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Equilibrium Calculations (equilibrium + calculation)
Kinds of Equilibrium Calculations Selected AbstractsThermodynamic Equilibrium Calculations for the Reforming of Coke Oven Gas with Gasification GasCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 1 2007B. Li Abstract Thermodynamic analyses of the reforming of coke oven gas with gasification gas for syngas were investigated as a function of coke oven gas-to-gasification gas ratio (1,3), oxygen-to-methane ratio (0,1.56), pressure (25,35,bar) and temperature (700,1100,°C). Thermodynamic equilibrium results indicate that the operating temperature should be approximately 1100,°C and the oxygen-to-methane ratio should be approximately 0.39, where about 80,% CH4 and CO2 can be converted at 30,bar. Increasing the operating pressure shifts the equilibrium toward the reactants (CH4 and CO2); increasing the pressure from 25 to 35,bar decreases the conversion of CO2 from 73.7,% to 67.8,%. The conversion ratio of CO2 is less than that in the absence of O2. For a constant feed gas composition (7,% O2, 31,% gasification gas, and 62,% coke oven gas), a H2/CO ratio of about 2 occurs at temperatures of 950,°C and above. Pressure effects on the H2/CO ratio are negligible for temperatures greater than 750,°C. The steam produced has an effect on the hydrogen selectivity, but its mole fraction decreases with temperature; trace amounts of other secondary products are observed. [source] Thermochemical Modeling of Oxide GlassesJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 12 2002Theodore M. Besmann A modified associate species approach is used to model the liquid phase in oxide systems. The relatively simple technique treats oxide liquids as solutions of end-member and associate species. The model is extended to representing glasses by treating them as undercooled liquids. Equilibrium calculations using the model allow the determination of species activities, phase separation, precipitation of crystalline phases, and volatilization. In support of nuclear waste glass development, a model of the Na2O,Al2O3,B2O3,SiO2 system has been developed that accurately reproduces its phase equilibria. The technique has been applied to the CaO,SiO2 system, which is used to demonstrate how two immiscible liquids can be treated. [source] Influence of ferric iron on the stability of mineral assemblagesJOURNAL OF METAMORPHIC GEOLOGY, Issue 6 2010J. F. A. DIENER Abstract Ferric iron is present in all metamorphic rocks and has the ability to significantly affect their phase relations. However, the influence of ferric iron has commonly been ignored, or at least not been considered quantitatively, mainly because its abundance in rocks and minerals is not determined by routine analytical techniques. Mineral equilibria calculations that explicitly account for ferric iron can be used to examine its effect on the phase relations in rocks and, in principle, allow the estimation of the oxidation state of rocks. This is illustrated with calculated pseudosections in NCKFMASHTO for mafic and pelitic rock compositions. In addition, it is shown that ferric iron has the capacity to significantly increase the stability of the corundum + quartz assemblage, making it possible for this assemblage to exist at crustal P,T conditions in oxidized rocks of appropriate composition. [source] Petrogenetic modelling of strongly residual metapelitic xenoliths within the southern Platreef, Bushveld Complex, South AfricaJOURNAL OF METAMORPHIC GEOLOGY, Issue 3 2010T. E. JOHNSON Abstract Xenoliths of quartz-absent Fe-rich aluminous metapelite are common within the platinum group element-rich mafic/ultramafic magmatic rocks of the Platreef. Relative to well-characterized protoliths, the xenoliths are strongly depleted in K2O and H2O, and have lost a substantial amount of melt (>50 vol.