Thermodynamic properties of methanol–benzene mixtures at elevated temperatures

The total pressure and the compositions of the vapour and liquid phases of the methanol–benzene system have been determined under equilibrium conditions at 100°, 120°, 140°, 160°, 180°, 200° and 220° for ten levels of concentration. The corresponding activity coefficients of methanol and benzene are reported; their values indicate that the equilibrium data are thermodynamically consistent. An azeotrope is found at all temperatures, its methanol content increasing as the temperature is increased. The relationship log P_az = 6·5098—(1,766/T) expresses the interdependence of the azeotrope vapour pressure P_az(lb/in² abs.) and temperature T(°K). Estimates of integral heat of mixing (H^E) and entropy change due to mixing (S^E) as functions of liquid composition (x_meth) have been made from the excess free energy of mixing G^E,(T) x_meth functions. Both H^E and S^E at a given x are positive increasing functions of temperature. These phenomena are discussed in terms of the dissociation of methanol ‘polymer’ and the formation of benzene–methanol ‘complexes’.     

Une éequation d'éetat de clausius modifiée repréeasentant l'éeatat liquide

The three parameters of a modified Clausius state equation have been generalized with a view to calculating thermodynamic properties of saturated pure substances, from the normal boiling temperature to the critical one. The method described in the paper, which only requires the knowledge of the characteristic properties of the pure substances (T_c, P_c, Z_c, ω) has been tested on 28 different compounds (saturated and unsaturated hydrocarbons, simple and polar molecules). The results obtained show that the state equation proposed correctly describes the liquid-vapour equilibrium (saturation vapour pressure and vaporization enthalpy) and moreover provides a satisfactory representation of the saturated liquid condition.     

Thermodynamic properties of the benzene and n-heptane system at elevated temperatures

The total vapour pressure and the composition of the liquid and vapour phases of the benzene and n-heptane system have been experimentally determined under equilibrium conditions at 110, 125, 140, 155, 170, 185, 200 and 215 °C. The corresponding composition of the vapour phase was also estimated using an expression for the liquid phase activity coefficient as a function of the composition of the liquid phase. Several expressions were compared and it has been found that the three-constant Redlich and Kister equation gave the best fit of the experimental vapour pressure data than the other equations. Comparison between the calculated and measured vapour compositions has shown a discrepancy of y_meas,—y_calc. of the order of 0.02 mol fraction or 10 times the experimental tolerance. Nevertheless, the experimental values were reasonably thermodynamically consistent. The low values of the liquid phase activity coefficients indicated that the behaviour of this particular system was not far from ideality. Also, it was found that the degree of non-ideality decreased with the increase in temperature. The behaviour of the vapour phase was shown also to be nearly ideal. The excess Gibbs free energy of mixing was calculated, and it was found to be non-symmetrical with mole fraction. On increasing the temperature of the system, the liquid composition corresponding to the maximum G^E tended to shift to a higher benzene concentration, whilst at a fixed liquid composition, G^E initially decreased and then remained stationary or increased again. This was thought to be due to differences in the molar volumes of the two components.     

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.     

Graphene–Fe3O4/PIL–PEDOT for the design of sensitive and stable quantum chemo-resistive VOC sensors

Quantum chemo-resistive vapour sensors have been synthesised from the assembly of magnetic nanoparticles-decorated reduced graphene oxide (Fe₃O₄–RGO) with poly(3,4-ethylene dioxythiophene) (PEDOT) and poly(ionic liquid) (PIL). This new hybrid sensing material demonstrated enhanced sensitivity, selectivity, signal-to-noise ratio and reduced response time compared to its elementary constituents (also sensitive), which suggests that a positive synergy of properties has been reached through the structuring of the conducting architecture by spray layer-by-layer. The Fe₃O₄-RGO/PIL–PEDOT sensor exhibited stable and reproducible signals at room temperature for both polar (ethanol, methanol, acetone, water) and non-polar (chloroform, styrene, dichlorobenzene, toluene) volatile organic compounds (VOC), considered as food degradation biomarkers. Since sensor’s responses are still well defined at the ppm level (and may be even at the subppm level) as attested by a SNR around 10, an application such smart packaging could be envisaged.     

