Modelling liquid–liquid equilibria for island type ternary systems

Closed miscibility gaps in ternary liquid mixtures, at constant temperature and pressure, are obtained if phase separations occur only in the ternary region, whilst all binary mixtures involved in the system are completely miscible. This type of behaviour, although not very frequent, has been observed for a certain number of systems. Nevertheless, we have found no information about the applicability of the common activity coefficient models, as NRTL and UNIQUAC, for these types of ternary systems. Moreover, any of the island type systems published in the most common liquid–liquid equilibrium data collections, are correlated with any model. In this paper, the applicability of the NRTL equation to model the LLE of island type systems is assessed using topological concepts related to the Gibbs stability test. A first attempt to correlate experimental LLE data for two island type ternary systems is also presented.

Mapping Binary Liquid-Vapor or Liquid-Liquid-Vapor Equilibria Regions, including the Different Azeotropic Behaviours, as a Function of the NRTL Binary Parameters

13th Mediterranean Congress of Chemical Engineering (Sociedad Española de Química Industrial e Ingeniería Química, Fira Barcelona, Expoquimia), Barcelona, September 30-October 3, 2014

Effect of Al2O3 and Cr2O3 on loquidus temperatures in the cristobalite and tridymite primary phase fields of the MgO-"FeO"-SiO2 ststem in equilibrium with metallic iron

The effects of alumina and chromite impurities on the liquidus temperatures in the cristobalite/tridymite (SiO2) primary phase fields in the MgO-FeO-SiO, system in equilibrium with metallic iron have been investigated experimentally. Using high temperature equilibration and quenching followed by electron probe X-ray microanalysis (EPMA), liquiclus isotherms have been determined in the temperatures range 1 673 to 1 898 K. The results are presented in the form of pseudo-ternary sections of the MgO-FeO-SiO, system at 2, 3 and 5 wt% Al2O3, 2 wt% Cr2O3, and 2 wt% Cr2O3+2 wt% Al2O3. The study enables the liquidus to be described for a range of SiO2/MgO and MgO/FeO ratios. It was found that liquiclus temperatures in the cristobalite and tridymite primary phase fields, decrease significantly with the addition of Al2O3 and Cr2O3.

Subliquidus glass-glass immiscibility along the albite-diopside join

A calorimetric study has shown that glasses along the albite-diopside join in the system albiteanorthite-diopside have positive enthalpies of mixing. Thermodynamic calculations based on these data describe a nearly symmetric, metastable, subliquidus irascibility gap along the join with a critical temperature at 910 K. The existence of the miscibility gap was tested experimentally by annealing an Ab50Di50 glass at 748 K and 823 K. Annealed glasses were examined by optical microscopy and by scanning and transmission electron microscopy. The glasses showed morphological and chemical features consistent with unmixing of two glass phases. The apparent mechanism of phase separation involves initial spinodal decomposition followed by coarsening to produce 0.1 μm–0.3 μm spherical glass phases.

Poorly characterized phases in C2M carbonaceous chondrites : proposed structures and significance

Poorly characterized phases (PCP's) may constitute up to 30 volume percent of some C2M carbonaceous chondrite matrices [1] and are an important key to an understanding of matrix evolution. PCPs are usually fine-grained (phases in the matrix of Murchison. Ramdohr [3] described a similar Fe-S-C phase with trace amounts of Ni in five carbonaceous chondrites and proposed that this mineral has a layer structure. Both the Fe-S-Ni-0 and Fe-S-Ni-C phases have similar optical properties and are conveniently described by the generic term PCP [1]. On the basis of recent high resolution electron microscopy (HREM) studies [4-9], we propose that these PCP's form at least two ordered, stable structures based upon alternating sequences of mackinawite- and brucite- (or amakinite-) type layers.

