Spinodal phase separation of unstable solid-state binary n-alkane mixtures

Two mixtures of unequal chain length n-alkanes in which one component is deuterated have been investigated by infrared spectroscopy as they demixed. The measurements followed the band shapes of the scissors vibrations as a function of time. The band envelopes are analyzed as composites of a number of reference mixtures of known concentration. The unequal-chain mixtures separate into phases that slowly change their composition toward pure alkane phases. The method of analysis, which reveals local concentrations, should be generally applicable to polymethylene systems.     

Liquid-liquid-vapor phase equilibria behavior of certain binary carbon dioxide + n-alkylbenzene mixtures

The liquid-liquid-vapor loci for the binary mixtures CO₂ + n-hexylbenzene, n-heptylbenzene, and n-octylbenzene were experimentally studied. The compositions and molar volumes of the liquid phases are reported along with the pressure and temperature. For these three alkylbenzenes, the nature of the liquid-liquid-vapor loci experiences a transition, with the CO₂ + n-heptylbenzene mixture exhibiting two separate liquid-liquid-vapor branches.     

Relative permittivities of binary mixtures of 1-butanol + n-alkane AT 298.15 k

A previous study on the physical properties of 1-alkanol + n-alkane has establised a correlation between dielectric permittivity at 1 GHz and excess molar volumes for all binary systems that were studied. In order to determine whether this behaviour is similar at lower frequencies, relative permittivity was measured at 100 kHz. The refractive index was measured to explore the effects at higher frequencies. Mixtures under study are in particular the systems (1-butanol + n-hexane, or n-octane, or n-decane) at the temperature of 298.15 K and atmospheric pressure, over the entire composition range. This revised version was published online in July 2006 with corrections to the Cover Date.     

Solid-liquid equilibrium using the SAFT-VR equation of state: Solubility of naphthalene and acetic acid in binary mixtures and calculation of phase diagrams

A solid-liquid equilibrium (SLE) thermodynamic model based on the SAFT-VR equation of state (EOS) is presented. The model allows for the calculation of solid-liquid phase equilibria in binary mixtures at atmospheric pressure. The fluid (liquid) phase is treated with the SAFT-VR approach, where molecules are modelled as associating chains of tangentially bonded spherical segments interacting via square-well potentials of variable range. The equilibrium between the liquid and solid phase is treated following a standard thermodynamic method that requires the experimental temperature and enthalpy of fusion of the solute. The model is used to calculate the solubilities of naphthalene and acetic acid in common associating and non-associating organic solvents and to determine the solid-liquid phase behaviour of binary mixtures with simple eutectics. The SAFT-VR pure component model parameters are determined by comparison to experimental vapour pressure and saturated liquid density data with the choice of association models according to the nature of the molecule; in addition, an unlike adjustable parameter (k_ij) is used to model the solutions. The solubility data of naphthalene and acetic acid in both associating and non-associating solvents are reproduced essentially within the accuracy of the experimental measurements. The phase boundaries and the position of the eutectic points in the binary mixtures considered are, in most cases, reproduced with the accuracy commensurate with the industrial applications. Overall, the results presented show that the SAFT-VR EOS can be used with confidence for the prediction of the SLE of binary systems at atmospheric pressure.     

Prediction of vapor-liquid equilibrium from excess enthalpy data for binary ether +n-alkane or cyclohexane mixtures

Vapor liquid equilibrium (VLE) is successfully predicted from excess enthalpy H^E data for binary ether + n-alkane or cyclohexane mixtures. Parameters for the continuous linear association model (CLAM) and for the UNIQUAC Model for the excess Gibbs energy G^E were determined from H^E data measured at a low temperature (ambient temperature). These parameters are used to predict VLE data at low and high temperatures. The dependence of the accuracy of predictions on the set of H^E data chosen to evaluate the parameters and on the model for G^E are discussed.     

Volumes and viscosities of benzene + n-alkane mixtures

Excess molar volumes, viscosities, excess molar viscosities and excess molar activation energies of viscous flow were determined for binary mixtures of benzene + n-hexane, + n-octane, + n-decane, + n-dodecane, + n-tetradecane and + n-hexadecane at 298.15 K. The effect of orientational order of n-alkane on solution molar volumes and viscosities is investigated as well as the adequacy of the absolute rate and free volume theories to predict solution viscosities. For longer n-alkane ΔG*^E and Δ 1n η are positive and associated with the orientational order.     

