Polymolecular adsorption and capillary condensation in narrow slit pores

Capillary condensation and polymolecular adsorption in narrow slits has been calculated, where the fields of surface forces overlap one another. The calculations were carried out on the basis of macroscopic theory of dispersion forces and the isotherms of lone adsorption layers at the free surface. It has been shown that under the effect of mutual attraction through a gap, polymolecular adsorption films lose their stability long before their thickness has approached the half-width of a flat slit. This results in hysteresis of the capillary condensation in an ensemble of plane-parallel slits.

In the case of systems having strong adsorbate-adsorbate interaction, there has been detected the existence of the lower limit of sizes of slit pores, wherein the capillary meniscus can coexist with adsorption films. With a slit width smaller than the critical one, the meniscus is likely to form a finite contact angle with “dry” surfaces of a slit. Thus an explanation has been given of the lower limit of the capillary condensation in an ensemble of flat-surface, slit pores. In the case of strong adsorbate-adsorbent interaction, the coexistence of meniscus with adsorption films within the scope of the approach used is possible in slits of any width.

The value of corrections for the surface forces effect to be entered in the calculations of slit pores dimensions has been analyzed on the basis of the capillary condensation data obtained.

In wedge-shaped slits there also exists, besides lower limit the upper limit of capillary hysteresis.     

Anisotropic dynamics of dipolar liquids in narrow slit pores

We report molecular dynamics simulation results for Stockmayer fluids confined to narrow slitlike pores with structureless, nonconducting walls. The translational and rotational dynamics of the dipolar particles have been investigated by calculating autocorrelation functions, diffusion coefficients, and relaxation times for various pore widths (five or less particle diameters) and directions parallel and perpendicular to the walls. The dynamic properties of the confined systems are compared to bulk properties, where corresponding bulk and pore states at the same temperature and chemical potential are determined in parallel grand canonical Monte Carlo simulations. We find that the dynamic behavior inside the pore depends on the distance from the walls and can be strongly anisotropic even in globally isotropic systems. This concerns especially the particles in the surface layers close to the walls, where the single particle and collective dipolar relaxation resemble that of true two-dimensional dipolar fluids with different in-plane and out-of-plane relaxations. On the other hand, bulklike relaxation is observed in the pore center of sufficiently wide pores.     

Dielectric response of polar liquids in narrow slit pores

Based on molecular dynamics (MD) simulations and a simple (Stockmayer) model we investigate the static and dynamic dielectric response of polar liquids confined to narrow slit pores. The MD simulations are used to calculate the time-dependent polarization fluctuations along directions parallel and perpendicular to the walls, from which the components of the frequency-dependent dielectric tensor can be derived via linear response theory. Our numerical results reveal that the system's response is strongly anisotropic. The parallel dielectric function, epsilonparallel(omega), has Debye-like character very similar to the corresponding isotropic bulk function, epsilonbulk(omega), at the same chemical potential. Indeed, the main confinement effect on epsilonparallel(omega) consists in a shift toward smaller values relative to the bulk function. On the other hand, in the perpendicular direction we observe a characteristic peak in the absorption part of the dielectric function, epsilonperpendicular(omega). This peak is absent in the bulk system and reflects strongly pronounced, damped oscillations in the polarization fluctuations normal to the walls. We discuss two possible origins of the oscillations (and the resulting absorption peak), that is collective oscillations of dipoles in clusters formed parallel to the walls, and the existence of a "dipolaron mode" previously observed in MD simulations of bulk polar fluids.     

Critical temperature of capillary condensation in narrow cylindrical pores

The dependence of the critical temperature of capillary condensation of an adsorbate in cylindrical pores on the diameter of pores is investigated. The calculation is carried out in the quasi-chemical approximation with a calibration function providing the agreement of results for small pores with exact values obtained by the fragment method. The contribution of the size effect to the calibration function as a function of the diameter of pores is considered in terms of the concept of quasi-one-dimensional behavior of the adsorbate in narrow pores. Various adsorbate-adsorbate potentials are considered.     