Investigation of ternary zirconia ceramics

Transformation toughening ceramics (TTCs) are engineering materials which combine ceramic properties such as hardness, corrosion resistance and low thermal conductivity with good toughness and mechanical strength. At elevated temperatures their use is limited due to destabilisation of the transformation toughening microstructure (partially stabilised zirconia or PSZ) or creep and hydrothermal degradation (tetragonal zirconia polycrystals or TZPs). Despite these limitations, the use of TTCs, particularly zirconia based, has become widespread. To date, most commercial TTCs are based on combinations of zirconia and one stabilising oxide. This work investigates a zirconia ceramic containing two stabilisers, namely yttria and titania in roughly equal proportions.

High-temperature, low-H₂O silicic magmas of the Yellowstone Hotspot: an experimental study of Rhyolite from the Bruneau-Jarbidge eruptive center, Central Snake River Plain, USA

The phase relations have been investigated experimentally at 200 and 500 MPa as a function of water activity for one of the least evolved (Indian Batt Rhyolite) and of a more evolved rhyolite composition (Cougar Point Tuff XV) from the 12·8-8·1 Ma Bruneau-Jarbidge eruptive center of the Yellowstone hotspot. Particular priority was given to accurate determination of the water content of the quenched glasses using infrared spectroscopic techniques. Comparison of the composition of natural and experimentally synthesized phases confirms that high temperatures (>900°C) and extremely low melt water contents (<1·5 wt % H₂O) are required to reproduce the natural mineral assemblages. In melts containing 0·5-1·5 wt % H₂O, the liquidus phase is clinopyroxene (excluding Fe-Ti oxides, which are strongly dependent on fO₂), and the liquidus temperature of the more evolved Cougar Point Tuff sample (BJR; 940-1000°C) is at least 30°C lower than that of the Indian Batt Rhyolite lava sample (IBR2; 970-1030°C). For the composition BJR, the comparison of the compositions of the natural and experimental glasses indicates a pre-eruptive temperature of at least 900°C. The composition of clinopyroxene and pigeonite pairs can be reproduced only for water contents below 1·5 wt % H₂O at 900°C, or lower water contents if the temperature is higher. For the composition IBR2, a minimum temperature of 920°C is necessary to reproduce the main phases at 200 and 500 MPa. At 200 MPa, the pre-eruptive water content of the melt is constrained in the range 0·7-1·3 wt % at 950°C and 0·3-1·0 wt % at 1000°C. At 500 MPa, the pre-eruptive temperatures are slightly higher (by 30-50°C) for the same ranges of water concentration. The experimental results are used to explore possible proxies to constrain the depth of magma storage. The crystallization sequence of tectosilicates is strongly dependent on pressure between 200 and 500 MPa. In addition, the normative Qtz-Ab-Or contents of glasses quenched from melts coexisting with quartz, sanidine and plagioclase depend on pressure and melt water content, assuming that the normative Qtz and Ab/Or content of such melts is mainly dependent on pressure and water activity, respectively. The combination of results from the phase equilibria and from the composition of glasses indicates that the depth of magma storage for the IBR2 and BJR compositions may be in the range 300-400 MPa (13 km) and 200-300 MPa (10 km), respectively.

Retrogressed eclogite (20 kbar, 1020 °C) from the Neoproterozoic Palghat–Cauvery suture zone, southern India

The Palghat–Cauvery suture zone in southern India separates Archaean crustal blocks to the north and the Proterozoic Madurai block to the south. Here we present the first detailed study of a partially retrogressed eclogite (from within the Sittampundi anorthositic complex in the suture zone) that occurs as a 20-cm wide layer in a garnet gabbro layer in anorthosite. The eclogite largely consists of an assemblage of coexisting porphyroblasts of almandine–pyrope garnet and augitic clinopyroxene. However, a few garnets contain inclusions of omphacite. Rims and symplectites composed of Na–Ca amphibole and plagioclase form a retrograde assemblage. Petrographic analysis and calculated phase equilibria indicate that garnet–omphacite–rutile–melt was the peak metamorphic assemblage and that it formed at ca. 20 kbar and above 1000 °C. The eclogite was exhumed on a very tight hairpin-type, anticlockwise P–T path, which we relate to subduction and exhumation in the Palghat–Cauvery suture zone. The REE composition of the minerals suggests a basaltic oceanic crustal protolith metamorphosed in a subduction regime. Geological–structural relations combined with geophysical data from the Palghat–Cauvery suture zone suggest that the eclogite facies metamorphism was related to formation of the suture zone. Closure of the Mozambique Ocean led to development of the suture zone and to its western extension in the Betsimisaraka suture of Madagascar.