Overtone spectroscopy of H2D+ and D2H+ using laser induced reactions

The method of laser induced reaction is used to obtain high-resolution IR spectra of H2D+ and D2H+ in collision with n-H2 at a nominal temperature of 17 K. For this purpose three cw-laser systems have been coupled to a 22-pole ion trap apparatus, two commercial diode laser systems in the ranges of 6100-6600 cm(-1) and 6760-7300 cm(-1), respectively, and a high-power optical parametric oscillator tunable in the range of 2600-3200 cm(-1). In total, 27 new overtone and combination transitions have been detected for H2D+ and D2H+, as well as a weak line in the nu1 vibrational band of H2D+ (2(20)<--1(01)) at 3164.118 cm(-1). The line positions are compared to high accuracy ab initio calculations, showing small but mode-dependent differences, being largest for three vibrational quanta in the nu2 symmetric bending of H2D+. Within the experimental accuracy, the relative values of the ab initio predicted Einstein B coefficients are confirmed.     

Molecular modeling of phase behavior and microstructure of acetone-chloroform-methanol binary mixtures

Force fields based on a Lennard-Jones (LJ) 12-6 plus point charge functional form are developed for acetone and chloroform specifically to reproduce the minimum pressure azeotropy found experimentally in this system. Point charges are determined from a CHELPG population analysis performed on an acetone-chloroform dimer. The required electrostatic surface for this dimer is determined from ab initio calculations performed with MP2 theory and the 6-31g++(3df,3pd) basis set. LJ parameters are then optimized such that the liquid-vapor coexistence curve, critical parameters, and vapor pressures are well reproduced by simulation. Histogram-reweighting Monte Carlo simulations in the grand canonical ensemble are used to determine the phase diagrams for the binary mixtures acetone-chloroform, acetone-methanol, and chloroform-methanol. The force fields developed in this work reproduce the minimum pressure azeotrope in the acetone-chloroform mixture found in experiment. The predicted azeotropic composition of x(CHCl3) = 0.77 is in fair agreement with the experimental value of x(CHCl3)expt = 0.64. The new force fields were also found to provide improved predictions of the pressure-composition behavior of acetone-methanol and chloroform-methanol when compared to other force fields commonly used for vapor-liquid equilibria calculations. NPT simulations were conducted at 300 K and 1 bar for equimolar mixtures of acetone-chloroform, acetone-methanol, and methanol-chloroform. Analysis of the microstructure reveals significant hydrogen bonding occurring between acetone and chloroform. Limited interspecies hydrogen bonding was found in the acetone-methanol or chloroform-methanol mixtures.     

Tunneling chemical reactions D + H2 --> DH + H and D + DH --> D2 + H in solid D2-H2 and HD-H2 mixtures: an electron-spin-resonance study

Tunneling chemical reactions D + H2 --> DH + H and D + DH --> D2 + H in solid HD-H2 and D2-H2 mixtures were studied in the temperature range between 4 and 8 K. These reactions were initiated by UV photolysis of DI molecules doped in these solids for 30 s and followed by measuring the time course of electron-spin-resonance (ESR) intensities of D and H atoms. ESR intensity of D atoms produced by the photolysis decreases but that of H atoms increases with time. Time course of the D and H intensities has the fast and slow processes. The fast process, which finishes within approximately 300 s after the photolysis, is assigned to the reaction of D atom with one of its nearest-neighboring H2 molecules, D(H2)n(HD)(12-n) --> H(H2)(n-1)(HD)(13-n) or D(H2)n(D2)(12-n) --> H(HD)(H2)(n-1)(D2)(12-n) for 12 > or = n > or = 1. Rate constant for the D + H2 reaction between neighboring D atom-H2 molecule pair is determined to be (7.5 +/- 0.7) x 10(-3) s(-1) in solid HD-H2 and (1.3+/-0.3) x 10(-2) s(-1) in D2-H2 at 4.1 K, which is very close to that calculated based on the theory of chemical reaction in gas phase by Hancock et al. [J. Chem. Phys. 91, 3492 (1989)] and Takayanagi and Sato [J. Chem. Phys. 92, 2862 (1990)]. This rate constant was found to be independent of temperature up to 7 K within experimental error of +/-30%. The slow process is assigned to the reaction of D atom produced in a cage fully surrounded by HD or D2 molecules, D(HD)12 or D(D2)12. This D atom undergoes the D + DH reaction with one of its nearest-neighboring HD molecules in solid HD-H2 or diffuses to the neighbor of H2 molecules to allow the D + H2 reaction in solid HD-H2 and D2-H2. The former is the main channel in solid HD-H2 below 6 K where D atoms diffuse very slowly, whereas the latter dominates over the former above 6 K. Rate for the reactions in the slow process is independent of temperature below 6 K but increases with the increase in temperature above 6 K. We found that the increase is due to the increase in hopping rate of D atoms to the neighbor of H2 molecules. Rate constant for the D + DH reaction was found to be independent of temperature up to 7 K as well.     