%). Mineral equilibria calculations in the NCKFMASHTO system yield results that are consistent with observations in natural samples. Lower-grade rocks that lack staurolite constrain peak pressures to ,2.5 kbar in the southern Platreef. Smaller xenoliths and the margins of larger xenoliths comprise micro-diatexite rich in coarse acicular corundum and spinel, which record evidence for the metastable persistence of lower-grade hydrous phases and rapid melting consequent on a temperature overstep of several hundred degrees following their incorporation in the mafic/ultramafic magmas. In the cores of larger xenoliths, temperatures increased more slowly enabling progressive metamorphism by continuous prograde equilibration and the loss of H2O by subsolidus dehydration; the H2O migrated to xenolith margins where it may have promoted increased melting. According to variations in the original compositional layering, layers became aluminosilicate- and/or cordierite-rich, commonly with spinel but only rarely with corundum. The differing mineralogical and microstructural evolution of the xenoliths depends on heating rates (governed by their size and, therefore, proximity to the Platreef magmas) and the pre-intrusive metamorphic grade of the protoliths. The presence or absence of certain phases, particularly corundum, is strongly influenced by the degree of metastable retention of lower-grade hydrates in otherwise identical protolith bulk compositions. The preservation of fine-scale compositional layering that is inferred to be relict bedding in xenolith cores implies that melt loss by compaction was extremely efficient. [source] The effect of TiO2 and Fe2O3 on metapelitic assemblages at greenschist and amphibolite facies conditions: mineral equilibria calculations in the system K2O,FeO,MgO,Al2O3,SiO2,H2O,TiO2,Fe2O3JOURNAL OF METAMORPHIC GEOLOGY, Issue 5 2000White Mineral equilibria calculations in the system K2O,FeO,MgO,Al2O3,SiO2,H2O,TiO2,Fe2O3 (KFMASHTO) using thermocalc and its internally consistent thermodynamic dataset constrain the effect of TiO2 and Fe2O3 on greenschist and amphibolite facies mineral equilibria in metapelites. The end-member data and activity,composition relationships for biotite and chloritoid, calibrated with natural rock data, and activity,composition data for garnet, calibrated using experimental data, provide new constraints on the effects of TiO2 and Fe2O3 on the stability of these minerals. Thermodynamic models for ilmenite,hematite and magnetite,ulvospinel solid solutions accounting for order,disorder in these phases allow the distribution of TiO2 and Fe2O3 between oxide minerals and silicate minerals to be calculated. The calculations indicate that small to moderate amounts of TiO2 and Fe2O3 in typical metapelitic bulk compositions have little effect on silicate mineral equilibria in metapelites at greenschist to amphibolite facies, compared with those calculated in KFMASH. The addition of large amounts of TiO2 to typical pelitic bulk compositions has little effect on the stability of silicate assemblages; in contrast, rocks rich in Fe2O3 develop a markedly different metamorphic succession from that of common Barrovian sequences. In particular, Fe2O3 -rich metapelites show a marked reduction in the stability fields of staurolite and garnet to higher pressures, in comparison to those predicted by KFMASH grids. [source] ,Forbidden zone' subduction of sediments to 150 km depth, the reaction of dolomite to magnesite + aragonite in the UHPM metapelites from western Tianshan, ChinaJOURNAL OF METAMORPHIC GEOLOGY, Issue 6 2003L. Zhang Abstract The solid-state reaction magnesite (MgCO3) + calcite (aragonite) (CaCO3) = dolomite (CaMg(CO3)2) has been identified in metapelites from western Tianshan, China. Petrological studies show that two metamorphic stages are recorded in the metapelites: (1) the peak mineral assemblage of magnesite and calcite pseudomorphs after aragonite which is only preserved as inclusions within dolomite; and (2) the retrograde glaucophane-chloritoid facies mineral assemblage of glaucophane, chloritoid, dolomite, garnet, paragonite, chlorite and quartz. The peak metamorphic temperatures and pressures are calculated to be 560,600 °C, 4.95,5.07 GPa based on the calcite,dolomite geothermometer and the equilibrium calculation of the reaction dolomite = magnesite + aragonite, respectively. These give direct evidence in UHP metamorphic rocks from Tianshan, China, that carbonate sediments were subducted to greater than 150 km depth. This UHP metamorphism represents a geotherm lower than any previously estimated for subduction metamorphism (< 3.7 °C km,1) and is within what was previously considered a ,forbidden' condition within Earth. In terms of the carbon cycle, this demonstrates that carbonate sediments can be subducted to at least 150 km depth without releasing significant CO2 to the overlying mantle wedge. [source] Temperature and Impurity Concentration Effects on Degradation of Nickel/Yttria-stabilised Zirconia Anode in PH3 -Containing Coal SyngasFUEL CELLS, Issue 1 2010M. Zhi Abstract Degradation of the Ni/yttria-stabilised zirconia (YSZ) anode of the solid oxide fuel cell has been evaluated in the coal syngas containing different PH3 concentrations in the temperature range from 750 to 900,°C. Thermodynamic equilibrium calculations show that PH3 in the coal syngas gas is converted mostly to P2O3 at 750,900,°C. The phosphorous impurity reacts with the Ni-YSZ anode to form phosphates. The P-impurity poisoning leads to the deactivation of the Ni catalyst and to the reduction in the electronic conductivity of the anode. The impurity poisoning effect on the anode is exacerbated by increase in the temperature and/or the PH3 concentration. [source] Emission of trace toxic metals during pulverized fuel combustion of Czech coalsINTERNATIONAL JOURNAL OF ENERGY RESEARCH, Issue 13 2003P. Danihelka Abstract A study of the trace elements emission (As, Se, Cd, Co, Cr, Cu, Zn, Hg, Tl, Pb, Ni, Sn, Sb, V, Mn and Fe) from pulverized coal combustion has been made at six heating and power stations situated in the Czech Republic. The amount of chlorine in coal has considerable influence on volatilization of some elements such as Zn, Cu, Pb, Hg and Tl, which is explained by the formation of thermodynamically stable compounds of these elements with chlorine. Generally, the affinities for Cl follows the order Tl > Cu > Zn > Pb > Co > Mn > Sn > Hg. The experimental data indicates enrichment of some of the trace toxic elements in the emissions (Cu, Zn, As, Se, Cd, Sn, Sb, Hg and Pb) and good agreement was obtained by thermodynamic equilibrium calculations with a few exceptions. In the case of Fe, Mn, Co, Cr and Sn calculated values are overestimated in the bottom ash and there are zero predicted amounts of these elements in the fly ash. In comparison, the results from experiments show up to 80% of these elements retained in fly ash. This implies that there exist additional steps leading to the enrichment by Fe, Mn, Co, Cr and Sn of small particles. Such mechanisms could include the ejection during devolatilization of small inorganic particles from the coal of bottom ash particles, or disintegration of the char containing these metals to small particles of fly ash. On the other hand, there are slightly overestimated or similar values of relative enrichment factors for As, V, Cu, Cd, Sb, Tl and Pb in the fly ashes and zero predicted values for bottom ashes. Our experimental results show about 5% or less of these elements are retained in bottom ashes, so they probably remain in the bottom ash inside unburned parts of coal. Copyright © 2003 John Wiley & Sons, Ltd. [source] Comparison of activity coefficient models for electrolyte systemsAICHE JOURNAL, Issue 5 2010Yi Lin Abstract Three activity coefficient models for electrolyte solutions were evaluated and compared. The activity coefficient models are: The electrolyte NRTL model (ElecNRTL) by Aspentech, the mixed solvent electrolyte model (MSE) by OLI Systems, and the Extended UNIQUAC model from the Technical University of Denmark (DTU). Test systems containing a single salt (NaCl), multiple salts, and mixed solvent aqueous electrolyte solutions were chosen. The performance of the activity coefficient models were compared regarding the accuracy of solid,liquid and vapor,liquid equilibrium calculations for the test systems. © 2009 American Institute of Chemical Engineers AIChE J, 2010 [source] Zeolites in fissures of granites and gneisses of the Central AlpsJOURNAL OF METAMORPHIC GEOLOGY, Issue 8 2010T. WEISENBERGER Abstract Six different Ca-zeolite minerals are widespread in various assemblages in late fissures and fractures in granites and gneisses of the Swiss Alps. The zeolites formed as a result of water,rock interaction at relatively low temperatures (<250 °C) in the continental upper crust. The