Solubilities of solids in supercritical fluids using dimensionally consistent modified solvate complex models

New dimensionally consistent modified solvate complex models are derived to correlate solubilities of solids in supercritical fluids both in the presence and absence of entrainers (cosolvents). These models are compared against the standard solvate complex models [J.Chrastil, J. Phys. Chem. 86 (1982) 3016-3021; J.C. Gonzalez, M.R.Vieytes, A.M. Botana, J.M. Vieites, L.M. Botana, J. Chromatogr. A 910 (2001) 119-125; Y. Adachi, B.C.Y. Lu, Fluid Phase Equilb. 14 (1983) 47-156; J.M. del Valle, J.M. Aguilera, Ind. Eng. Chem. Res. 27 (1988) 1551-1553] by correlating the solubilities of 13 binary and 12 ternary systems. Though the newly derived models are not significantly better than the standard models in predicting the solubilities, they are dimensionally consistent. (C) 2009 Elsevier B.V. All rights reserved.

Gibbs Energy of Formation of MnO: Measurement and Assessment

Based on the measurements of Alcock and Zador, Grundy et al. estimated an uncertainty of the order of +/- 5 kJ mol(-1) for the standard Gibbs energy of formation of MnO in a recent assessment. Since the evaluation of thermodynamic data for the higher oxides Mn3O4, Mn2O3, and MnO2 depends on values for MnO, a redetermination of its Gibbs energy of formation was undertaken in the temperature range from 875 to 1300 K using a solid-state electrochemical cell incorporating yttria-doped thoria (YDT) as the solid electrolyte and Fe + Fe1-delta O as the reference electrode. The cell can be presented as Pt, Mn + MnO/YDT/Fe + Fe1+delta O, Pt Since the metals Fe and Mn undergo phase transitions in the temperature range of measurement, the reversible emf of the cell is represented by the three linear segments. Combining the emf with the oxygen potential for the reference electrode, the standard Gibbs energy of formation of MnO from alpha-Mn and gaseous diatomic oxygen in the temperature range from 875 to 980 K is obtained as: Delta G(f)(o)/Jmol(-1)(+/- 250) = -385624 + 73.071T From 980 to 1300 K the Gibbs energy of formation of MnO from beta-Mn and oxygen gas is given by: Delta G(f)(o)/Jmol(-1)(+/- 250) = -387850 + 75.36T The new data are in excellent agreement with the earlier measurements of Alcock and Zador. Grundy et al. incorrectly analyzed the data of Alcock and Zador showing relatively large difference (+/- 5 kJ mol(-1)) in Gibbs energies of MnO from their two cells with Fe + Fe1-delta O and Ni + NiO as reference electrodes. Thermodynamic data for MnO is reassessed in the light of the new measurements. A table of refined thermodynamic data for MnO from 298.15 to 2000 K is presented.

Trends in the stability of ternary oxides: Systems M-Pb-O (M = Ca, Sr, Ba)