Characteristic features of phase diagrams describing condensation of adsorbate in narrow pores

The phase diagrams describing condensation of adsorbate in micro- and mesoporous adsorbents having slit-shaped and cylindrical pores whose size varied from 1 to 20 monolayers were constructed. The study was performed using the lattice-gas model in the quasichemical approximation to take into account the intermolecular interactions. The phase diagrams for various values of the potential arising from different types of adsorbate--adsorbent interaction were analyzed for adsorption of helium, neon, methane, and carbon tetrachloride in graphite pores. Other adsorption systems are considered and the relationship between the pressure and temperature of adsorbate condensation is discussed. A nonmonotonic variation of the critical densities for pore widths from 3 to 10 molecular diameters was found. The pattern of this variation depends on the ratio of the energy of lateral interactions of the adsorbate molecules to the energy of interaction of the adsorbate molecules with pore walls. The critical temperature decreases monotonically with a decrease in the pore width. The stronger the adsorbate interaction with the pore walls, the greater the decrease in the critical temperature.     

Unusual mechanism of capillary condensation in pores modified with chains forming pillars

Density functional approach is applied to study the phase behavior of Lennard-Jones(12,6) fluid in pillared slit-like pores. Our focus is in the evaluation of phase transitions in fluid adsorbed in the pore of a fixed width. If the length of pillars is sufficiently large, we observe additional phase transitions of the first and second order due to the symmetry breaking of the distribution of chain segments and fluid species with respect to the slit-like pore center. Re-entrant symmetry changes and additional critical, critical end points and tricritical points then are observed. The scenario of phase changes is sensitive to the energy of fluid-solid interaction, the amount, and the length of the pillars. Quantitative trends and qualitative changes of the phase diagrams topology are examined depending on the values of these parameters.     

From chains to rings, and back again: structural rearrangements during evaporation and condensation

The mechanistic details of the sequence of structural changes that occur in weakly bound molecular complexes upon change in phase have yet to be presented in detail. Consider the structural rearrangements that occur at the interface between the liquid and its vapor for species such as hydrofluoric acid or the low molecular weight aliphatic acids. There are both experimental and theoretical evidence that liquid HF consists of extended zig-zag chains [1], whereas the vapor consists predominantly of non-planar cyclic structures [2]. Similarly, the cyclic structures of gaseous aliphatic acid dimers was established decades ago but in the solid and liquid phases, the molecular configurations are zig-zag chains [3].     

Modeling molecular transport in slit pores

We examine the transport of methane in microporous carbon by performing equilibrium and nonequilibrium molecular dynamics simulations over a range of pore sizes, densities, and temperatures. We interpret these simulation results using two models of the transport process. At low densities, we consider a molecular flow model, in which intermolecular interactions are neglected, and find excellent agreement between transport diffusion coefficients determined from simulation, and those predicted by the model. Simulation results indicate that the model can be applied up to fluid densities of the order to 0.1-1 nm(-3). Above these densities, we consider a slip flow model, combining hydrodynamic theory with a slip condition at the solid-fluid interface. As the diffusion coefficient at low densities can be accurately determined by the molecular flow model, we also consider a model where the slip condition is supplied by the molecular flow model. We find that both density-dependent models provide a useful means of estimating the transport coefficient that compares well with simulation.     

Relaxation and short time dynamics of bulk liquids and fluids confined in spherical cavities and slit pores

The density of states for bulk and confined fluids have been modeled using a recently proposed gamma distribution (Krishnan, S. H.; Ayappa, K. G. J. Chem. Phys. 2004, 121, 3197). The gamma distribution results in a closed form analytical expression for the velocity autocorrelation function and the relaxation time of the fluid. The two parameters of the gamma distribution are related analytically to the second and fourth frequency moments of the fluid using short time expansions. The predictions by the proposed gamma model are compared with the velocity autocorrelation functions obtained using the theory of instantaneous normal modes (INMs) and from molecular dynamics simulations. The model is applied to a bulk soft sphere liquid and fluids confined in a spherical cavity and slit-shaped pores. The gamma model is able to capture the resulting changes in relaxation time due to changes in density and temperature extremely well for both the bulk liquid and confined inhomogeneous fluid situations. In all cases, the predictions by the gamma model are superior to those obtained from the INM theory. In the case of the fluid confined in a slit pore, the loadings were obtained from a grand canonical Monte Carlo simulation where the pore is equilibrated with a bulk fluid. This is similar to a confinement situation in a surface force apparatus. The predicted relaxation times vs pore widths from the gamma model are seen to accurately capture the oscillations due to formation and disruption of layers within the slit pore.     

