Liquid–liquid equilibrium correlations using lattice fluid equation of state with hydrogen bonding

The nonrandom lattice equation of state with hydrogen bonding (NLF-HB EOS) was examined for the correlation of liquid–liquid equilibria (LLE) for binary alcohol and hydrocarbon mixture in a wide pressure range. For hydrocarbon + alcohol mixtures the consideration of a hydrogen-bonding term in the lattice equation of state clearly improves the prediction for vapor–liquid equilibrium (VLE) as shown in previous works, but the prediction of LLE is still in question. In this paper, LLE data for alcohols (methanol and ethanol) + hydrocarbons (n-hexane to n-hexadecane) were correlated by NLF-HB EOS and results were compared with a cubic equation of state (Peng–Robinson EOS with the T–K Wilson based G^E model). Both equations of state showed similar degree of accuracies but with different number of adjustable parameters. The Peng–Robinson EOS based approach requires six temperature dependent coefficients for accurate calculation whereas NLF-HB EOS requires only two temperature dependent coefficients. The effects of varying hydrogen-bonding energies for NLF-HB EOS are discussed.     

Experimental data and modeling for excess enthalpies of 2-Pentanol with n-alkanes(C7–C9) at T =(293.15, 298.15 and 303.15) K

Excess molar enthalpies, H~E, for the binary mixtures of 2-pentanol with n-alkanes(n-heptane, n-octane, and nnonane) have been determined at three different temperatures T =(293.15, 298.15 and 303.15) K and normal atmospheric pressure over the entire composition range using a Calvet microcalorimeter. All mixtures show endothermic mixing with the maximum values of the excess enthalpies occurring in the n-alkane-rich region. The H~Edata are smoothed using Redlich–Kister equation. The applicability of the Treszczanowicz–Benson, ERAS,Renon–Prausnitz and Chen–Bagley models to correlate H~Eof studied mixtures is tested, and the agreement between experimental and theoretical results is satisfactory. Each model includes a self-association equilibrium constant that represents hydrogen bonding and an adjustable parameter that reflects physical interactions.     

Excess molar volumes for titanium butoxide contained binary and ternary systems at 298.15 K

The reported mixture properties of metal alkoxide are almost none in spite of their increasing usages. In this work, the excess molar volumes (V^E) were determined from measured densities for six binary systems of titanium butoxide (1) + ethanol (2), titanium butoxide (1) + 1-propanol (2), titanium butoxide (1) + 1-butanol (2), ethanol (1) + 1-propanol (2), 1-propanol (1) + 1-butanol (2) and ethanol (1) + 1-butanol (2) at 298.15 K. The experimental V^E were correlated with the Redlich–Kister polynomial. The partial excess molar volumes at infinite dilution were calculated with fitted binary parameters. Additionally the ternary V^E data at 298.15 K were also predicted for three systems of titanium butoxide (1) + ethanol (2) + 1-propanol (3), titanium butoxide (1) + ethanol (2) + 1-butanol (3) and titanium butoxide (1) + 1-propanol (2) + 1-butanol (3) by using the binary contribution model of Radojkovič with the binary Redlich–Kister parameters.     

Formulating a low-alkalinity, high-resistance and low-heat concrete for radioactive waste repositories

Investigations were carried out in order to formulate and characterize low-alkalinity and low-heat cements which would be compatible with an underground waste repository environment. Several systems comprising Ordinary Portland Cement (OPC), a fast-reacting pozzolan (silica fume (SF) or metakaolin (MK)) and, in some cases, a slow-reacting product (fly ash (FA) or blastfurnace slag (BFS)) were compared. Promising results were obtained with some binary mixtures of OPC and SF, and with some ternary blends of OPC, SF and FA or BFS: pH of water in equilibrium with the fully hydrated cements dropped below 11. Dependence of the properties of standard mortars on the high contents of FA and SF in the low-pH blends was examined. Combining SF and FA seemed attractive since SF compensated for the low reactivity of FA, while FA allowed to reduce the water demand, and dimensional variations of the mortars. Finally, low-heat (ΔT < 20 °C under semi-adiabatic conditions) and high strength (≈ 70–80 MPa) concretes were prepared from two low-pH cements: a binary blend made from 60% of OPC and 40% of SF, and a ternary blend including 37.5% OPC, 32.5% SF and 30% FA.     

