The effect of temperature on phase equilibria of polyethylene glycol (PEG8000)-K2SO4-H2O at T = (288.15, 298.15, 308.15) K

The phase behavior of potassium sulfate (K₂SO₄) in polyethylene glycol with molecular weight 8000 (PEG8000) and water (H₂O) mixed solvent at 288.15, 298.15, and 308.15 K were determined. According to the results, when the temperature are 288.15 and 298.15 K, there is only a solid–liquid phase equilibrium relationship in the system, and the phase diagrams are both divided into three parts which respectively are the regions of unsaturated homogeneous liquid (L), one liquid and one solid K₂SO₄ (L + S) and one liquid and two solids K₂SO₄ and PEG8000 (L + 2S). The solubility of K₂SO₄ in PEG8000-H₂O mixed solvent decreased with the addition of the PEG8000 in the solution. Comparing the diagrams of 288.15 and 298.15 K, the sizes of regions of (L) and (L + S) increased and that of (L + 2S) decreased with the increase of temperature. While at 308.15 K, solid–liquid and liquid–liquid equilibrium coexist, and there are six parts in the complete phase diagram at 308.15 K, adding the areas of one liquid and one solid K₂SO₄ (L + S), two liquids (2 L), two liquids and one solid K₂SO₄ (2 L + S). The equations developed by Merchuk, Hu, and Jayapal were used to fit the binodal curves data of the system at 308.15 K, meanwhile, the experimental tie-line data of the system at 308.15 K were correlated by Othmer-Tobias equation and Bancroft equation.     

Notes on the issues of equilibrium in the Fischer–Tropsch synthesis

The product distribution for the Fischer–Tropsch synthesis is normally described using the kinetically derived (Anderson–Schultz–Flory) ASF model. Variations of the kinetic model have been proposed to explain deviations from the ASF distribution. The Fischer–Tropsch system can be equally well described using a pseudo‐element (CH₂, H₂, O) equilibrium approach. A one‐parameter equilibrium model is derived for the product distributions for alkenes, alkanes and alcohols. The Fischer–Tropsch system should be considered as three separate partial equilibria systems: the product homologous series; the water gas shift system, and the redox behaviour of the catalyst with the H₂/O ratio of the gas. This approach correctly predicts the impacts of changes in a variety of parameters (temperature pressure, feed composition) on the ASF product distribution. In addition, the catalyst phase changes with gas composition and pressure, indicative of an equilibrium response. Equilibrium is of much greater importance to the Fischer–Tropsch system than previously thought, and the decision to use a complex kinetics‐based model rather than a simpler equilibrium based model should be taken with care.     

Solubilities of solid n‐alkanes in methane: Data analysis and models assessment

This article reviews the results of experiments underway since 1950 studying the solid solubility of n‐alkanes (from ethane up to n‐triacontane) in methane and the factors influencing the global phase equilibrium behavior of the related binary mixtures. The methodology used consists of a series of comparisons of data in the composition‐temperature and pressure‐temperature diagrams. The kind of global phase diagram of the binary mixtures of methane referred to in the present article is found to be dependent of the ratio between the triple‐point temperature of the generic n‐alkane and the critical‐point temperature of methane. The Peng‐Robinson (1976), Predictive Soave‐Redlich‐Kwong, and Predictive Peng‐Robinson (1978) equations of state have been applied and compared with respect to the calculation of bivariant, univariant, and invariant equilibrium data involving solid n‐alkanes in binary mixture with methane. The fugacities of the solid n‐alkanes have been calculated by means of the so‐called classic approach. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2219–2239, 2018     

Lignocellulosic substrates influence on TTT and CHT curing diagrams of polycondensation resins

Lignocellulosic substrates such as wood were found to have a marked modifying influence on a well‐defined region of CHT diagrams during hardening of phenol–formaldehyde (PF) and urea–formaldehyde (UF) polycondensates. This was ascribed to more complex resin phase transitions due to resin/substrate interactions peculiar to these substrates. The chemical and physical mechanisms of the interactions of the resin and substrate causing such CHT diagram modifications are presented and discussed. The Di Benedetto equation describing the glass transition temperature T_g of the system as a function of the resin degree of conversion p has been slightly modified to take into account the modified CHT diagram. The modified CHT diagram can be used to good effect to describe the behavior of polycondensation resins when used as wood adhesives during their curing directly into the wood joint. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 915–925, 1999     

