Large attractive depletion interactions in soft repulsive-sphere binary mixtures

We consider binary mixtures of soft repulsive spherical particles and calculate the depletion interaction between two big spheres mediated by the fluid of small spheres, using different theoretical and simulation methods. The validity of the theoretical approach, a virial expansion in terms of the density of the small spheres, is checked against simulation results. Attention is given to the approach toward the hard-sphere limit and to the effect of density and temperature on the strength of the depletion potential. Our results indicate, surprisingly, that even a modest degree of softness in the pair potential governing the direct interactions between the particles may lead to a significantly more attractive total effective potential for the big spheres than in the hard-sphere case. This might lead to significant differences in phase behavior, structure, and dynamics of a binary mixture of soft repulsive spheres. In particular, a perturbative scheme is applied to predict the phase diagram of an effective system of big spheres interacting via depletion forces for a size ratio of small and big spheres of 0.2; this diagram includes the usual fluid-solid transition but, in the soft-sphere case, the metastable fluid-fluid transition, which is probably absent in hard-sphere mixtures, is close to being stable with respect to direct fluid-solid coexistence. From these results, the interesting possibility arises that, for sufficiently soft repulsive particles, this phase transition could become stable. Possible implications for the phase behavior of real colloidal dispersions are discussed.     

Adsorption equilibria of binary ethylmercaptan/hydrocarbon mixtures on a NaX zeolite

We present here coadsorption data of ethylmercaptan with n-heptane or toluene on NaX at 298 K in the aim to use this adsorbent for removing mercaptans from natural gas. Results show that NaX has an adsorption affinity for sulphur compound strong enough to perform a deep desulphurization. NaX adsorbs preferentially ethylmercaptan over a large domain of pore filling. A displacement of n-heptane by ethylmercaptan is even observed. However, toluene becomes preferentially adsorbed at high filling. The dependence of filling and composition on selectivities and failed prediction of coadsorption equilibria by the IAS Theory indicate that the adsorbed mixture behaves as a non-ideal solution. Calorimetric measurements of coadsorption heats show that the coadsorption process is not governed by enthalpic effects but by entropic effects consecutive to steric hindrance of molecules in confined spaces.     

Modifying zeolite particle morphology and size using water/oil/surfactant mixtures as confined domains for zeolite growth

Here we report the synthesis of silicalite-1 particles using microemulsions wherein the particle size and morphology can be varied.     

Adsorption and desorption of binary mixtures in confined geometry: A pilot positron annihilation study

In confined (nanometer-scale) geometry, the effects of substrate forces and finite size produce a shift of the gas liquid phase boundary from that found in corresponding bulk. The pore transitions also show marked hysteresis. The phase behaviour of a binary gas mixture in confined geometry is likely to depend on the miscibility of the system and the interaction between the substrate and the individual fluid molecules/atoms. Here, we present the results of a pilot positronium annihilation study of the condensation and evaporation of argon-nitrogen mixtures confined in 4 nm diameter cylindrical pores in VYCOR glass.     

Unusual phase behavior of decane-dodecane mixtures confined in SBA-15:Size effect on binary phase diagram

Phase behavior of normal decane-dodecane(n-C₁₀H₂₂-C₁₂H₂₆,C₁₀-C₁₂) system confined in SBA-15（Santa Barbara Amorphous,pore diameters 3.8,7.8,and 17.2 nm） has been studied by using differential scanning calorimetry.It has been found solid-liquid phase diagram of the C₁₀-C₁₂/SBA-15 system is composed of a straight line（3.8 nm）,a curve（7.8 nm） and a loop line （17.2 nm）.The growth of the phase diagram clearly shows the size effect on phase behavior of binary alkanes.Phase behavior has been compared among the systems C₁₀H₂₂-C₁₂H₂₆/SBA-15,C₁₂H₂₆-C₁₄H₃₀/SBA-15 and C₁₄H₃₀-C₁₆H₃₄/SBA-15.     