zeolites typically overgrow earlier minerals of the fissure assemblages, but zeolites also occur as monomineralic fissure fillings. They represent the youngest fissure minerals formed during uplift and exhumation of the Alpine orogen. A systematic study of zeolite samples showed that the majority of finds originate from three regions particularity rich in zeolite-bearing fissures: (i) in the central and eastern part of the Aar- and Gotthard Massifs; (2) Gibelsbach/Fiesch, in a fissure breccia located at the boundary of Aar Massif and Permian sedimentary rocks; and (3) in Penninic gneisses of the Simano nappe at Arvigo (Val Calanca). Rail and road tunnel construction across the Aar- and Gotthard Massif provided excellent data on zeolite frequency in Alpine fissures. It was found that 32% (Gotthard NEAT rail base tunnel, Amsteg section) and 18% (Gotthard road tunnel) of all studied fissures are filled with zeolites. The number of different zeolites is limited to six species: laumontite, stilbite and scolecite are abundant and common, whereas heulandite, chabazite and epistilbite occur occasionally. Calcium is the dominant extra-framework cation, with minor K and Na. Heulandite and chabazite contain Sr up to 29 and 10 mol.% extra-framework cations respectively. Na and K contents in zeolites tend to increase during growth as a result of changes in fluid composition and/or temperature. The K enrichment of stilbite found in surface outcrops compared to subsurface samples may indicate late stage cation exchange with surface water. Texture data, relative age sequences derived from fissure assemblages and equilibrium calculations show that the Ca-dominated zeolites precipitated from fluid with decreasing temperature in the order (old to young = hot to cold): scolecite, laumontite, heulandite, chabazite and stilbite. The necessary components for zeolite formation are derived from dissolving primary granite and gneiss minerals. The nature of these minerals depends, among other factors, on the metamorphic history of the host rock. Zeolites in the Aar Massif derived from the dissolution of epidote, secondary calcite and albite that were originally formed during Alpine greenschist metamorphism from primary granite and gneiss assemblages. Zeolite fissures occur in areas of H2O-dominated fluids. This is consistent with equilibrium calculations that predict a low CO2 tolerance of zeolite assemblages, particularly at low temperature. [source] Petrology of coesite-bearing eclogite from Habutengsu Valley, western Tianshan, NW China and its tectonometamorphic implicationJOURNAL OF METAMORPHIC GEOLOGY, Issue 9 2009Z. LÜ Abstract Coesite inclusions in garnet have been found in eclogite boudins enclosed in coesite-bearing garnet micaschist in the Habutengsu Valley, Chinese western Tianshan, which are distinguished from their retrograde quartz by means of optical characteristics, CL imaging and Raman spectrum. The coesite-bearing eclogite is mainly composed of porphyroblastic garnet, omphacite, paragonite, glaucophane and barroisite, minor amounts of rutile and dotted (or banded) graphite. In addition to coesite and quartz, the zoned porphyroblastic garnet contains inclusions of omphacite, Na-Ca amphibole, calcite, albite, chlorite, rutile, ilmenite and graphite. Multi-phase inclusions (e.g. Czo + Pg ± Qtz, Grt II + Qtz and Chl + Pg) can be interpreted as breakdown products of former lawsonite and possibly chloritoid. Coesite occurs scattered within a compositionally homogenous but narrow domain of garnet (outer core), indicative of equilibrium at the UHP stage. The estimate by garnet-clinopyroxene thermometry yields peak temperatures of 420,520 °C at 2.7 GPa. Phase equilibrium calculations further constrain the P,T conditions for the UHP mineral assemblage Grt + Omp + Lws + Gln + Coe to 2.4,2.7 GPa and 470,510 °C. Modelled modal abundances of major minerals along a 5 °C km,1 geothermal gradient suggests two critical dehydration processes at ,430 and ,510 °C respectively. Computed garnet composition patterns are in good agreement with measured core-rim profiles. The petrological study of coesite-bearing eclogite in this paper provides insight into the metamorphic evolution in a cold subduction zone. Together with