Differential capacitance of liquid/liquid interfaces of finite thicknesses: a finite element study

Finite element simulations were used to investigate the effect of a smooth variation of permittivity across a polarized liquid/liquid interface on the differential capacitance. The results show that a relative permittivity profile can account for the variation of ion solvation in the interfacial region, and therefore upon the diffuse double layer itself. The width and the symmetry of this profile across the interface are shown to be crucial parameters for interfacial distributions and fitting of capacitance data has been used to estimate the width of the interfacial region.     

A molecular model of water based on the lattice gas model

A lattice gas model is used to describe the vapor-liquid state of water molecules. The orientationally directed interaction of the water molecules via their tetrahedral structure and dipole-dipole interaction are considered in the theory, along with the Lennard-Jones contributions to the potential of molecular interaction, which stabilize the system with dipole interaction. We studied how the radius of the molecular interaction potential affects the equilibrium characteristics of the system (the phase separation curves of the vapor-liquid system, and the relationship between the fluid density and the chemical potential value).     

Differential capacitance of ionic liquid interface with graphite: the story of two double layers

We combine electronic density functional theory for the screening properties of graphite with a mean-field theory of the double layer in ionic liquids to reveal what underpins the morphology of the voltage dependence of electrical capacitance of a flat graphite/ionic liquids interface.     

Simulation of polymer--polymer interdiffusion using the dynamic lattice liquid model

In this paper, we present computer simulation results concerning interdiffusion of fully compatible components in symmetric binary (AB) polymer mixtures in solutions. The simulation is performed in two dimensions using the algorithm based on the dynamic lattice liquid model. The solvent molecules are taken into account explicitly. The evolution of the concentration profiles in time at an interface is studied for chain lengths N=2,4,8,16 for three polymer concentrations phi=0.1,0.5,0.9. The tracer diffusion coefficients for polymer chains and for the solvent are obtained by monitoring the mean square displacements of their center of mass. The relationships between coefficients of interdiffusion and self-diffusion are tested.     

Fractal approach of nucleation in liquid and gas phases

Summary The authors present a generalised fractal treatment of the nucleation from the liquid solution or gas-phase reactant.     

Analysis of surface anchored lattice plane orientation in blue phase liquid crystal and its in-plane electric field-dependent capacitance response

Uniformly oriented macroscopic monodomain of cholesteric blue phase liquid crystal has been realised by the influence of surface anchoring. Orientation of the lattice planes in surface-treated (ST) and non-surface-treated (NST) cell were analysed and compared by Kossel diagram technique. NST cell has revealed the green and blue domains corresponding to reflection from oriented (110) and (112) planes of the body-centred cubic lattice. However, in the ST cell only the lattice plane (110) oriented uniformly and tailored the macroscopic monodomain. Electric field driven reorientation of the (110) lattice plane was noticed in NST cell whereas for ST cell such reorientation was absent. Two distinct electric field-induced capacitive responses have been observed in the two different cells. In NST cell anomalous electrostriction was observed, whereas for ST cell normal electrostriction was observed. Interestingly, the capacitance has decreased with an increasing electric field for anomalous electrostriction in NST cell, whereas for normal electrostriction in ST cell it was increased with increasing the field. Such a capacitive change behaviour is explained by dielectric anisotropic change followed by the electric field induced elongation and contraction of the cubic unit cell along and perpendicular to the electric field.     

Wrong gas/liquid partition data by gas chromatography

In a paper published in 1992 [K.S. Reddy, J.-Cl. Dutoit, E.sz. Kováts, Pair-wise interactions by gas chromatography. I. Interaction free enthalpies of solutes with non-associated primary alcohol groups, J. Chromatogr. 609 (1992) 229] retention indices and standard chemical potential differences (SPOT-s) are given for about 160 solutes on a liquid branched paraffin hydrocarbon of the carbon number, z = 78. For the temperature dependence of the SPOT-s the proposal of Kirchhoff was accepted i.e. that at higher temperatures the molar heat capacity difference of the solute between the gas phase and the solution is nearly constant in a broad temperature range. The data were determined under conditions where the effect of adsorption could be neglected. By comparing the published data with those determined on another branched paraffin of the carbon number, z = 87 [F. Riedo, D. Fritz, G. Tarján, E.sz. Kováts, A tailor-made C87 hydrocarbon as a possible non-polar standard stationary phase for gas chromatography, J. Chromatogr. 126 (1976) 63] it is shown that the reported thermodynamic constants of solutes determined experimentally at higher temperatures (the group "H") are wrong on C78. In the present paper, the method of correction and the resulting corrected data are given. In later papers retention data are given on eight polar derivatives of the hydrocarbon C78 relative to those measured on the nonpolar standard [R. Cloux, G. Défayes, K. Fóti, J.-Cl. Dutoit, E.sz. Kováts, Pair-wise interactions by gas chromatography. III. Synthesis of isosteric stationary phases for gas chromatography, Synthesis (1993) 909; G. Défayes, K.S. Reddy, A. Dallos, E.sz. Kováts, Pair-wise interactions by gas chromatography. V. Interaction free enthalpies of solutes with primary chloro- and bromo-alkanes, J. Chromatogr. A 699 (1995) 131; K.S. Reddy, E.sz. Kováts, Pair-wise interactions by gas chromatography. II. Sociation free enthalpies of some hydrogen bonding solutes with non-associated primary alcohol groups, Chromatographia 34 (1992) 249; K.S. Reddy, R. Cloux, E.sz. Kováts, Pair-wise interactions by gas chromatography. IV. Interaction free enthalpies of solutes with trifluoromethyl-substituted alkanes, J. Chromatogr. A 673 (1994) 181; K.S. Reddy, R. Cloux, E.sz. Kováts, Pair-wise interactions by gas chromatography. VI. Interaction free enthalpies of solutes with primary methoxyalkane, cyanoalkane and alkanethiol groups, J. Chromatogr. A 704 (1995) 387; A. Dallos, A. Sisak, Z. Kulcsár, E.sz. Kováts, Pair-wise interactions by gas chromatography. VII. Interaction free enthalpies of solutes with secondary alcohol groups, J. Chromatogr. A 904 (2000) 211]. Obviously, the same data which are wrong in the nonpolar standard are also wrong in these solvents. The corrected data in the polar solvents are given in supplementary tables.     