Anisotropic diffusion in confined colloidal dispersions: the evanescent diffusivity

We employ an analogy to traditional dynamic light scattering to describe the inhomogeneous and anisotropic diffusion of colloid particles near a solid boundary measured via evanescent wave dynamic light scattering. Following this approach, we generate new expressions for the short-time self- and collective diffusivities of colloidal dispersions with arbitrary volume fraction. We use these expressions in combination with accelerated Stokesian dynamics simulations to calculate the diffusivities in the limit of large and small scattering wave numbers for evanescent penetration depths ranging from four particle radii to one-fifth of a particle radius and volume fractions from 10% to 40%. We show that at high volume fractions, and larger penetration depths, the boundaries have little effect on the dynamics of the suspension parallel to the wall since, to a first approximation, the boundary acts hydrodynamically much as another nearby particle. However, near and normal to the wall, the diffusivity shows a strong dependence on penetration depth for all volume fractions. This is due to the lubrication interactions between the particles and the boundary as the particle moves relative to the wall. These results are novel and comprehensive with respect to the range of penetration depth and volume fraction and provide a complete determination of the effect of hydrodynamic interactions on colloidal diffusion adjacent to a rigid boundary.     

Discrete solvation layering in confined binary liquids

The solvation force profiles of squalane/octamethylcyclotetrasiloxane (OMCTS) mixtures confined between Si3N4 tips and highly oriented pyrolytic graphite (HOPG) and hexadecane/OMCTS confined between alkanethiol-functionalized tips and freshly cleaved mica have been measured by atomic force microscopy. Measurements on HOPG reveal oscillatory behavior where discrete solvation layers of both squalane and OMCTS are observed in a single force curve. The large repulsive force of the first solvation layer (squalane) on HOPG indicates that it is strongly bound. Oscillatory behavior is also observed for hexadecane/OMCTS on mica excepting that the oscillations are found in the attractive regime. The OMCTS layers in this case are less ordered with slightly larger (approximately 1 A) periodicities. These results are in agreement with computer simulations for binary liquid mixtures but differ qualitatively from surface force apparatus experiments.     

Synergisms in binary surfactant mixtures

Significant correlations become apparent between synergisms of micelle formation in surfactant mixtures and a series of physico-chemical properties and applications. Examples are emulsifying, dispersing, wetting, flotation, washing and cleaning ability. As a result, the effect of a co-surfactant with respect to problems of application can be predicted by a few surface tension measurements only.     

Raoult's law as applied to binary solvent mixtures

The inapplicability of the original statement of Raoult's law to binary solvent mixtures has been known for many years. An appropriate form for binary solvent mixtures is developed from the fundamental thermodynamic concept of fugacity, and is shown to be quantitatively applicable to the water+tetrahydrofuran solvent system and qualitatively applicable to the results which have been obtained for other aqueous organic solvent mixtures.     

Nucleation versus spinodal decomposition in confined binary solutions

Basic features of spinodal decomposition, on one side, and nucleation, on the other side, and the transition between both mechanisms are analyzed within the framework of a generalized thermodynamic cluster model based on the generalized Gibbs approach. Hereby the clusters, representing the density or composition variations in the system, may change with time both in size and in their intensive state parameters (density and composition, for example). In the first part of the analysis, we consider phase separation processes in dependence on the initial state of the system for the case when changes of the state parameters of the ambient system due to the evolution of the clusters can be neglected as this is the case for cluster formation in an infinite system. As a next step, the effect of changes of the state parameters on cluster evolution is analyzed. Such depletion effects are of importance both for the analysis of phase formation in confined systems and for the understanding of the evolution of ensembles of clusters in large (in the limit infinite) systems. The results of the thermodynamic analysis are employed in both cases to exhibit the effect of thermodynamic constraints on the dynamics of phase separation processes.     

Solvation effects in near-critical binary mixtures

A Ginzburg-Landau theory is presented to investigate solvation effects in near-critical polar fluid binary mixtures. Concentration dependence of the dielectric constant gives rise to a shell region around a charged particle within which solvation occurs preferentially. As the critical point is approached, the concentration has a long-range Ornstein-Zernike tail representing strong critical electrostriction. If salt is added, strong coupling arises among the critical fluctuations and the ions. The structure factors of the critical fluctuations and the charge density are calculated and the phase transition behavior is discussed.     