A Combined Experimental and Computational Thermodynamic Investigation of the U–Th–O System

The thermodynamics of the U–Th–O system have been assessed using the Calphad method. The compound energy formalism (CEF) and a partially ionic two‐sublattice liquid model (TSLM) were used for the fluorite U_1–yTh_yO_2±x, γ‐(U,Th)₄O₉, and the U–Th–O melt. The O₂ activity of fluorite U_1–yTh_yO_2±x with temperature and composition was determined by thermogravimetric analysis. Thermodynamic studies for the Th–O binary and U–Th–O ternary available in the open literature were critically reviewed. A self‐consistent data set was selected and compiled with the equilibrium oxygen pressures determined by thermogravimetry in order to optimize the adjustable parameters of models selected to represent the phases in the Th–O and U–Th–O systems.     

A modified Peng–Robinson equation of state for phase equilibrium calculation of liquefied,synthetic natural gas,and gas condensate mixtures

A modified Peng–Robinson equation of state, MPR2 EOS, is introduced by incorporating a new alpha function and a temperature dependent function for covolume, b. The modified cubic EOS has three input per each substance: critical temperature, critical pressure, and acentric factor. The coefficients of temperature dependence of the alpha and beta functions, relating to the parameters a and b of the new cubic EOS, are obtained by simultaneous fitting of saturated experimental vapour pressure and liquid density data for several pure components. The percent absolute average deviation (AAD%) of 1.38, 4.80 and 2.89 are obtained to correlation of the saturation vapour pressure, liquid density and vapour volume, respectively. Also the ADD% of 2.575 is computed for prediction of saturation enthalpy of vapourisation of the pure compounds. For calculation of phase equilibrium of mixture, the modified PR EOS is used for prediction of liquid density of the LNG mixtures. Also the new EOS is applied for construction of the phase envelop of synthetic natural gas, SNG, mixtures and calculation vapour–liquid equilibria of gas condensates. The results demonstrate that the new MPR2 EOS can be used for calculation of vapour–liquid equilibrium of pure components and mixtures with good accuracy.     

Simultaneous liquid–liquid and vapour–liquid equilibria predictions of selected oxygenated aromatic molecules in mixtures with alkanes,alcohols, water,using the polar GC-PC-SAFT

Phase equilibria of oxygen-bearing aromatic compounds, hydrocarbons and water mixtures are of essential interest in many processes using feeds originating from biomass. The strong non-ideal thermodynamic behavior of these systems sometimes results in immiscibility with both water and alkanes.To address this problem, the GC-PPC-SAFT equation of state [Tamouza et al., 2004; Nguyen-Huynh et al., 2008a] is extended to some selected components: phenol, alkyl-phenols, alkyl-benzoates, benzaldehyde and anisole. However, as in these multifunctional compounds, the proximity of polar functional groups may result in a lack of transferability of the parameters from the monofunctional homologous species, some parameters have been adapted in view of physical arguments. Next, liquid–vapour and liquid–liquid equilibria of mixtures with n-alkanes were evaluated, using a predictive method for the binary interaction parameters (k_ij) [Nguyen-Huynh et al., 2008b]. Finally, mixtures with other associating compounds, as alcohols and water have also been considered.In all cases, both correlations and predictions are qualitatively and quantitatively satisfactory. The relative deviations obtained on bubble pressure of vapor–liquid equilibria are 4–8%, that is comparable to those obtained on previously investigated systems.     