Adsorption of water molecules in slit pores

We report molecular dynamics (MD) simulations on the adsorption of water in attractive and repulsive slit pores, where the slit and a bulk region are in contact with each other. Water structure, surface force and adsorption behavior are investigated as a function of the overall density in the bulk region. The gas–liquid transition in both types of pores occurs at similar densities of the bulk region.     

Fluid in a closed narrow slit

The behavior of a fluid inside a closed narrow slit between solid walls is examined on the basis of the density functional theory. It is shown that the constraint of constant number of molecules leads to interesting effects which are absent when the slit is open and in contact with a reservoir. If the slit walls are identical, the density profiles at low temperatures or at high average densities rhoav of the fluid molecules in the slit have a sharp maximum in the middle of the slit, the value of the density at maximum being comparable to that of a liquid. The density of fluid at the walls is in this case comparable to the density of a vapor phase. At high temperatures or at low rhoav the fluid density in the middle of the slit is of the same order of magnitude as at the walls. For nonidentical walls the density maximum is shifted towards the wall with a stronger wall-fluid interaction. The transition between the two types (with and without the sharp maximum) of density profiles with the change of temperature in the slit occurs in a narrow range of temperatures, this range being larger for narrower slits. The pressures which the fluid exerts on the walls as well as the forces per unit area arising due to stresses in the sidewalls of the system can decrease with increasing rhoav. Such a behavior is not possible for homogeneous systems and can be explained by analyzing the fluid density at the walls when rhoav increases. The normal and transversal components of the pressure tensor were calculated as functions of the distance from the wall using the equation of hydrostatic equilibrium and direct calculation of the forces between molecules, respectively. The normal component decreases with increasing distance near the wall in contrast to the normal component near the liquid-vapor interface reported previously in the literature. The behavior of the transverse component does not depend on the fluid-solid interaction and is comparable to that for a liquid-vapor interface.     

Accurate relations between pore size and the pressure of capillary condensation and the evaporation of nitrogen in cylindrical pores

To examine the theoretical and semiempirical relations between pore size and the pressure of capillary condensation or evaporation proposed so far, we constructed an accurate relation between the pore radius and the capillary condensation and evaporation pressure of nitrogen at 77 K for the cylindrical pores of the ordered mesoporous MCM-41 and SBA-15 silicas. Here, the pore size was determined from a comparison between the experimental and calculated X-ray diffraction patterns due to X-ray structural modeling recently developed. Among the many theoretical relations that differ from each other in the degree of theoretical improvements, a macroscopic thermodynamic approach based on Broekhoff-de Boer equations was found to be in fair agreement with the experimental relation obtained in the present study.     

Kinetics and isotherms of asphaltene adsorption in narrow pores

New data relating to the kinetics and adsorption isotherms of asphaltene in consolidated sandstone core samples are reported. The data were obtained from the measurements of electrokinetics of consolidated sandstone core samples in asphaltene/toluene solutions and petroleum oils. The numerical reduction in the (negative) zeta potential of the sandstone samples were attributed to the adsorption of positively charged molecules of asphaltenes. The hydrodynamics thickness δ of adsorption of asphaltene were followed by monitoring the pressure increase that occurred as the adsorbed layer restricted the rock pores and applying Poiseuille's equation. The flow rates indicated a plateau of asphaltene adsorption at a pore blocking thickness of about δ/r = 0.3, which was also the point at which the streaming current reached a plateau. After increasing to about 30% of the pore radius, the adsorbed layer thickness δ stopped growing either with time or with concentration of asphaltene in the flowing liquid. Alternative hypotheses involving asphaltene adsorption isotherms have been investigated. A theoretical treatment advanced describing particle adsorption in the same terms as molecular adsorption and the Langmuir isotherm, with the free energy of asphaltene adsorption on the rock surface (modeled on silica) calculated on the basis of van der Waals attraction. Acceptable agreement was obtained with the electrokinetic measurements.     

Branched versus linear alkane adsorption in carbonaceous slit pores

The presence of carbonaceous deposits on the internal surfaces of a spark ignition engine has been linked in the literature to impaired vehicle performance, as manifested by increased knocking, higher fuel consumption, higher emissions and other adverse effects. One of the proposed mechanisms, in which the deposits affect the processes in the engine, is the adsorption and desorption of fuel components in the pores within the deposit. In this article we investigate this mechanism in more detail by considering single component adsorption of normal and branched alkanes in selected model slit pores representing the structure of the deposits. We further extend these studies to the binary mixture of normal heptane and isooctane, corresponding to a primary reference fuel blend. In particular, we show that in larger pores adsorption selectivity towards isooctane is about 1.2 on average throughout the pressure range. However, in the smaller 10 Å pore selectivity towards isooctane can be in excess of three as a result of packing effects. These results are then placed in the context of engine performance issues.     

