A thermodynamic approximation for the estimation of velocity correlation coefficients in binary liquid mixtures

An equation is derived using the relations of equilibrium thermodynamics to estimate limiting distinct diffusion coefficients, (or velocity cross-correlation coefficients) in binary non-electrolyte mixtures. It is tested against 13 mixtures. Good agreement is obtained with distinct diffusion coefficients derived experimentally in the case of near deal systems. For non-ideal mixtures the calculated values appear to follow the experimental coefficients to some extent. For this reason, the thermodynamic approximation is not as suitable for a reference equation as a structural approximation previously derived.     

Thermodynamics of liquid mixtures of krypton+ethane

The total vapour pressure, the excess Gibbs energy Q^E (at 115.77 K), the excess enthalpy H^E (at 117.0 K) and the excess molar volume V^E (at 115.77 K) are reported for liquid mixtures of krypton and ethane. The results are interpreted in the light of some recent statistical theories of liquid mixtures.     

Study of molecular properties using acoustic non-linearity parameter in the ternary liquid mixtures at different temperatures

The parameters of non-linearity (B/A) of ternary liquid mixtures, namely phenol and o-cresol with dimethyl sulfoxide (DMSO) in carbon tetrachloride have been evaluated at 293.15, 303.15 and 313.15?K. The non-linearity parameter has been computed by three different methods, namely Tong and Dong's method, Beyer's method and Beyer's method using Tong–Dong coefficients. The excess values of non-linearity parameter (B/A)^E have also been evaluated and discussed in the light of intermolecular interactions present in the liquid mixtures. Sehgal's relations for evaluating molecular properties for pure liquids are extended to ternary liquid mixtures.     

Flow microcalorimetry and thermokinetics of liquid mixtures

The identification of the calorimetric curves corresponding to liquid mixtures for different injection flows, given by a flow microcalorimeter, permits to classify in a kinetic way the studied mixtures. For this purpose, it is determined the establishment time constant of the mixture (τ_mix) that allows us to estimate the length occupied by the dissipation (through the parameter λ_mix) and thus to justify the sensitivity variation obtained in different chemical calibrations.     

Anomalies in the twist elastic behaviour of mixtures of calamitic and bent-core liquid crystals

ABSTRACT

The splay, twist and bend elastic constants (K₁₁, K₂₂ and K₃₃) have been measured as a function of temperature in bent-core/calamitic mixtures based on three different calamitic materials (5CB, 8CB and ZLI1132) and two bent-core dopants. The behaviour of the splay and bend constants are as expected; a reduction in K₃₃ of ~20%, in line with predictions from mixing rules and other observations. Interestingly, no change is seen in the splay constant, K₁₁ of the calamitic hosts. Surprisingly though, the twist elastic constant exhibits a reduction of 30 – 40% in all mixtures across the nematic range, an effect not previously reported and much larger than mixing rules can explain. The elastic behaviour is universal in our mixtures. We explain part of the reduction in the twist deformation by considering the influence of the chiral conformer fluctuations of the bent-core molecules on the twist elastic constants of the mixtures. However, the dramatic reduction can only be fully explained by also including contributions from chiral conformer fluctuations of the calamitic host, a form of chiral amplification.     

Surface tension and density of binary mixtures of monoalcohols,water and acetonitrile: equation of correlation of the surface tension

Measurements of the surface tension (σ) and density (ρ) of binary mixtures of monoalcohols, water and acetonitrile at 298.15 K and at atmospheric pressure, as a function of mole fraction (x) have been made. The experimental values of the deviation of surface tension and the excess of molar volume (Δσ, V ^E) have been correlated by the Redlich–Kister equation. An empirical correlation equation is presented for the study of the surface tension of these mixtures, and comparisons are made of the experimental values of surface tension versus those obtained with the correlation equation and with other models of correlation. Finally, with the purpose of corroborating the validity of the correlation equation, the latter is applied to other reference binary mixtures.     

Parametrization of the radial distribution function of a Yukawa fluid

We give semi-empirical expressions for five terms in an inverse temperature expansion of the radial distribution function of a Yukawa fluid. The parameters in these terms are chosen to fit what we believe should be an accurate equation of state when either the energy or pressure routes is used. Thus, a measure of self consistency is achieved. The equation of state which is the basis of our fit is the inverse temperature expansion of the Yukawa fluid free energy, obtained from the mean spherical approximation but modified to give reasonable results at low densities.     

Molecular solvent/ionic liquid binary mixtures: designing solvents based on the determination of their microscopic properties

This work aims at analyzing the microscopic features of binary solvent systems formed by a molecular solvent (dimethylsulfoxide or acetonitrile or methanol) and an ionic liquid cosolvent (ethylammonium nitrate). The empirical solvatochromic solvent parameters E _T(30), π*, α and β were determined from the solvatochromic shifts of adequate indicators. The behavior of the solvent systems was analyzed according to their deviation from ideality. The study pays particular attention to the identification of solvent mixtures with relevant solvating properties. We have focused our attention on the most remarkable microscopic property of the explored systems, acidity, selecting three mixtures with particular hydrogen bond donating characteristics.     