Thermodynamics and separation process for quaternary acrylic systems

Vapor‐liquid equilibrium (VLE) and liquid‐liquid equilibrium (LLE) data of binary and ternary acrylic systems were systematically measured. Subsequently, VLLE phase diagrams of binary systems, tridimensional VLE phase diagrams of methyl acrylate (MA)‐methanol (Me)‐H₂O ternary system, and quaternary LLE phase diagrams of MA‐Me‐H₂O‐methyl acetate (MeOAc) system were constructed. These diagrams clearly demonstrated the effects of temperature on phase equilibrium. The experimental data was fitted by the NRTL and UNIQUAC models, and the best‐fitted parameters were used to predict interaction properties of ternary and quaternary mixture. Therefore, the phase equilibrium data were provided as reference for the design of acrylic systems rectification or extraction process. Residue curve was mapped out for MA‐Me‐H₂O system through Aspen plus software. Finally, using thermodynamics and residue curve as theoretical basis, two novel separation processes were proposed and applied to the quaternary acrylic systems. © 2015 American Institute of Chemical Engineers AIChE J, 62: 228–240, 2016     

The Microstructure and Dielectric Properties of SiBCN Ceramics Fabricated Via LPCVD/CVI

Low‐pressure chemical vapor deposition and infiltration was used for the first time to fabricate SiBCN ceramics with proper dielectric properties to lower the preparation temperature. SiBCN ceramics indicated by thermodynamic phase diagram with different phase compositions from CH₃SiCl₃–NH₃–BCl₃‐H₂ could be obtained through adjustable parameters. The as‐prepared SiBCN ceramics fabricated above 900°C showed proper dielectric properties with dielectric loss of about 0.1, which was due to the generation of amorphous carbon and SiC nanocrystals.     

Theoretical pressure dependency of carbon dioxide solubility under hydrate–liquid water equilibrium

The effect of pressure on carbon dioxide solubility in water is significantly smaller than that of temperature under hydrate–liquid water (H–L_w) equilibrium. As a result, experimental values of carbon dioxide solubility in the water rich liquid phase under H–L_w equilibrium are often inconclusive and in some cases contradictory. This work proposes a theoretical derivation, based on fundamental thermodynamics, of the gas hydrate former solubility dependency on pressure for any binary system under two‐phase equilibrium. The obtained expression is applied to the carbon dioxide–water system under both hydrate–liquid water and vapour–liquid water equilibrium. It is shown that the solubility of carbon dioxide in the water rich liquid phase increases with increasing pressure under H–L_w equilibrium. The predicted trend is then compared to the limited experimental data available in the literature.     

Solubility measurement and prediction of phase equilibria in the quaternary system LiCl + NaCl + KCl + H_2O and ternary subsystem LiCl+ NaCl + H_2O at 288.15 K

Using isothermal dissolution method, the phase equilibrium relationship in quaternary system LiCl + NaCl + KCl+ H_2O and the ternary subsystem LiCl + NaCl + H_2O at 288.15 K were investigated. Each phase diagram of two systems was drawn. The phase diagram of LiCl + NaCl + H_2O system contains two solid phase regions of crystallization LiCl·2H_2O and NaCl. In the phase diagram of LiCl + NaCl + KCl + H_2O system, there are three crystallization regions: LiCl·2H_2O, NaCl and KCl respectively. In this paper, the solubilities of phase equilibria in two systems were calculated by Pitzer's model at 288.15 K. The predicted phase diagrams generally agree with the experimental phase diagrams.     

Synthesis of Mo–W carbide via propane carburization of the precursor sulfide: Kinetic analysis

Thermogravimetric analysis (TGA) has been used to investigate the carburization kinetics of Mo–W sulfide using an H₂:C₃H₈ feed mixture. The effect of heating rate over the range 1–10 K min^?1 showed that up to four different carburized products may be formed but the critical (peak) temperature for formation of these species and the amount (peak height) of each species formed are highly dependent on the heating rate employed. The critical temperature increased linearly with heating rate for each of the four products. The four TGA peaks corresponding to the four phase transformation species are consistent with XRD identifiable species, namely; α‐Mo₂C, β‐Mo₂C, W and MoC_1?x. Isothermal conversion–time data at three different temperatures are described by a reaction‐controlled shrinking core model implicating a first‐order dependency on the H₂:C₃H₈ ratio. The reaction exhibited fractional order dependence on the metal sulfide concentration, the associated global activation energy estimated as 227 kJ mol^?1 is representative of a non‐catalytic gas–solid reaction. Copyright © 2004 Society of Chemical Industry     