An apparatus for determining high-pressure liquid-vapour equilibrium data. I. The methanol—ethanol system

An apparatus for determining high-pressure liquid–vapour equilibrium data has been developed and proved to operate satisfactorily. The apparatus operates isothermally. Results have been obtained for the ethanol–methanol system at the following temperatures: 100°, 120°, 140° and 160°. The results are shown to be thermodynamically consistent within the limits of the accuracy of their determination. The ‘ideal activity coefficients’ (i.e. calculated assuming that the gas phase behaviour is ideal) are correlated with the mole fraction of the component in the liquid phase by Margules-type equations (1) and (2). The accuracy of these equations is greater than predictions based on fugacities. From equations (5), (6) and (1) or (2) in the paper it is possible to estimate any pair of liquid-vapour equilibrium compositions for any specified pressure P and temperature T. Alternatively, for a specified P and liquid composition, the corresponding T and vapour composition may be calculated.     

Prediction of equilibrium solubility of CO2 in aqueous alkanolamines using differential evolution algorithm

The design of sour‐gas treating processes with alkanolamine solvents requires knowledge of the vapour–liquid equilibrium (VLE) of the aqueous acid gas–alkanolamine systems. Representation of the experimental data with a thermodynamically rigorous model is required, so that one can systematically correlate and predict the VLEs of these systems. The modified Clegg–Pitzer equations have been used to correlate and predict the VLE of CO₂ in the aqueous N‐methyldiethanolamine (MDEA) and 2‐amino‐2‐methyl‐1‐propanol (AMP) systems. Differential evolution (DE), an evolutionary computational technique, has been used for parameter estimation of the developed VLE model in an effort to predict the VLE of CO₂ in aqueous MDEA and AMP solutions with a comparable accuracy to that by using the non‐traditional simulated annealing (SA) and deterministic technique like Levenberg–Marquardt (LM), if not better. In this work, the DE/rand‐best/1/bin strategy has been used for finding near global minimum solutions to the multivariable optimization problem as a part of the numerical solution of the developed model.     

Estimates of the Properties of Liquids

An equation which relates the volume term (V=M/_(ρL-ρg)) of unassociated liquids to pressure P and temperature T has been obtained by the combination of (a) 03V(?I/?V)_P→0=T_x-T for the effect of temperature on V at low (atmospheric) pressure and (b) - V(?P/?V)_T = P_x V_x/⁶/V⁶ _p→0+9(P-p) for the effect of pressure on volume at constant temperature. In the equations, p is the vapour pressure; pL the density of the liquid and pg the vapour density. Often pg can be neglected compared with pL and p is small compared with the large pressures required to affect the densities of liquids appreciably. There are three constants: Tx, Px, which equals 4.455 × 10⁹ N m², and Vx which can be calculated by the addition of atomic values for all the atoms in the molecule and subtraction of a value (6.56 × 10⁶ m³ mol¹) for each bond. When V approximates to M/ρL, the molar volume, the equation can be integrated to give the work and heat of isothermal compression. The viscosity of a liquid is related to the work of compression and solubilities in a liquid to the work required to bring the solute to the compressibility of the liquid. Many relationships can be derived and can be used to estimate properties of unassociated liquids.     

Influence of magnesium on dielectric properties of Ca9–xMgxBi(VO4)7 ceramics

Solid solution of Ca_9‐xMg_xBi(VO₄)₇ in powder and ceramic forms are obtained by solid‐state reactions. Details of their crystal structures are determined for x = 0.25 and x = 0.5 by synchrotron radiation diffraction and the Rietveld method. The refinement has confirmed that Mg²⁺ is replacing Ca²⁺ in M5 position of a polar (S.G. R3c) β‐Ca₃(PO₄)₂‐type structure. Thermal analysis, dielectric and second harmonic generation experiments in broad temperature regions have proved this polar structure is formed for 0 ≤ x ≤ 0.7. Magnesium for calcium substitution enhances optical nonlinear activity of Ca_9‐xMg_xBi(VO₄)₇ in 0 < x ≤ 0.5. Two phase transitions have been found, one of which from polar to centrosymmetric phase is accompanied by dielectric constant peak of ferroelectric type. The other is upper on temperature, marked with smaller dielectric anomaly, and goes between 2 centrosymmetric phases. Temperatures of the phase transition only slightly depend on x, the first being near 1050 K, the second near 1100 K. Electric conductivity quickly rises with temperature in the polar phase. At higher temperature it changes according to the Arrhenius law with small activation energy, E_a ~ 0.7 eV for bulk conductivity and E_gb ~ 2.0‐2.5 eV for grain boundary conductivity. The analysis of bulk and grain boundary conductivities agrees with Ca²⁺‐ion fast transport in ceramics. The bulk conductivity slowly decreases with magnesium content, the grain boundary conductivity does not notably depend on the composition.     