On the thermodynamic driving force for nucleation at large undercoolings

The molar free energy difference ΔG_f, between amorphous and crystalline phases, is computed using heat capacity data over a large temperature range between the melting (T_m⁰) and the glass transition temperatures. These values are used to assess the validity of the approximate correction factors, f^H1 = T/T_m⁰ and f^H2 = 2T/(T + T_m⁰), suggested by Hoffman [Thermodynamic driving force in nucleation and growth processes. J Chem Phys 1958;29(5):1192–93], and widely used in the literature for a variety of polymers to account for the change in free energy with temperature, T. Surprisingly, for polyethylene and isotactic polypropylene, which are industrially important polymers, it is found that the performance of these correction factors is worse than uncorrected estimates. For isotactic polystyrene and polyethylene oxide, it is found that the correction factor f^H2 offers a good approximation for the free energy of fusion at moderate to large undercoolings, although Hoffman's criterion recommends the use of f^H1. Empirical correction factors that provide a better fit with the experimental data, and a computer program used to determine them are also provided.     

Theory of “Cohesive” vs “Adhesive” Separation in an Adhering System

It is shown that there is limited validitity to the doctrine that true interfacial separation, in an adhering system, is highly improbable. An analysis employing the Griffith-Irwin crack theory yields these results: The important parameters are, difference in elastic moduli, ΔE; differences in g, the energy dissipation per unit crack extension; thickness, Δ₁ or δ₂, of the region where dissipation occurs; and the presence or absence of strong interfacial bonds. If the forces across the interface are appreciably weaker than the cohesive forces in either phase, there is a strong minimum in g at the interface. For flaws of equal size, an interfacial flaw will be the site of initiation of failure. If strong interfacial bonds are present, then if Δg and ΔE have the same sign, failure is most probable, deep within one phase. If Δg and ΔE have opposite signs, failure may be initiated, and may propagate, at a distance δ from the interface, in the phase with lower g. This may be mistaken for weak-boundary layer failure.     

Effect of dissolved inorganic salts on the isothermal vapor–liquid equilibrium of the propionic acid–water mixture

Propionic acid–water is one of the minimum boiling point azeotropic binary mixtures. Alteration of the vapor–liquid equilibrium (VLE) by addition of inorganic salts is of interest, since it allows bypassing the azeotropic point due to salt-in and salt-out effects. The effect of NaCl, NH₄Cl, CaCl₂, and AlCl₃ at salt concentrations of 1 m and the effect of NaCl molality (0.5–3 m) on the VLE of the binary propionic acid–water mixture has been experimentally investigated at 60 °C using the headspace gas chromatography (HSGC) technique. The alteration in the VLE of the system was salt type and salt concentration dependent. Salting out of the propionic acid was observed when salts were added and was most obvious in the case of AlCl₃ salt. The salt effect parameter, determined from the Furter's equation was a function of the liquid concentration.     

Dry grinding kinetics of binary mixtures of ceramic raw materials by Bond milling

The kinetics of batch dry grinding of binary mixtures of ceramic raw materials, namely quartz–kaolin, quartz–potassium feldspar and kaolin–potassium feldspar, from the feed sizes of −3.350 + 2.360, −2.000 + 1.400, −0.850 + 0.600, −0.500 + 0.355 and −0.300 + 0.212 mm have been determined using a Bond mill with a mixture of ball sizes of 38.10, 31.75, 25.40, 19.05 and 12.70 mm diameter and total mass of 22.648 kg. The Bond mill used was a size of 30.5 cm diameter, 30.5 cm length, with a total volume of 22,272 cm³. The fractional ball filling was 22% of mill volume and the mill speed was 70 rpm. The breakage parameters were obtained for those mineral mixtures to predict the product size distributions. As the feed sized given above, which were ground in the mill, increase, the specific rate of breakage (S_i) values also increase, which means faster breakage with higher S_i value occurs in the order of quartz–kaolin, quartz–potassium feldspar and kaolin–potassium feldspar mixtures when comparing the characteristic values (slope of S_i versus size relationship with higher value). The cumulative breakage distribution function (B_i,j) values obtained for these mineral mixtures were slightly different in terms of the fineness factor, γ. This means that quartz–potassium feldspar mixture produced less fines with higher γ value, while kaolin–potassium feldspar gave more fines with lower γ value. The simulations of the product size distribution for these mixing were very close to the experimental data. Finally, slowing down effect, treated with false time concept, started earlier than the expected for these binary mixtures. There were some correlations found between the simulated time (θ) and experimental time (t).     