Separation of fullerenes C60 and C70 using a crystallization‐based process

A crystallization‐based process that separates pure fullerenes C₆₀ and C₇₀ from their mixture using o‐xylene as the solvent has been developed. Isothermal solid–liquid equilibrium phase diagrams of the C₆₀‐C₇₀‐o‐xylene ternary system for a number of temperatures were first determined at 1 atm. Taking advantage of the shift in solvent‐free composition of the C₆₀‐C₇₀ double saturation point with temperature and based on the solid solution‐forming phase behavior between C₆₀ and C₇₀, the flowsheet of a general crystallization process was then synthesized. It involved the fractionation of a C₆₀‐C₇₀ fullerene mixture into C₆₀‐rich and C₇₀‐rich solid solutions using temperature‐swing crystallization, followed by purification of the solid solutions with multistage crystallization into pure C₆₀ and C₇₀ solids. To demonstrate process feasibility, bench‐scale batch experiments were performed using a commercially available fullerene mixture that was pretreated by adsorption to remove higher fullerenes. C₆₀ and C₇₀ solids of purity higher than 99 wt % were obtained. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Humidity Related Low Temperature Conductivity Hysteresis of Ce1–xZrxO2 (0 ≤ x ≤ 1) Ceramics. Structural Disorder Relationship

Ion‐electron mixed conductivity of the Ce_1–xZr_xO₂ (0 < x < 1) series, prepared by solid‐state reaction, has been measured as a function of temperature, pO₂ and pH₂O relative pressures. The structural analysis of this series shows the formation of monoclinic, tetragonal, and cubic phases as the Ce content increases. The temperature used in samples preparation, 1,923 K, favors at intermediate compositions the homogeneous Ce and Zr mixing in the metastable tetragonal t′ phase. The variation of conductivity with the relative oxygen pressure indicates that electronic contribution increases, becoming preponderant, as the Ce‐content increases. The modifications in conductivity observed in Ce‐rich samples have been ascribed to the enhancement of the electronic contribution at the grain‐boundary of ceramics. The differences observed at low temperatures in electronic dc‐conductivity of Ce‐rich samples during heating and cooling treatments, have been ascribed to the incorporation of water as hydroxide defects at the grain boundary and interior of the particles. The surface hydroxylation is maximal in samples with improved OSC capacity, decreasing drastically in samples heated at 740 K. Finally, the potential application of prepared materials in intermediate temperature solid oxide fuel cells (SOFC) is discussed.     

Critical Evaluation and Thermodynamic Modeling of the MgO–MnO–Mn2O3–SiO2 System

A complete literature review, critical evaluation, and thermodynamic optimization of phase diagrams and thermodynamic properties of the MgO–MnO–Mn₂O₃–SiO₂ system at 1 atm pressure are presented. The molten oxide phase was described by the Modified Quasichemical Model considering the short‐range ordering in molten oxide, and the Gibbs energies of solid solutions were described using the Compound Energy Formalism considering the crystal structure of each solid solution. A set of optimized model parameters of all phases was obtained which reproduces all available and reliable thermodynamic data and phase diagrams within experimental error limits from 25°C to above the liquidus temperatures over the entire range of composition under the oxygen partial pressures from metallic saturation to 1 atm. The database of the model parameters can be used along with software for the Gibbs energy minimization to calculate any phase diagram section and thermodynamic property within the present system.     

The Effect of H2S on the Performance of SOFCs using Methane Containing Fuel

In recent years, the interest for using biogas derived from biomass as fuel in solid oxide fuel cells (SOFCs) has increased. To maximise the biogas to electrical energy output, it is important to study the effects of the main biogas components (CH₄ and CO₂), minor ones and traces (e.g. H₂S) on performance and durability of the SOFC. Single anode‐supported SOFCs with Ni–Yttria‐Stabilised‐Zirconia (YSZ) anodes, YSZ electrolytes and lanthanum‐strontium‐manganite (LSM)–YSZ cathodes have been tested with a CH₄–H₂O–H₂ fuel mixture at open circuit voltage (OCV) and 1 A cm^–2 current load (850 °C). The cell performance was monitored with electric measurements and impedance spectroscopy. At OCV 2–24 ppm H₂S were added to the fuel in 24 h intervals. The reforming activity of the Ni‐containing anode decreased rapidly when H₂S was added to the fuel. This ultimately resulted in a lower production of fuel (H₂ and CO) from CH₄. Applying 1 A cm^–2 current load, a maximum concentration of 7 ppm H₂S was acceptable for a 24 h period.     

Combined experimental and computational investigation of thermodynamics and phase equilibria in the CaO–TiO2 system

Phase relations in the CaO–TiO₂ system are of considerable interest in geology, metallurgy, and ceramics. Despite a number of studies of phase equilibria in the CaO–TiO₂ system, there are still some open questions regarding the stability of intermediate compounds. In this work, a series of specimens with different CaO:TiO₂ ratios were prepared by solid‐state reaction. The heat capacities of Ca₃Ti₂O₇ and Ca₄Ti₃O₁₀ from 300 to 1073 K were measured by differential scanning calorimetry and their formation enthalpies from the component oxides at 298 K were measured by high temperature oxide melt solution calorimetry. Using phase diagram information and thermodynamic data from the literature and the present measurements, thermodynamic optimization of the CaO–TiO₂ system was carried out by the CALPHAD technique. The phase diagram and the thermodynamic properties of the CaO–TiO₂ system were calculated using the obtained thermodynamic database, which clarify the stable and metastable phase equilibria of the system. The thermodynamic stability of the various compounds was discussed.     