Liquid—liquid—vapor phase equilibria behavior of certain binary ethane + n-alkylbenzene mixtures

The liquid—liquid—vapor loci for the binary mixtures ethane + n-nonylbenzene, ethane + n-decylbenzene and ethane + n-undecylbenzene were experimentally studied. The pressure, temperature, and compositions and molar volumes of the liquid phases are reported along the loci. n-Nonylbenzene was found to be the first member of the n-alkylbenzene homologous series to exhibit liquid—liquid—vapor immiscibility with ethane. For the three alkylbenzenes studied, the liquid—liquid—vapor loci have the same type of behavior: they extend from a lower critical end point (LCEP) to an upper critical end point (K-point).     

Activity coefficients in binary electrolyte mixtures HCl + MgCl2 + H2O at 298.15°K

Activity coefficients of hydrochloric acid in aqueous mixed solutions with magnesium chloride have been determined at 298.15°K from electromotiveforce measurements of the cell Pt, H₂(g, 1 atm.)HCl(m_A), MgCl₂(m_B)AgClAg at constant total ionic strengths of 0.1, 0.5, 1.0, 2.0, and 3.0 moles-kg^–1. The data were interpreted in terms of Scatchard's and Pitzer's equations whereupon it was found that the former gave a better fit of the experimental data but the latter were reasonably adequate. Activity coefficients for magnesium chloride in the mixtures were derived using Pitzer's equations.     

Solid-fluid and solid-solid phase equilibrium in a model of n-alkane mixtures

Solid-fluid and solid-solid phase equilibrium for binary mixtures of hard sphere chains modeling n-hexane, n-heptane, and n-octane has been calculated using Monte Carlo computer simulations. Thermodynamic integration was used to calculate the Gibbs free energy and chemical potentials in the solid and fluid phases from pure component reference values. A multiple stage free energy perturbation method was used to calculate the composition derivative of the Gibbs free energy. Equation of state and free energy data for the fluid phase indicate ideal solution behavior. Nonideality is much more significant in the solid phase with only partial solubility of shorter chains in the longer chains and essentially no solubility at the other end of the composition range. The miscibility decreases with increasing chain length difference between the components. For the model of n-hexane/n-octane mixtures solid--solid phase separation has been observed directly in some of the simulations, with the components segregating between the layers of the solid structure. The behavior is similar to that seen in some binary n-alkane mixtures with longer chain lengths but comparable chain length ratios between the components. Such phase separation, although indicated thermodynamically, is not seen directly in the simulations of the n-heptane/n-octane mixture due to the difference in the pure component crystal structures.     

A study on the phase behavior of the system CO2 + CO + H2 + 1-hexene + heptanal

The phase behavior of a system of importance for the hydroformylation reaction of 1-hexene in supercritical CO₂ has been studied in the range of 303.2–348.2 K with different CO₂ mole fractions. The conversion of 1-hexene varies from 0 to 1. The density of the reaction mixture at different conditions are also determined. It is demonstrated that the phase behavior changes with conversion of 1-hexene. At zero conversion, the phase separation pressure increases with increasing concentration of the reactants in the reaction system and decreases slightly with the increase of temperature. At other conversions, the phase separation pressure increases as temperature rises. The density of the reaction mixture at phase separation point is higher at the larger conversions.     

Excess enthalpies of binary mixtures of 2-, 3-, 4-picoline+n-alkane (C6H14-C10H22) at 298.15 K. Comparison with theory

The molar excess enthalpies measured for binary mixtures of 2-, 3-, 4-picoline +n-alkane (C₆H₁₄-C₁₀H₂₂) at 298.15 K have been compared with the Prigogine-Flory-Patterson theory and the Extended Real Associated Solution model estimations.

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Zusammenfassung Die bei 298.15 K gemessenen molaren Zusatzenthalpien binärer Mischungen aus 2-,3-,4-Picolin und einemn-Alkan (C₆H₁₄-C₁₀H₂₂) wurden mit den nach der Prigonine-Flory-Patterson-Theorie und den nach dem erweiterten Modell real assoziierter Lösungen (ERAS) berechneten Weiten verglichen.

     

A novel approach to the modelling of the fluid multiphase behaviour of ternary mixtures of carbon dioxide + n-alkane + 1-alkanol

In this work, modelling of the phase behaviour in ternary systems composed of CO₂ + n-alkanes + 1-alkanols is described. The model assumes that the ternary system is congruent to binary systems composed of CO₂ + n-alkanes and that the phase behaviour of the ternary system can be related to the average molecular size of the solute molecules. The average molecular size of the solute molecules is calculated taking into account alkanol aggregation. Although some crude assumptions have been made, the model is able to describe experimental results qualitatively. Values for model parameters like the degree of aggregation and the equilibrium constant of the aggregation reaction correspond very well to values for these parameters obtained from IR-spectroscopy.