MAGNETOTHERMAL CONVECTION OF POLYATOMIC GASES IN HOMOGENEOUS MAGNETIC FIELDS Part I: Theory

The theory of magnetothermal convection of gases in homogeneous magnetic fields is developed from magnetogas-dynamic theory. Application is made to nonionized paramagnetic and diamagnetic gases between parallel vertical plates. An additive contribution to the natural thermal convection heat transfer results from the temperature dependence of the magnetic permeability of the gas. The result may be expressed parametrically in a dimensionless magnctoconvection number, which characterizes the magnetothermal contribution to the total heat transfer just as the Grashof number characterizes the natural thermal contribution. For oxygen gas at low pressure the magnetothermal contribution is shown to be proportional to p³H²(ΔT)² /ηT⁵ where p is the gas pressure, H is the magnetic field strength, ΔT is the temperature difference between plates, η is the viscosity coefficient and T is the absolute temperature.     

Adsorption of methane/ethane mixtures on dry coal at elevated pressure

The binary adsorption characteristics of methane and ethane on dry coal to 40 atm pressure have been calculated from pure-component isotherms. In some coal seams, pressures exceeding 40 atm have been recorded and the methane sampled from the virgin coal often shows a few percent of ethane. The binary adsorption characteristics were calculated by employing the ideal adsorbed solution theory of Myers and Prausnitz, and experimentally-determined (Type I) pure gas isotherms at 0, 30 and 50 °C. The coal used in this investigation was high-volatile ‘A’ bituminous (hvab) from the Pennsylvania Pittsburgh seam. Gas nonideality was accounted for by replacing pressure with fugacity. Adsorption of methane on dry coal is purely physical; the isosteric heat of adsorption does not exceed 2.4 kcal/mol^* at 30 °C on the above coal. Isobars on the resulting binary equilibrium diagram exhibited an unexpected phenomenon of intersecting each other which might be attributable to the above nonideality considerations. The region of a few percent of ethane, which is of practical importance from the viewpoint of coal seams, was expanded and reduced to an equation: V(CH₄) = −21.52 + 7.18(VF) + 16.88(VF)² −0.395(P) − 0.00661(P)² + 0.824(T) − 0.00030(T)² + 0.928(VF)(P) − 0.858(VF)(T). V(Total) = 25.9 − 23.6(VF) + 0.655(P) − 0.00875(P)² − 0.795(T) + 0.743(VF)(T) where V(CH₄) and V(Total) = cm³(STP)CH₄ and total gas respectively adsorbed per g dry coal; VF = vol. fraction of methane as analysed at 1 atm (0.94 VF 1.0); P = seam pressure, atm (0 P 40); T=seam temperature, °C(−10 T 50).     

Measurement and correlation of liquid-liquid equilibrium for the ternary system (water + 1,2-dichloroethane + sulfolane) at 288.15, 298.15, and 308.15 K

Sulfolane is an important aprotic polar solvent. Liquid-liquid equilibrium(LLE) data for the ternary systems of water + 1,2-dichloroethane + sulfolane were measured at temperatures of 288.15, 298.15 and 308.15 K under the atmospheric pressure. The distribution coefficient and selectivity were determined from the measured LLE data, which showed that 1,2-dichloroethane is a suitable extractant for the recovery of sulfolane from its aqueous solution. The nonrandom two-liquid(NRTL) model and the uni...     

Reversible heat effects in high temperature batteries: Transported entropy and thomson coefficients in cells with β″-alumina

The transported entropy and the Thomson coefficient for charge conducting ions are needed to predict reversible heat effects in batteries. Transported entropies and Thomson coefficients have been calculated from Seebeck coefficients of the cell Fe(s, T₁)|Me| β″ alumina | Me | Fe(s, T₂) for Na and K (Me). The result is S*_Na⁺ = 56 ± 3 J K⁻¹ mol⁻¹ at 500 K, with a Thomson coefficient τ_Na⁺ = 30 ± 2 J K⁻¹ mol⁻¹ in the temperature interval 333–773 K. The transported entropy of Na⁺ did not change by freezing Na at 370. The results for K⁺ are identical to those of Na⁺ within the accuracy of the experiments. The Thomson coefficient derived from measurements at different values of T₁ was consistent with the observed variation in emf with ΔT for a given T₁. The reversible heat changes at the electrodes have been calculated for sodium sulphur and potassium sulphur batteries. During discharge both batteries produce a net reversible heat, the production always being largest at the alkali metal anode. At the cathode, the heat effect becomes relatively small when the composition of Na and S is within the one phase region. A change in composition from the one phase to the two phase region is expected to lead to changes in local temperature gradients. The systems were described by the electric work method, a method which has practical advantages compared to other electrochemical methods.     