Pressure driven flow of polymer solutions in nanoscale slit pores

Polymer solutions subject to pressure driven flow and in nanoscale slit pores are systematically investigated using the dissipative particle dynamics approach. The authors investigated the effect of molecular weight, polymer concentration, and flow rate on the profiles across the channel of the fluid and polymer velocities, polymer density, and the three components of the polymers radius of gyration. They found that the mean streaming fluid velocity decreases as the polymer molecular weight and/or polymer concentration is increased, and that the deviation of the velocity profile from the parabolic profile is accentuated with increase in polymer molecular weight or concentration. They also found that the distribution of polymers conformation is highly anisotropic and nonuniform across the channel. The polymer density profile is also found to be nonuniform, exhibiting a local minimum in the center plane followed by two symmetric peaks. They found a migration of the polymer chains either from or toward the walls. For relatively long chains, as compared to the thickness of the slit, a migration toward the walls is observed. However, for relatively short chains, a migration away from the walls is observed.     

Orientational orders of small anisotropic molecules confined in slit pores

Based on a constant-pressure Monte Carlo molecular simulation, we have studied orientationally ordered transitions of small anisotropic molecules confined in two parallel hard walls. These molecules are modeled by the hard Gaussian overlap model. The molecular elongations of the chosen molecules are so small that the molecules cannot form stable liquid-crystal (LC) phases in the bulk. But in the slit pores, we found, while the distance between two walls of the pores decreases to the molecular scale, an orientationally ordered phase can form. It shows that even hard confining surfaces favor the alignment of the small anisotropic molecules. Thus we conclude that the required molecular elongation for forming LC phases will decrease in confinement. Our results indicate that some non-LC small molecules may form stable LC phases due to the inducement of confining surfaces.     

Molecular dynamics simulation of benzene in graphite and amorphous carbon slit pores

It is well known that confining a liquid into a pore strongly alters the liquid behavior. Investigations of the effect of confinement are of great importance for many scientific and technological applications. Here, we present a study of the behavior of benzene confined in carbon slit pores. Two types of pores are considered–graphite and amorphous carbon ones. We show that the effect of different pore structure is of crucial importance for the benzene behavior. © 2013 Wiley Periodicals, Inc.     

Freezing of hard spheres confined in narrow cylindrical pores

Monte Carlo simulations for the equation of state and phase behavior of hard spheres confined inside very narrow hard tubes are presented. For pores whose radii are greater than 1.1 hard sphere diameters, a sudden change in the density and the microscopic structure of the fluid is neatly observed, indicating the onset of freezing. In the high-density structure the particles rearrange in such a way that groups of three particles fit in sections across the pore.     

Monte Carlo simulation of n-alkane adsorption isotherms in carbon slit pores

The single component adsorption of alkanes in carbon slit pores was studied using configurational-biased grand canonical Monte Carlo simulations. Wide ranges of temperature, pressure, alkane chain length, and slit height were studied to evaluate their effects on adsorption. Adsorption isotherms and density and orientation profiles were calculated. The behavior of long alkanes at high temperatures was found to be similar to short alkanes at lower temperatures. This suggests that the isotherms may be related through the Polanyi potential theory.     

Adsorption of short heteropolymers in slitlike pores

Adsorption of short linear heteropolymers in slitlike pores is studied using the density functional theory and Monte Carlo simulations. The molecules are assumed to be freely jointed tangent hard spheres. The segments have different affinity with regard to the walls. Each molecule contains one surface-binding segment that interacts with the walls via Lennard-Jones (3,9) potential and a number of segments interacting with surfaces via the hard-wall potentials. A position of the surface-binding segment in the chain can be arbitrarily chosen. We have studied the influence of the pore width, the chain length and the chemical structure of molecules on adsorption and the microscopic structure of the confined fluid. The theoretical predictions are compared with Monte Carlo simulations carried out for different 'isomeric' pentamers.