Excess compressibility in binary liquid mixtures

Brillouin scattering experiments have been carried out on some mixtures of molecular liquids. From the measurement of the hypersonic velocities we have evaluated the adiabatic compressibility as a function of the volume fraction. We show how the quadratic form of the excess compressibility dependence on the solute volume fraction can be derived by simple statistical effects and does not imply any interaction among the components of the system other than excluded volume effects. This idea is supported by the comparison of the experimental results with a well-established prototype model, consisting of a binary mixture of hard spheres with a nonadditive interaction potential. This naive model turns out to be able to produce a very wide spectrum of structural and thermodynamic features depending on values of its parameters. An attempt has made to understand what kind of structural information can be gained through the analysis of the volume fraction dependence of the compressibility.     

Solvophobic effects in binary nonaqueous mixtures

In the framework of the Mc Millan-Mayer theory, the enthalpy, volume, and heat capacity coefficients of binary and ternary interactions of amides, alcohols, and acetonitrile in water and nonaqueous solvents were obtained at various temperatures. No pronounced regularities in changes in the coefficients of multiple interactions observed in aquous solutions were found for nonaqueous solutions of the substances studied. None of the considered coefficients can be used as a criterion for solvophobicity. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1587–1591, September, 1997.     

Stability limits in binary fluids mixtures

The stability limits in binary fluid mixtures are investigated on the basis of the global phase diagram approach employing a model for the attracting hard-sphere fluid. In addition to the diffusion spinodals the mechanical spinodals are included. As a result one finds topologically different types of the diffusion spinodals while only one shape exists for the mechanical spinodals which are present in the region of liquid-vapor equilibria only. The diffusion spinodals represent the underlying properties of the phase behavior. The types of stable phase behavior therefore resemble that of the spinodal behavior. The different shapes of the spinodals can be important for nonequilibrium processes in nature and technology.     

Spectral density function approach to homogenization of binary mixtures

The effective permittivity of binary mixtures having the spectral density function of the β distribution form is considered. Some particular cases such as low-concentration limit, weak and high dielectric contrast limit are considered in more detail. Finally, the validity of the approach for some microgeometries is supported by its good agreement with independent methods.     

Phase behavior in thin films of confined colloid-polymer mixtures

Using self-consistent-field and density-functional theories, we first investigate colloidal self-assembly of colloid-polymer films confined between two soft surfaces grafted by polymers. With increasing colloidal concentrations, the film undergoes a series of transitions from disordered liquid --> sparse square --> hexagonal (or mixed square-hexagonal) --> dense square --> cylindrical structures in a plane, which results from the competition between the entropic elasticity of polymer brushes and the steric packing effect of colloidal particles. A phase diagram displays the stable regions of different in-layer ordering structures as the colloidal concentration is varied and layering transitions as the polymer-grafted density is decreased. Our results show a new control mechanism to stabilize the ordering of structures within the films.     

Phase behavior of undecane-tetradecane mixtures confined in SBA-15

Phase behavior of undecane-tetradecane (n-C11H24-C14H30, C11-C14) mixtures in bulk and confined in SBA-15 have been studied using differential scanning calorimetry. The bulk C11-C14 system shows multiple phase regions due to rotator phase. Confined in the pores of SBA-15 (pore diameters 3.8-7.8 nm), the mixtures only show a melting boundary of a straight line and a curve, respectively. In SBA-15 (17.2 nm), phase behavior of themixtures has some similarity to that of the bulk. Under confinement, the phase diagrams of the mixtures vary with the pore size, temperature, and compositions.     

Preferential solvation of acridine in binary mixtures

Preferential solvation studies of acridine have been investigated using optical absorption technique. The preferential solvation parameter shows that in dimethyl formamide (DMF)+ethanol mixture, the acridine is preferentially solvated by ethanol in DMF rich region and by DMF in ethanol rich region. In the case of DMF+Carbon tetrachloride mixture acridine is preferentially solvated by DMF.     

Soret motion in non-ionic binary molecular mixtures

We study the Soret coefficient of binary molecular mixtures with dispersion forces. Relying on standard transport theory for liquids, we derive explicit expressions for the thermophoretic mobility and the Soret coefficient. Their sign depends on composition, the size ratio of the two species, and the ratio of Hamaker constants. Our results account for several features observed in experiment, such as a linear variation with the composition; they confirm the general rule that small molecules migrate to the warm, and large ones to the cold.