Vapor—liquid equilibria at high temperatures and pressures in binary mixtures containing H2, CH4 and CO2 with high boiling hydrocarbons: experimental equipment and results

An apparatus was designed, built and operated with the purpose of studying vapor—liquid equilibria at temperatures 450 < T < 650 K and pressures 1 < p < MPa or critical pressure. The liquid in the high pressure equilibrium cell was agitated by a magnetically driven mixer. Samples can be taken from the vapor and the liquid phase. The composition was determined by a combination of gravimetric and volumetric measurements. Test measurements were performed on binary systems investigated previously by others in order to check the reproducibility and accuracy of the measurements.     

含甲基叔丁基醚的四元体系液液相平衡

为了考察甲基叔丁基醚对汽油主要成分烃类化合物与水相互溶解性的影响,在298.15 K和常压下,测定了2个四元体系水-甲基叔丁基醚-异辛烷-异丙醇和水-甲基叔丁基醚-异辛烷-甲苯的液液相平衡数据,并用含有二元、三元和四元相互作用参数的Extended UNIQUAC模型和Modified UNIQUAC模型对液液相平衡数据进行了关联计算。结果表明:在298.15 K时测得的四元体系液液相平衡数据和模型的计算结果很吻合,Extended UNIQUAC和Modified UNIQUAC模型成功地描述了四元混合液的液液相平衡,这些基础数据对化工生产过程的设计和分离操作条件的选择都是非常有意义的。     

Effect of cooling rate and frequency on the calorimetric measurement of the glass transition

The glass transition of thermoplastics of different polydispersity and thermosets of different network structure has been studied by conventional differential scanning calorimetry (DSC) and temperature modulated DSC (TMDSC). The cooling rate dependence of the thermal glass transition temperature T_g measured by DSC, and the frequency dependence of the dynamic glass transition temperature T measured by TMDSC have been investigated. The relation between the cooling rate and the frequency necessary to achieve the same glass transition temperature has been quantified in terms of a logarithmic difference Δ=log₁₀[|q|]−log₁₀(ω), where |q| is the absolute value of the cooling rate in K s⁻¹ and ω is the angular frequency in rad s⁻¹ necessary to obtain T_g(q)=T(ω). The values of Δ obtained for various polymers at a modulation period of 120 s (frequency of 8.3 mHz) are between 0.14 and 0.81. These values agree reasonably well with the theoretical prediction [Hutchinson JM, Montserrat S. Thermochim Acta 2001;377:63 [6]] based on the model of Tool–Narayanaswamy–Moynihan with a distribution of relaxation times. The results are discussed and compared with those obtained by other authors in polymeric and other glass-forming systems.     

Thermal effects in styrene-butadiene rubber at high hydrostatic pressures

The temperature changes as a result of rapid hydrostatic pressure applications are reported for unvulcanized styrene-butadiene rubber (SBR) in the reference temperature range from 292 to 405 K and in the pressure range from 13.8 to 200 MN m⁻². The thermal effects were found to be a function of pressure and temperature. A curve fitting analysis showed that the empirical curve (∂T/∂P)=ab(ΔP)^b−1, described the experimental thermoelastic coefficients obtained from the experiments. The data were analysed by determining the predicted thermoelastic coefficients derived from the Thomson equation (∂T/∂P)=T_o/C_p. The experimental and the predicted Grüneisen parameter γ_T were also estimated. Close agreement was found at low pressure but differences were observed at higher pressures between the experimental and expected values for the thermoelastic coefficients and the Grüneisen parameter.     