Poly(Vinyl chloride)/plasticizer-mixture interactions—mixtures of various plasticizers of industrial importance

The Flory-Huggins interaction parameter, x, has been determined as a function of plasticizer composition, ?₂, for several ternary mixtures of poly(vinyl chloride) (PVC) and different pairs of plasticizers, selected mainly from the family of aliphatic esters. The method employed was the micro-determination of the apparent melting temperature of a PVC particle in excess plasticizer. In some systems X changed fairly gradually as a function of ?₂, while other systems exhibited a pronounced minimum in the X – ?₂ plots. Attention has been drawn to the similarity of this latter behavior to the well known co-solvency effect. The existence of such minima is of partical interest in plasticized PVC formulations.     

Water vapour permeability,diffusion and solubility in latex films

Water vapour diffusion D, solubility S and permeability P coefficients have been determined for films obtained from carboxylated styrene-butadiene (SB) copolymer latexes. The experimental method is water vapour sorption performed in the range 30–60d?C. Using the small angle neutron scattering (SANS) method and a selective labelling with D₂O vapour, it has been shown that water molecules mainly diffuse in the films through the particle-particle interfaces, which consist of a polar carboxyl-rich copolymer. It has been shown that the degree of cross-linking of the particles does not significantly affect the values of D and S. Moreover, the effect of neutralization conditions, regarding both the pH value of the initial latex and the nature of the neutralizing agent, has also been investigated. It has been found that D does not depend on these parameters, whereas S appears to be very sensitive to them. The results have been interpreted on the basis of the structural modifications of the films induced by neutralization. Finally, the hydrophilicity (or hydrophobicity) of the neutralizing agent has been identified as one of the key features for controlling the affinity of the latex film for water vapour and hence its permeability properties.     

Phase relations of the MgO–SiO2–CrOx system at 1600°C in air and reducing atmospheres

The equilibrium phase relations of the MgO–SiO₂–CrO_x system were investigated at 1600°C in air and at pO₂ of 10^–10 to 10^–11 atm using a high-temperature isothermal equilibration technique followed by rapid quenching and direct phase composition analyses with electron probe X-ray microanalysis. Two-phase equilibria (liquid–cristobalite, liquid–spinel, liquid–corundum, and liquid–olivine) and three-phase equilibria (liquid–cristobalite–spinel, liquid–olivine–spinel, liquid–spinel–corundum, and cristobalite–spinel–corundum) were observed. The 1600°C isothermal sections at various oxygen partial pressures were constructed for the MgO–SiO₂–CrO_x system based on the experimentally determined liquid and solid compositions. Data from the literature and the predictions by FactSage and MTDATA software were compared with the present experimental results.     

NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> emission from incineration of organic liquid waste in a circulating fluidized bed

An incineration test of a toxic chemical organic waste liquid was conducted on a circulating fluidized bed (CFB) incinerator. The flue gas was measured online with the advanced SAE-19 flue gas analyzer. The effects of several factors, in terms of flow rate of waste liquid, ratio of waste liquid injected into dense bed of the CFB, excess air coefficient, the secondary air fraction and bed temperature on NO _x emissions, were verified. The experimental results show that NO emissions in flue gas increase with increase in the flow rate of the waste liquid injected into the bed or the excess air coefficient or the bed temperature and those decrease with increase in the ratio of waste liquid injected into the dense bed of the CFB or the secondary air fraction. During the test runs, NO _x concentration in flue gas met the national regulation on NO _x emissions due to suppressive effect of low temperature and staged combustion in CFB on NO _x formation. This paper was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Rational design of double salt ionic liquids as extraction solvents: Separation of thiophene/n-octane as example