Recent experimental investigations of phase equilibria and thermodynamic properties of the systems M-Pb-O, where M = Ca, Sr or Ba, indicate a regular increase in thermodynamic stability of ternary oxides, MPbO3 and M2PbO4, with increasing basicity of the oxide of the alkaline-earth metal. Number of stable interoxide compounds at 1100 K in the systems M-Pb-O (M = Mg, Ca, Sr, Ba) increases in unit increments from Mg to Ba. In this paper, experimentally determined standard Gibbs energies of formation of M2PbO4 (M = Ca, Sr, Ba) and MPbO3 (M = Sr, Ba) from their component binary monoxides and oxygen gas are combined with an estimated value for CaPbO3 to delineate systematic trends in thermodynamic stability of the ternary oxides. The trends are interpreted using concepts of tolerance factor and acid-base interactions. All the ternary oxides in these systems contain lead in the tetravalent state. The small Pb4+ ions polarize the surrounding oxygen ions and cause the formation of oxyanions which are acidic in character. Hence, the higher oxidation state of lead is stabilized in the presence of basic oxides of alkaline-earth group. A schematic subsolidus temperature-composition phase diagram is presented for the system BaO-PbO-O-2 to illustrate the change in oxidation states in binary and ternary oxides with temperature.

Tie lines and activities in the system NiO-MgO-SiO2 at 1373 K

The isothermal section of the phase diagram for the system NiO-MgO-SiO2 at 1373 K is established, The tie lines between (NiXMg1-X)O solid solution with rock salt structure and orthosilicate solid solution (NiYMg1-Y)Si0.5O2 and between orthosilicate and metasilicate (NiZMg1-Z)SiO3 crystalline solutions are determined using electron probe microanalysis (EPMA) and lattice parameter measurement on equilibrated samples, Although the monoxides and orthosilicates of Ni and Mg form a continuous range of solid solutions, the metasilicate phase exists only for 0 < Z < 0.096, The activity of NiO in the rock salt solid solution is determined as a function of composition and temperature in the range of 1023 to 1377 K using a solid state galvanic cell, The Gibbs energy of mixing of the monoxide solid solution can be expressed by a pseudo-subregular solution model: Delta G(ex) = X(1 - X)[(-2430 + 0.925T)X + (-5390 + 1.758T)(1 - X)] J/mol, The thermodynamic data for the rock salt phase are combined with information on interphase partitioning of Ni and Mg to generate the mixing properties for the orthosilicate and the metasilicate solid solutions, The regular solution model describes the orthosilicate and the metasilicate solid solutions at 1373 K within experimental uncertainties, The regular solution parameter Delta G(ex)/Y(1 - Y) is -820 (+/-70) J/mol for the orthosilicate solid solution, The corresponding value for the metasilicate solid solution is -220 (+/-150) J/mol, The derived activities for the orthosilicate solid solution are discussed in relation to the intracrystalline ion exchange equilibrium between M1 and M2 sites. The tie line information, in conjunction with the activity data for orthosilicate and metasilicate solid solutions, is used to calculate the Gibbs energy changes for the intercrystalline ion exchange reactions, Combining this with the known data for NiSi0.5O2, Gibbs energies of formation of MgSi0.5O2, MgSiO3, and metastable NiSiO3 are calculated, The Gibbs energy of formation of NiSiO3, from its component oxides, is equal to 7.67 (+/-0.6) kJ/mol at 1373 K.

Activities in the spinel solid solution FeXMg1−XAl2O4

Abstract: Activities in the spinel solid solution FexMg1-xAl2O4 saturated with alpha-Al2O3 have been measured for the compositional range 0 < X < 1 between 1100 and 1350 K using a bielectrolyte solid-state galvanic cell, which may be represented as Pt, Fe + FexMg1-xAl2O4 + alpha-Al2O3//(Y2O3)ThO2/ (CaO)ZrO2//Fe + FeAl2O4 + alpha-Al2O3, Pt Activities of ferrous and magnesium aluminates exhibit small negative deviations from Raoult's law. The excess free energy of mixing of the solid solution is a symmetric function of composition and is independent of temperature: Delta G(E) = -1990 X(1 - X J/mol. Theoretical analysis of cation distribution in spinel solid solution also suggests mild negative deviations from ideality. The lattice parameter varies linearly with composition in samples quenched from 1300 K. Phase relations in the FeO-MgO-Al2O3 system at 1300 K are deduced from the results of this study and auxiliary thermodynamic data from the literature. The calculation demonstrates the influence of intracrystalline ion exchange equilibrium between nonequivalent crystallographic sites in the spinel structure on intercrystalline ion exchange equilibrium between the monoxide and spinel solid solutions (tie-lines). The composition dependence of oxygen partial pressure at 1300 K is evaluated for three-phase equilibria involving the solid solutions Fe + FexMg1-xAl2O4 + alpha-Al2O3 and Fe + FeyMg1-yO + FexMg1-xAl2O4. Dependence of X, denoting the composition of the spinel solid solution, on parameter Y, characterizing the composition of the monoxide solid solution with rock salt structure, in phase fields involving the two solid solutions is elucidated. The tie-lines are slightly skewed toward the MgAl2O4 corner.