Electrical model of a liquid crystal pixel with dynamic, voltage history-dependent capacitance value

The voltage history-dependent nature of a liquid crystal pixel capacitance becomes an important issue in active matrix addressing as large storage capacitors are replaced with more intelligent circuitry such as in-pixel frame buffers. In this paper, a simple but flexible Spice macro model is introduced that allows accurate simulations of the electrical behaviour of a nematic liquid crystal pixel capacitance. The model correctly predicts voltage drops caused by the increasing dielectric constant when liquid crystal molecules align themselves to the electric field. An internal node of the macro model represents the average director orientation and can also be used to predict the optical response. In its basic embodiment, the model uses a first-order, low pass RMS filter to implement the dynamic behaviour of the pixel, which suffices to predict response delays and asymmetric rise and fall times. However, the model also supports more elaborated filters that offer more control over the simulated dynamic behaviour. A number of simulations are performed that illustrate the usefulness of the new model during the design of novel 'smart' pixel architectures.     

Thermodynamic and dynamic anomalies in a one-dimensional lattice model of liquid water

We investigate the occurrence of waterlike thermodynamic and dynamic anomalous behavior in a one dimensional lattice gas model. The system thermodynamics is obtained using the transfer matrix technique and anomalies on density and thermodynamic response functions are found. When the hydrogen bond (molecules separated by holes) is more attractive than the van der Waals interaction (molecules in contact) a transition between two fluid structures is found at null temperature and high pressure. This transition is analogous to a 'critical point' and intimately connects the anomalies in density and in thermodynamic response functions. Monte Carlo simulations were performed in the neighborhood of this transition and used to calculate the self diffusion constant, which increases with density as in liquid water.     

Dependence of gas/solid energy transfer on lattice chain length

Effects of the length of one-dimensional semi-infinite lattice chains on atom/chain energy transfer processes have been studied through calculations of time evolution of the dynamical variables in classical mechanics. The amount of energy transfer varies strongly with number of lattice atoms. For a given atom/chain system, the chain length needed to determine energy transfer can be very long at low collision energies, but length rapidly decreases with rising energy. The presence of a light surface impurity atom can significantly reduce the required length.     

Controllable gas/liquid/liquid double emulsions in a dual-coaxial microfluidic device

This article presents a simple and novel approach to prepare monodispersed gas-in-oil-in-water (G/O/W) and gas-in-water-in-oil (G/W/O) double-emulsions in the same dual-coaxial microfluidic device. The effects of three phase flow rates on the sizes of microbubbles and droplets and the number of the encapsulated microbubbles were systematically studied. We successfully synthesized two different types of gas/liquid/liquid (G/L/L) double emulsions with different inner structures in the same geometry by adjusting the flow rates sequentially. Mathematical models were developed to predict the size and structures of the double emulsions. This simple approach gives a new idea for preparing hollow and porous microspheres with microbubbles as the direct core/pores templates.     

A theory of a curved vapor-liquid separation boundary: The lattice gas model

Molecular theory of curved vapor-liquid interphase boundaries was considered in terms of the lattice gas model. The theory uses the quasi-thermodynamic concept of curved layers of a separation boundary with a large radius. The transition from a rectangular lattice to such layers is performed by the introduction of a variable number of the nearest neighbors. The problems (1) of the transition from distributed molecular models to layer models reflecting macroscopic symmetry of the interphase boundary and (2) of a minimum linear size of the surface region to which thermodynamic approaches are applicable were considered. Equations for the quasi-equilibrium distribution of molecules at the vapor-liquid boundary in a metastable system were constructed in the quasi-chemical approximation taking into account direct correlations between the nearest interacting molecules. A metastable state is maintained by a pressure jump described by the macro-scopic Laplace equation on a separation surface inside the interphase region. Equations for local mean pressure values and normal and tangential pressure tensor components inside the interphase region were constructed. These equations were used to obtain microscopic difference mechanical equilibrium equations for curved boundaries of spherical and cylindrical drops in the metastable state. The relation between the micro-scopic difference mechanical equilibrium equations and similar differential equations and the macroscopic Laplace equation, which described pressure jump in a metastable system, was considered. Various definitions of surface tension are discussed.     

