tension is small and the solution of the diffusion equation for a planar gas-liquid surface can be used to describe the dynamic adsorption onto the air bubbles. The experimental data obtained with SDBS were well described by the Frumkin adsorption isotherm and the molecular diffusion. The model description for the experimental data obtained with Dowfroth 250 required the kinetic equations. The paper is relevant for further analysis of the role of the adsorbed surfactants in the particle collection.

Jan 1, 2005

By S. Combrink, N. Naude

Hydrocyclones are widely used in wet mineral classification applications and can be notoriously prone to wear. The methods currently used for quantifying hydrocyclone wear profiles are mostly twodimensional. In this paper it was attempted to quantify and monitor wear in three-dimensions, using a micro-CT scanner (Nikon XTH 225 ST). Hydrocyclone wear and, more specifically, spigot wear was investigated on a Multotec HC250 (Dc 250 mm, barrel diameter) hydrocyclone. The hydrocyclone is lined by a vulcanised natural rubber compound within a metal shell, with a thermosetting polyurethane spigot and vortex finder. Tests were conducted on the hydrocyclone in a pilot-scale recirculating test setup. The wear rate of the spigot was quantified by measuring the volume change within the spigot over 122 days in operation, using the micro-CT scanner. After 122 days in operation (recirculating feed materials) the wear in the hydrocyclone led to only a 13.67% loss of spigot volume. The relatively low wear rate could be related to the fact that material recirculation led to particle smoothing and a reduction in size, thereby decreasing the wear rate. This also shows the enormous influence that particle shape and size have on wear. The research was conducted with the support of Multotec, NECSA and the University of Pretoria. Keywords: Wear, hydrocyclone, micro-CT

Jan 1, 2020

By R. Blickensderfer

Several thin film absorber stacks with spectrally selective characteristics were developed by the Bureau of Mines. The stacks consisted of a silicon thick film or a zirconium compound thin film on a reflective thin film of silver. The zirconium absorber films, with the general formula ZrCxOyNz, were prepared by reactively sputtering zirconium or zirconium carbide in argon with small amounts of oxygen, nitrogen, or both, or by oxidizing zirconium films in air. A few similar types of films were prepared from titanium. The short-wave absorptance over the solar spectrum, a(s), and thermal emittance at 600 K, e(600 K), of the solar absorber stacks were calculated from room-temperature reflectance data. The values of a(s) ranged from 0.47 to 0.93, e(600 K) from 0.49 to 0.034, and the ratio a(s)/e(600 K) from 1.7 to 34. The specimen with the best combination of properties, a ZrNx-Ag stack, had a solar absorptance a(s) of 0.85 and a ratio, a(s)/e(600 K), of 24. The effect of film thickness and composition on spectral selectivity was determined. An emissometer for measuring normal total emittance up to 800 K and a method for determining a (s), e(T) (hemispherical), and a(s)/e(T) using simulated solar radiation are described. A calorimetric method for measuring a(s) and e(T) (hemispherical) at elevated temperature is also described. Measurements made on several specimens agreed favorably with calculated values.

Jan 1, 1976

By J. J. Talja

An investigation of oxidation of various nickel concentrates was carried out using differential scanning calorimetry (DSC). The aim of this study was to determine the ignition temperature and investigate other oxidation behavior of various sulfide-based nickel concentrates. Variables in the experiments were mineralogy, particle size and partial pressure of oxygen with temperature increasing linearly at 25 K/min from 323 to 1023 K (50-750 °C). The igni¬tion temperature was determined to represent the starting point of rapid oxidation. The reac¬tion enthalpies of the concentrates were determined and the amount of heat generated up to various time were used to calculate the extent of reaction. Mineralogical changes at various stages of oxidation were also investigated. For this purpose a second set of DSC-experiments were carried out in which each experiment was interrupted at a desired temperature between 673-873 K. From these tests the weight loss of samples were determined and changes in the individual constituent of sulfide minerals were analyzed. For pentlandite-based Ni-concentrates the ignition temperature was 705-710 K (approximately 435 °C). Pyrite was the first sulfide to oxidize. Reactivity of the violarite-based concentrate was greater than those of the pentlandite-based concentrates. The stoi-chiometry of pentlandite changed before ignition because of preferential oxidation of iron. Rapid oxidation of the pentlandite mineral occurred at about 823 K (550 °C). By 900 K about 90 % of the iron in pentlandite was converted to hematite, and NiS containing some iron was formed.

Jan 1, 1994