other reported localities of UHP rocks from the entire orogen of Chinese western Tianshan, it is concluded that the regional extent of UHP-LT metamorphism in Chinese western Tianshan is extensive and considerably larger than previously thought, although intensive retrogression has erased UHP-LT assemblages at most localities. [source] Prograde metamorphic sequence of REE minerals in pelitic rocks of the Central Alps: implications for allanite,monazite,xenotime phase relations from 250 to 610 °CJOURNAL OF METAMORPHIC GEOLOGY, Issue 5 2008E. JANOTS Abstract The distribution of REE minerals in metasedimentary rocks was investigated to gain insight into the stability of allanite, monazite and xenotime in metapelites. Samples were collected in the central Swiss Alps, along a well-established metamorphic field gradient that record conditions from very low grade metamorphism (250 °C) to the lower amphibolite facies (,600 °C). In the Alpine metapelites investigated, mass balance calculations show that LREE are mainly transferred between monazite and allanite during the course of prograde metamorphism. At very low grade metamorphism, detrital monazite grains (mostly Variscan in age) have two distinct populations in terms of LREE and MREE compositions. Newly formed monazite crystallized during low-grade metamorphism (<440 °C); these are enriched in La, but depleted in Th and Y, compared with inherited grains. Upon the appearance of chloritoid (,440,450 °C, thermometry based on chlorite,choritoid and carbonaceous material), monazite is consumed, and MREE and LREE are taken up preferentially in two distinct zones of allanite distinguishable by EMPA and X-ray mapping. Prior to garnet growth, allanite acquires two growth zones of clinozoisite: a first one rich in HREE + Y and a second one containing low REE contents. Following garnet growth, close to the chloritoid,out zone boundary (,556,580 °C, based on phase equilibrium calculations), allanite and its rims are partially to totally replaced by monazite and xenotime, both associated with plagioclase (± biotite ± staurolite ± kyanite ± quartz). In these samples, epidote relics are located in the matrix or as inclusions in garnet, and these preserve their characteristic chemical and textural growth zoning, indicating that they did not experience re-equilibration following their prograde formation. Hence, the partial breakdown of allanite to monazite offers the attractive possibility to obtain in situ ages, representing two distinct crystallization stages. In addition, the complex REE + Y and Th zoning pattern of allanite and monazite are essential monitors of crystallization conditions at relatively low metamorphic grade. [source] Neon abundances in normal late-B and mercury,manganese starsMONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 4 2000M. M. Dworetsky We make new non-local thermodynamic equilibrium calculations to deduce the abundances of neon from visible-region echelle spectra of selected Ne i lines in seven normal stars and 20 HgMn stars. We find that the best strong blend-free Ne line that can be used at the lower end of the effective temperature Teff range is ,6402, although several other potentially useful Ne i lines are found in the red region of the spectra of these stars. The mean neon abundance in the normal stars (log A=8.10) is in excellent agreement with the standard abundance of neon (8.08). However, in HgMn stars neon is almost universally underabundant, ranging from marginal deficits of 0.1,0.3 dex to underabundances of an order of magnitude or more. In many cases, the lines are so weak that only upper limits can be established. The most extreme example found is , Her with an underabundance of at least 1.5 dex. These underabundances are qualitatively expected from radiative acceleration calculations, which show that Ne has a very small radiative acceleration in the photosphere, and that it is expected to undergo gravitational settling if the mixing processes are sufficiently weak and there is no strong stellar wind. According to theoretical predictions, the low Ne abundances place an important constraint on the intensity of such stellar winds, which must be less than 10,14 M, yr,1 if they are non-turbulent. [source] | ||||||||||