Catalytic reduction of N2O over steam-activated FeZSM-5 zeolite: Comparison of CH4, CO, and their mixtures as reductants with or without excess O2

The catalytic reduction of N₂O by CH₄, CO, and their mixtures has been comparatively investigated over steam-activated FeZSM-5 zeolite. The influence of the molar feed ratio between N₂O and the reducing agents, the gas-hourly space velocity, and the presence of O₂ on the catalytic performance were studied in the temperature range of 475–850 K. The CH₄ is more efficient than CO for N₂O reduction, achieving the same degree of conversion at significantly lower temperatures. The apparent activation energy for N₂O reduction by CH₄ was very similar to that of direct N₂O decomposition (140 kJ mol⁻¹), being much lower for the N₂O reduction by CO (60 kJ mol⁻¹). This suggests that the reactions have a markedly different mechanism. Addition of CO using equimolar mixtures in the ternary N₂O + CH₄ + CO system did not affect the N₂O conversion with respect to the binary N₂O + CH₄ system, indicating that CO does not interfere in the low-temperature reduction of N₂O by CH₄. In the ternary system, CO contributed to N₂O reduction when methane was the limiting reactant. The conversion and selectivity of the reactions of N₂O with CH₄, CO, and their mixtures were not altered upon adding excess O₂ in the feed.     

On the predictive capabilities of CPA for applications in the chemical industry: Multicomponent mixtures containing methyl-methacrylate,dimethyl-ether or acetic acid

The predictive performance of the CPA (Cubic-Plus-Association) equation of state for applications relevant to the chemical industry is illustrated in this work. Three such applications inspired by industrial requests/interest are illustrated here, all of which involve aqueous multicomponent mixtures exhibiting vapor–liquid (VLE) and/or liquid–liquid (LLE) equilibrium. The first two cases include mixtures of methyl-methacrylate with acetone or methanol and dimethyl-ether with ethanol, respectively. In these two cases, the classical form of CPA is used. The third case involves aqueous mixtures with acetic acid, esters, ethers and alcohols, and in this case for water–acetic acid the CPA-Huron Vidal (CPA-HV) version of the model is used. For the latter binary mixture, new CPA-HV binary parameter sets are estimated using, among others, data for activity coefficients at infinite dilutions. The modeling approach is similar in all three cases, i.e. the binary parameters are solely fitted to binary data and thus all multicomponent calculations are considered predictions.It is shown that CPA correlations for binary systems are excellent in all cases using temperature independent parameters except for the acetic acid–water system for which different parameter sets at different temperatures can be recommended. Even with the use of CPA-HV mixing rules, modeling of the acetic acid–water system with few interaction parameters remains a challenging task. Excellent simultaneous VLE and LLE correlation is obtained for complex systems such as aqueous mixtures with ethers and esters. The multicomponent results are, with a few exceptions, very satisfactory, especially for the vapor–liquid equilibrium cases. For the demanding aqueous acetic acid–water containing systems, one parameter set is recommended at the end for modeling ternary or multicomponent mixtures containing acetic acid and water.     

CALCULATION OF VAPOR LIQUID EQUILIBRIUM AND EXCESS ENTHALPY WITH THE UNIQUAC EQUATION

The UNIQUAC equation was used for calculation of vapor liquid equilibrium (VLE)as well as excess enthalpy (h^E). Four sets of binary interaction parameters were applied: first, parameters estimated only from VLE data, then parameters from h^E data for both the original UNIQUAC equation and the Anderson modification, and finally parameters estimated from h^E and VLE data simultaneously. Calculations were performed for seven binary systems with polar components, representing different h^E behavior. The cross-prediction of h^E from VLE data works better than the reversed prediction. The model with parameters estimated simultaneously to both kinds of data can be applied successfully to both kinds of calculations, but it is a compromise between the models estimated from one kind of data.     

A COMPARATIVE ANALYSIS OF THE DERIVATION OF INFINITE DILUTION ACTIVITY COEFFICIENTS FROM ΔT— x AND ΔP — x DATA

The experimental determination of infinite dilution activity coefficients (γ^∞) of liquid mixtures is carried out by gas chromatographic and ebulliometric techniques. Both methods show inaccuracies due to experimental difficulties.

This paper provides a comparative analysis of the influence of errors in measurements on the evaluation of γ^∞ using ΔT — x and ΔP — x experimental data. It is shown that the errors in the determination of γ^∞ from ΔP — x data are generally lower than those from ΔT — x ones