Thermodynamics of electrolyte mixtures. Activity and osmotic coefficients consistent with the higher-order limiting law for symmetrical mixing

The parameters for symmetrical mixing of ions of the same sign in the virial-coefficient (Pitzer) system are evaluated from literature data for 25°C in a manner consistent with the higher-order limiting law of Friedman. Twenty-four systems involve cation mixing with a common anion and fourteen involve anion mixing with a common cation. Heat of mixing data were similarly treated in a recent publication; the results give the temperature coefficients of some of these same parameters. The combined results yield the mixing parameters as functions of temperature on a basis both self-consistent and in accord with the limiting law. The results also yield, for a few systems without a common ion, predicted values in good agreement with experimental data.on leave from Liaoning University, Shenyang, China.     

Algorithms for GPU‐based molecular dynamics simulations of complex fluids: Applications to water,mixtures, and liquid crystals

A custom code for molecular dynamics simulations has been designed to run on CUDA‐enabled NVIDIA graphics processing units (GPUs). The double‐precision code simulates multicomponent fluids, with intramolecular and intermolecular forces, coarse‐grained and atomistic models, holonomic constraints, Nosé–Hoover thermostats, and the generation of distribution functions. Algorithms to compute Lennard‐Jones and Gay‐Berne interactions, and the electrostatic force using Ewald summations, are discussed. A neighbor list is introduced to improve scaling with respect to system size. Three test systems are examined: SPC/E water; an n‐hexane/2‐propanol mixture; and a liquid crystal mesogen, 2‐(4‐butyloxyphenyl)‐5‐octyloxypyrimidine. Code performance is analyzed for each system. With one GPU, a 33–119 fold increase in performance is achieved compared with the serial code while the use of two GPUs leads to a 69–287 fold improvement and three GPUs yield a 101–377 fold speedup. © 2015 Wiley Periodicals, Inc.     

Determination of the orientation distribution function of anisotropic paramagnetic species from the angular dependence of the ESR spectra

A method for determination of the orientation distribution function of anisotropic paramagnetic species from the angular dependence of the ESR spectra based on simulation of the spectra was developed. The orientation distribution function is represented as a sum of orthonormal functions. The weight coefficients are determined by minimizing the deviations of the theoretical spectra from experimental ones. The method was numerically tested. The method is relatively insensitive to the presence of noise and foreign ESR signals not related to the sample orientation in the magnetic field.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2595–2601, December, 2004.     

Simulation of adsorption of liquid mixtures of N2 and O2 in a model faujasite cavity at 77.5 K

Grand canonical Monte Carlo simulations of adsorption of N₂ and O₂ and their mixtures in a model zeolitic cavity 14 Å in diameter were performed at 77.5 K for pressures ranging from zero up to saturation, where the adsorbed phase is in equilibrium with coexisting vapor and liquid phases. The same intermolecular potential functions were employed for gas-gas interactions in the vapor, liquid, and adsorbed phases. The gas-solid interaction potential includes dispersion-repulsion energy, induced electrostatic energy, and an ion-quadrupole term to model the interaction of the electric field in zeolites like NaX with polar molecules like N₂. The simulation of the coexisting vapor and liquid phases reproduces the saturation properties of pure liquid oxygen and nitrogen at 77.5 K. Activity coefficients in the adsorbed phase derived from simulations as a function of cavity filling and composition show negative deviations from Raoult's law, even though the non-idealities in the bulk liquid phase have the opposite sign. The simulation of the surface excess isotherm for adsorption from liquid mixtures exhibits preferential adsorption of N₂ and has the commonly-observed quadratic shape skewed toward the more strongly adsorbed component. Micropore condensation is observed for oxygen but not for nitrogen. The condensation of oxygen is similar to a first order phase transition but because of the small number of molecules that can fit into a micropore, coexistence of the two phases is replaced by oscillations between gas- and liquid-like densities.     

A proposed equation of correlation for the study of thermodynamic properties (density,viscosity, surface tension and refractive index) of liquid binary mixtures

The literature on the physicochemical properties of liquid binary mixtures shows that most such systems exhibit nonlinear behavior. As a result, rigorous data and equations capable of affording a reliable estimate of the behavior of such mixtures are needed.     

Deconvolution and quantitation of unresolved mixtures in liquid chromatographic-diode array detection using evolving factor analysis

Summary A recently developed self-modeling curve resolution method based in different factor analysis techniques has been applied for the first time to the study of liquid-chromatography-diode array data under situation where the separation of two components is not achieved. Two applications are reported: the resolution and quantitation of a coeluted mixture of carbamate pesticides pirimicarb and 1-naphthol, and the estimation of the concentration profiles of the double peak obtained in the elution of the triazine metabolite chlorodiamino-s-triazine. Different methods of quantitation are compared, including Evolving Factor Analysis and Rank annihilation. Quantitation from the area of the elution profiles once the component spectra have been transformed for their area contribution to the signal, gives a relative composition for pirimicarb and naphthol pesticides which agrees with the known sample composition. In the case of the unknown triazine mixture, an approximate quantitation of the two peaks obtained for this metabolite is obtained by assuming equal signal contribution or equal maximum absorbance of the individual spectra of the two detected components.     