Modeling the solubilities of fatty acids in supercritical carbon dioxide

A thermodynamic model was developed for modeling the solubilities of fatty acids in supercritical carbon dioxide. The model combines the Peng-Robinson equation of state (EOS) with the two parameter van der Waal's mixing rules. The model is applied to predict the solubilities of various fatty acids. The two adjustable interaction parameters in the model are found to vary linearly with the chain length of the fatty acids. Thus this model can be used to predict the solubilities of various fatty acids in supercritical carbon dioxide. (C) 2003 Elsevier Science B.V. All rights reserved.

Thermodynamic properties of SmFeO3(S) and SM3R5O12(S)

The enthalpy increments and the standard molar Gibbs energy (G) of formation of SmFeO3(S) and SM3Fe5O12(s) have been measured using a Calvet micro-calorimeter and a solid oxide galvanic cell, respectively. A X-type transition, related to magnetic order-disorder transformation (antiferromagnetic to paramagnetic), is apparent from the heat capacity data at similar to673 K for SmFeO3(s) and at similar to560 K for Sm3Fe5O12(S). Enthalpy increment data for SmFeO3(s) and SM3Fe5O12(s), except in the vicinity of X-transition, can be represented by the following polynomial expressions: {H-m(0)(T) - H-m(0)(298.15 K){/J mol-(1)(+/-1.2%) = -54 532.8 + 147.4 . (T/K) + 1.2 . 10(-4) . (T/K)(2) +3.154 . 10(6) . (T/K)(-1); (298.15 less than or equal to T/K less than or equal to 1000) for SmFeO3(s), and {H-m(0)(T) - H-m(0)(298.15 K)}/J mol(-1) (+/-1.4%) = -192 763 + 554.7 . (T/K) + 2.0 . 10(-6) . (T/K)(2) + 8.161 . 10(6) - (T/K)(-1); (298.15 less than or equal to T/K less than or equal to 1000) for Sm3Fe5O12(s). The reversible emf of the solid-state electrochemical cells, (-)Pt/{SmFeO3(s) + Sm2O3(S) + Fe(s)) // YDT / CSZ // {Fe(s) + Fe0.95O(s)} / Pt(+) and (-)Pt/{Fe(s) + Fe0.95O(S)} // CSZ // {SmFeO3(s) + Sm3Fe5O12(s) + Fe3O4(s) / Pt(+), were measured in the temperature ranges of 1005-1259 K and 1030-1252 K, respectively. The standard molar G of formation of solid SmFeO3 and Sm3Fe5O12 calculated by the least squares regression analysis of the data obtained in the current study, and data for Fe0.95O and Sm2O3 from the literature, are given by: Delta(f)G(m)(0)(SmFeO3, s)/kj . mol(-1)(+/-2.0) = -1355.2 + 0.2643 . ; (1005 less than or equal to T/K less than or equal to 1570) and Delta(f)G(m)(0)(Sm3Fe5O12, s)/kj . mol(-1) (+/- 3.1) = -4891.0 + 1.0312 . (T/K); (1030 less than or equal to T/K less than or equal to 1252) The uncertainty estimates for Delta(f)G(m)(0) include the standard deviation in the emf and uncertainty in the data taken from the literature. Based on these thermodynamic data, the oxygen potential diagram for the system Sm-Fe-O was constructed at 1250 K.