Although double salt ionic liquids (DSILs) offer significant advantages over classical two-ion ionic liquids as separation solvents, relevant studies are still scarce and a systematic DSIL selection method is thus highly desirable. In this contribution, a rational method for designing DSILs as extraction solvents is proposed and exemplified by the thiophene/n-octane separation. The effects of additional degrees of freedom for DSIL design (i.e., double cations and/or anions and the ion ratio) on the thermodynamic properties are first analyzed by COSMO-RS. Then, a multilevel DSIL design method combining the prediction of infinite dilution thermodynamic properties, the estimation of physical properties, the evaluation of phase equilibrium behavior, and the experimental validation is proposed. By applying this method, [C₂MIm][OAc] _x[NO₃]_1-x (x = [0, 1]) and [C₂MIm][OAc] _x[SCN]_1-x (x = [0.70, 1]) are identified as promising DSIL solvents for the thiophene/n-octane separation. Correspondingly, the liquid–liquid equilibria of {DSILs + thiophene + n-octane} with the designed DSILs are experimentally studied.     

Vapour—liquid equilibria of the systems acetone—benzene,benzene—cyclohexane and acetone—cyclohexane at 25°C

Vapour—liquid equilibrium data for the binary systems acetone—benzene, benzene—cyclohexane and acetone—cyclohexane have been determined experimentally at 25°C. The reduction producers based on P - x - y as well as on P - x isothermal data sets, which incorporate usual thermodynamically consistent models expressing the dependence of activity coefficients of liquid composition, have been examined for representing the reported results. Nonideal behaviour of the both phases has been taken into account. Thermodynamic consistency of the data has been shown by comparing of the experimentally obtained vapour compositions with those calculated from P - x data using the best of the examined models for activity coefficients.     

Synthesis,structural evolution,and dielectric properties of a new perovskite solid solution (Pb0.5Sr0.5)(Zr0.5Ti0.5)O3–PbTiO3

To explore lead-reduced dielectric materials in the SrTiO₃–PbTiO₃–PbZrO₃ ternary system, a novel solid solution between relaxor ferroelectric (Pb_0.5Sr_0.5)(Zr_0.5Ti_0.5)O₃ and ferroelectric PbTiO₃, namely (1 − x)(Pb_0.5Sr_0.5) (Zr_0.5Ti_0.5)O₃–xPbTiO₃ (lead–strontium–zirconate–titanate [PSZT]–PT), has been synthesized in the perovskite structure by high-temperature solid-state reaction method in the form of ceramics. The crystal structure and phase symmetry of the materials synthesized were analyzed and resolved based on X-ray powder diffraction (XRD) data through both the Pawley and Rietveld refinements. The results of the structural refinements indicate that at low PT-concentration end of the solid solution system, for example, x = 0.05, the PSZT–PT solid solution exhibits a cubic structural symmetry (with the space group Pm-3m). As the PT concentration (x) increases, the structure of (1 − x)PSZT–xPT gradually transforms from the cubic to a tetragonal (P4mm) phase. In the composition range of x = 0.10–0.25, a mixture of the cubic and tetragonal phases was identified. As the concentration of PT increases, the proportion of the tetragonal phase increases at the expense of the cubic phase. For a composition of x > 0.25, a pure tetragonal phase is observed. The dielectric properties of the materials were studied by measuring the permittivity as a function of temperature at various frequencies. For the composition of x = 0.05, the temperature dependence of dielectric constant shows typical relaxor behavior. For x = 0.35, the dielectric peaks indicate a normal ferroelectric phase transition. Overall, a structural transformation from a central-symmetric, nonpolar cubic phase to a non-centrosymmetric, polar tetragonal phase is induced by the substitution of PT for PSZT in the pseudo-binary solid solution of (1 − x)PSZT–xPT, which also reveals an interesting relaxor to ferroelectric crossover phenomenon.