Electroviscoelasticity of liquid/liquid interfaces: fractional-order model

A number of theories that describe the behavior of liquid-liquid interfaces have been developed and applied to various dispersed systems, e.g., Stokes, Reiner-Rivelin, Ericksen, Einstein, Smoluchowski, and Kinch. A new theory of electroviscoelasticity describes the behavior of electrified liquid-liquid interfaces in fine dispersed systems and is based on a new constitutive model of liquids. According to this model liquid-liquid droplet or droplet-film structure (collective of particles) is considered as a macroscopic system with internal structure determined by the way the molecules (ions) are tuned (structured) into the primary components of a cluster configuration. How the tuning/structuring occurs depends on the physical fields involved, both potential (elastic forces) and nonpotential (resistance forces). All these microelements of the primary structure can be considered as electromechanical oscillators assembled into groups, so that excitation by an external physical field may cause oscillations at the resonant/characteristic frequency of the system itself (coupling at the characteristic frequency). Up to now, three possible mathematical formalisms have been discussed related to the theory of electroviscoelasticity. The first is the tension tensor model, where the normal and tangential forces are considered, only in mathematical formalism, regardless of their origin (mechanical and/or electrical). The second is the Van der Pol derivative model, presented by linear and nonlinear differential equations. Finally, the third model presents an effort to generalize the previous Van der Pol equation: the ordinary time derivative and integral are now replaced with the corresponding fractional-order time derivative and integral of order p<1.     

Influence of the ionic liquid/gas surface on ionic liquid chemistry

Applications such as gas storage, gas separation, NP synthesis and supported ionic liquid phase catalysis depend upon the interaction of different species with the ionic liquid/gas surface. Consequently, these applications cannot proceed to the full extent of their potential without a profound understanding of the surface structure and properties. As a whole, this perspective contains more questions than answers, which demonstrates the current state of the field. Throughout this perspective, crucial questions are posed and a roadmap is proposed to answer these questions. A critical analysis is made of the field of ionic liquid/gas surface structure and properties, and a number of design rules are mined. The effects of ionic additives on the ionic liquid/gas surface structure are presented. A possible driving force for surface formation is discussed that has, to the best of my knowledge, not been postulated in the literature to date. This driving force suggests that for systems composed solely of ions, the rules for surface formation of dilute electrolytes do not apply. The interaction of neutral additives with the ionic liquid/gas surface is discussed. Particular attention is focussed upon H(2)O and CO(2), vital additives for many applications of ionic liquids. Correlations between ionic liquid/gas surface structure and properties, ionic liquid surfaces plus additives, and ionic liquid applications are given.     

An alternative approach to rubber elasticity theory based on a lattice model

An alternative rubber elasticity theory for bulk elastomers has been developed. It is based on the model of a cubic lattice which is filled completely with long flexible chains. The dependence of the configurational entropy on the orientation factor of Hermans has been derived for a uniaxial homogeneous orientation of the system. With the assumption of a constant stress-optical coefficient, the dependence of the true stress Γ on the deformation λ = L/L₀, with L the length of the sample, can be described approximately as τ ∝︁ in λ both for uniaxial extension and compression, which agrees quite well with experimental results on bulk elastomers.     

A thermodynamic approach to understanding liquid crystal selectivity in gas chromatography

Summary The thermodynamics of four new liquid crystals were investigated in order to understand their selectivity as stationary phases in gas chromatography. In this case study, liquid crystals with a benzoyloxy azobenzene mesogenic core substituted with heptyloxy (C7) and/or dioxyethylene ether (DOE) groups, were used. The chromatographic separations of linalool and citronellal, and of xylene, tetraethylbenzene and cresol isomers, which were achieved with the liquid crystal stationary phases, have been related to the dissolution thermodynamics of the solutes. The results gave us an insight into the mechanism of the molecular recognition involved in the separation processes.     

Structure and anomalous solubility for hard spheres in an associating lattice gas model

In this paper we investigate the solubility of a hard-sphere gas in a solvent modeled as an associating lattice gas. The solution phase diagram for solute at 5% is compared with the phase diagram of the original solute free model. Model properties are investigated both through Monte Carlo simulations and a cluster approximation. The model solubility is computed via simulations and is shown to exhibit a minimum as a function of temperature. The line of minimum solubility (TmS) coincides with the line of maximum density (TMD) for different solvent chemical potentials, in accordance with the literature on continuous realistic models and on the "cavity" picture.