Zu den pseudobinären Zustandssystemen Bi2Ch3-BiX3 und den ternären Phasen auf diesen Schnitten (Ch = S, Se, Te; X = Cl, Br, I), I: Bismutsulfidhalogenide/The Pseudobinary Systems Bi2Ch3-BiX3 and the Ternary Phases on their Boundary Lines (Ch = S, Se, Te; X = Cl, Br, I), I: Bismuth Sulfide Halides

The phase diagrams of the systems Bi2S3-BiX3 were constructed from results of DTA and total pressure measurements and x-ray analysis. The phases: BiSCl, Bi4S5Cl2 and Bi19S27Cl3 for X = Cl; BiSBr and Bi19S27Br3 for X = Br; BiSI and Bi19S27I3 for X = I exist on the boundary lines. The enthalpies of formation and standard entropies of the phases follow from the coexistence decomposition pressure functions. The data are:ΔH°B(BiSClf,298) =−49,6 ± 1,6 kcal/mol S°(BiSClf,298) = 30,3 ± 2,5 cal/K·molΔH°B(Bi4S5Cl2,f,298) =−144,4 ± 3 kcal/mol S°(Bi4S5Cl2,f,298) = 114,0 ± 4,6 cal/K·molΔH°B(Bi19S27Cl3,f,298) = −520 ± 10 kcal/mol S°(Bi19S27Cl3,f,298) = 490 ± 10 cal/K·molΔH°B(BiSBrf,298) = −40,2 ± 1,4 kcal/mol S°(BiSBrf,298) = 32,0 ± 3 cal/K·molΔH°B(Bi19S27Br3,f,298) = −493,6 ± 6,7 kcal/mol S°(Bi19S27Br3,f,298) = 499,8 ± 17 cal/K·molΔH°B(BiSIf,298) =−27,8 ± 1,4 kcal/mol S°(BiSIf,298) = 36,1 ± 2,5 cal/K·molΔH°B(Bi19S27I3,f,298) =−464,4 ± 15 kcal/mol S°(Bi19S27I3,f,298) = 502,7 ± 15 cal/K·mol

The Effect of Temperature on Tensile and Compressive Strengths and Young's Modulus of Oil Shale

The analysis of underground oil-shale recovery processes requires knowledge of the mechanical properties of oil shale at various temperatures. The tensile strength, compressive strength, and Young's modulus are of special importance. The variation of these properties with temperature is important when assessing the strength of underground columns and confining walls for process cavities. This paper presents the results of an experimental study to quantify this temperature dependence. We found that both tensile and compressive strengths of oil shale show a marked decrease in strength as temperature increased, for a given richness. For example, for 15.6 gal/ton oil shale, the tensile strength at 400 deg. F is only 28% of its room temperature value. For 19.2 gal/ton shale, the compressive strength at 400 deg. F with 500-psi confining pressure is 43% of its value at room temperature. At a given temperature, both the tensile and compressive strengths decrease as richness increases, although the rate of decrease diminishes at richnesses of about 42 gal/ton and higher. Equations are developed to permit estimates of the various parameters involved. The compressive Young's moduli show a considerable decrease with temperature. At 400 deg. F the modulus is reduced to 51% of its room temperature value. Introduction In-situ processes for recovery of oil from nahcolite-bearing oil shale usually involve some heating or pyrolysis of the shale. Wet processes (steam, hot water) also involve dissolution of nahcolite to generate pore space and to create permeability. If the leaching of nahcolite is conducted at a sufficiently high temperature, some stress will develop in the rock beyond the heated cavity boundary because of CO2 generation and possibly water vapor, as follows. 2NaHCO3 goes to Na2CO3 + H2O + CO2. When the decomposition pressure of nahcolite is high enough, the rock tends to fracture ("popcorn effect"). Rubbling of the formation then can occur. To predict conditions suitable for fracturing and rubbling, we need to know how the rock tensile strength varies with temperature. McLamore measured the oil-shale tensile strength as a function of orientation of stress. So far as we know, no measurements of tensile strength as a function of temperature have been reported for oil shale. We also need to know the variation of nahcolite decomposition pressure with temperature. This pressure variation was measured by Templeton. The variation of Young's modulus, compressive strength, and Poisson's ratio also have been reported for various richnesses. Logan and Heard studied the compressive Young's modulus and thermal expansion as functions of richness. Compressive strength of oil shale has been studied extensively. This parameter was measured as a function of oil-shale richness for various confining pressures in triaxial tests at temperatures up to 300 deg. C (572 deg. F). The effect of temperature on rocks other than oil shale has also been studied. Knowledge of the compressive strength is important when assessing the possibility of failure of underground supporting walls in mines or with process cavities. Since the reacted oil shale probably will support the walls or the roofs of the process cavities very little, the strength of the supporting walls and roof under process conditions will determine the tendency for subsidence or intercavity communication. SPEJ P. 301^