Phase diagrams of thermally stable,polymer‐dispersed liquid crystals: Exploring the impact of chain length and chemical structure

Polymer‐dispersed liquid crystals (PDLCs) have garnered significant interest and motivated the investigation of the phase behavior of thermally stable smectic liquid crystals (LCs) via thermally induced phase separation (TIPS). In this study, we examined a series of two, biphenyl‐based smectic LCs suitable for high temperature polymer blend processing. Phase diagrams for LC/polystyrene (PS) blends at various compositions (0–60 wt%) were constructed. Less than 15 wt% of 8B8 (1,1′‐biphenyl‐4,4′‐diyl dioctanoate) LC in PS led to good polymer miscibility, while phase separation was induced at concentrations higher than 15 wt%. The LC concentration at saturation decreased with increasing aliphatic chain length. We also investigated the chain length (C6‐C16) effect on the PS glass transition temperature (T_g) at the LC saturation point. The T_g increased with increasing chain length due to reduced plasticization. We further examined the role of chemical structure (relatively less polar ether vs. more polar ester) on the phase diagram regions and the T_g of the nonpolar PS matrix, respectively. It is anticipated that these LC/PS phase diagrams will benefit elevated temperature processing for TIPS by highlighting the role of LC chemical structure and chain length on blend morphology. POLYM. ENG. SCI., 56:388–393, 2016. © 2016 Society of Plastics Engineers     

Preparation of sorbitol from D‐glucose hydrogenation in gas–liquid–solid three‐phase flow airlift loop reactor

A new process for D ‐glucose hydrogenation in 50 wt% aqueous solution, into sorbitol in a 1.5 m³ gas–liquid–solid three‐phase flow airlift loop reactor (ALR) over Raney Nickel catalysts has been developed. Five main factors affecting the reaction time and molar yield to sorbitol, including reaction temperature (T_R), reaction pressure (P_R), pH, hydrogen gas flowrate (Q_g) and content of active hydrogen, were investigated and optimized. The average reaction time and molar yield were 70 min and 98.6% under the optimum operating conditions, respectively. The efficiencies of preparation of sorbitol between the gas–liquid–solid three‐phase flow ALR and stirred tank reactor (STR) under the same operating conditions were compared. Copyright © 2004 Society of Chemical Industry     

Some New Perspective on the Reaction Mechanism of MgO–SiO2–H2O System

The application of MgO–SiO₂–H₂O system, one of the most popular basic refractories, is greatly limited because of the hydration of MgO. In this work, the phase and morphological development of MgO–SiO₂–H₂O system during aging were analyzed using various techniques. It is found that Mg(OH)₂ initially appears and the amount increases after 10 days aging at room temperature. At elevated temperature, the heat treatment can facilitate the hydration reaction. Mg(OH)₂ covers the surface of silica fume particles. The combination product connects with each other and distributes homogeneously around MgO particles to produce M–S–H gels, which inhibit the further hydration.     

Thermochemistry of BaSm2O4 and thermodynamic assessment of the BaO–Sm2O3 system

The BaO–Sm₂O₃ system is of interest for the optimization of synthesis of electroceramics. The only systematic experimental study of phase equilibria in the system was performed more than 40 years ago. The reported experimental values of the enthalpy of formation of BaSm₂O₄ are in conflict, and the reported compound Ba₃Sm₄O₉ has never been confirmed. In this work we synthesized BaSm₂O₄ by solid‐state reaction and determined its heat capacity, enthalpy of formation, and phase transitions by differential scanning calorimetry, high‐temperature oxide melt solution calorimetry and ultra‐high‐temperature differential thermal analysis, respectively. We confirmed the existence of Ba₃Sm₄O₉ and its apparent stability from 1873 to 2273 K by X‐ray diffraction on quenched laser‐melted samples but were not able to obtain single‐phase material for calorimetric measurements. The CALPHAD method was used to assess phase equilibria in the BaO–Sm₂O₃ system, using both available literature data and our new measurements. A self‐consistent thermodynamic database and the calculated phase diagram of the BaO–Sm₂O₃ system are provided. This work can be used to model and thus to understand the relationships among composition, temperature, and microstructure for multicomponent systems with BaO and Sm₂O₃.