Phase behavior of ternary mixtures {aliphatic hydrocarbon + aromatic hydrocarbon + ionic liquid}: Experimental LLE data and their modeling by COSMO-RS

Separation of aromatic and aliphatic hydrocarbons is a complex process in the petrochemical industry due to overlapping boiling points and azeotrope formation. In this paper, liquid extraction of aromatic compounds (toluene and ethylbenzene) from aliphatic compounds (hexane and cyclohexene) using ionic liquids (1-butyl-3-methylimidazolium methylsulfate, BMimMSO₄, 1-propyl-3-methylimidazolium bis{trifluoromethylsulfonyl}imide, PMimNTf₂, and 1-butyl-3-methylimidazolium bis{trifluoromethylsulfonyl}imide, BMimNTf₂) as solvent was studied. (Liquid + liquid) equilibrium (ELL) data for the ternary systems {hexane (1) + ethylbenzene (2) + BMimMSO₄, or BMimNTf₂, or PMimNTf₂ (3)}, {hexane (1) + toluene (2) + BMimMSO₄ (3)} and {cyclohexene (1) + ethylbenzene (2) + BMimMSO₄ (3)} were experimentally determined at T = 298.15 K and atmospheric pressure. Moreover, an analysis of the influence of the structure of each compound on the phase behavior was also carried out. The ability of the studied ILs to separate aromatic from aliphatic compounds was evaluated in terms of the solute distribution ratio, β, and the selectivity, S. The Non Random Two-Liquid (NRTL) and UNIversal QUAsiChemical (UNIQUAC) thermodynamic models were used to correlate the experimental LLE data. Furthermore, the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) was applied to predict the (liquid + liquid) equilibrium. The suitability of this model to describe the phase behavior of the studied mixtures was evaluated comparing the experimental and calculated data.     

Schulz distribution function and the polydispersity of the binary suspension of charged macroions

Bidispersity of binary suspensions of charged macroions due to different sizes and charges are reduced into one-component model (OCM) using Schulz distribution function. Ordering in charged macroions has been studied using rescaled mean spherical approximation (RMSA) method with modified Derjaguin, Landau, Verwey and Overbeek (DLVO) potential. The results obtained are compared with the experiment, weight-average and Roger–Young (RY) schemes. It is inferred that Schulz distribution function is a plausible model to average out size and charges of macroions to study the structural behavior of the binary suspension of macroions. An ordering with co-ordination number 12 has been reported in the binary suspension of charged macroions.     

A simple approach to treat anisotropic elastic collisions in Monte Carlo calculations of the electron energy distribution function in cold plasmas

A simplified method allowing one to treat anisotropic electron heavy species elastic scattering in MonteCarlo models of gas discharges with the proper value for collision frequency is proposed The method is applied to an electric discharge in a Ne · Xe/HCl mixture, and the results are compared with the solution of the two-term expansion of the Boltzmann equation under the same conditions. Methods for reduction of computational time in Monte Carlo codes and the use of the Monte Carlo flux method are also discussed.     

Role of electronic partition function in quantitative SIMS using the Saha-Eggert equation

Methods of obtaining the electronic partition functionsZ were discussed with an intention to use them for the Saha-Eggert quantification in SIMS. The Lagrange's interpolation formula and the least-squares method were applied to the published values ofZ to obtain the expression for calculatingZ at arbitrary temperatures. With the aid of the Saha-Eggert equation, the secondary-ion currents from Ni-Cr and Fe-Ni-Cr alloys were converted into the elemental concentrations for the two types ofZ: those obtained with the above methods and those with the approximate fifthorder polynomials presented by de Galan and others. It was proved, from the comparison of the calculated concentrations, that the latter are valid for the quantification in SIMS using the Saha-Eggert equation. The largest error in the elemental concentrations was 22% for the Ni-Cr alloy and 7% for the Fe-Ni-Cr alloy.     

Speed of sound and isentropic compressibilities of nonelectrolyte liquid mixtures. I. Binary mixtures containingp-dioxane

The speed of sound was measured for mixtures of p-dioxane with cyclohexane, n-hexane, benzene, toluene, carbon tetrachloride, chloroform, 1,1,2,2-tetrachloroethane, pentachloroethane and ethyl acetate over the whole mole fraction range at 30°C. These data were combined with densities and molar volumes to obtain isentropic compressibilities and Rao's molar sound functions. Excess isentropic compressibilities and excess speeds of sound have also been calculated. The behavior of the present mixtures is discussed in terms of possible molecular interactions and the Prigogine-Flory-Patterson theory of liquid mixtures.