Van T. Nguyen

Application of the kinetic Monte Carlo method in the microscopic description of argon adsorption on graphite

We present an application of kinetic Monte Carlo (kMC) in the canonical ensemble to a calculation of vapour liquid equilibrium and to describe the adsorption of argon on a flat graphite surface and in a slit-like graphitic pore. Simulations at 77 and 87.3 K accurately describe the experimental data. The kMC method is simple to implement and, unlike conventional Monte Carlo, no rejection trials are necessary. The only move is a uniform sampling of the volume space, which makes the determination of the chemical potential straightforward using real particles in the simulation, in the same spirit as the Widom inverse potential distribution. This avoids the need to freeze the real particles before the trial insertion of test particles as is necessary in other methods, such as the Widom method and its variants.

A Monte Carlo scheme based on mid-density in a hysteresis loop to determine equilibrium phase transition

A new and simple method to determine equilibrium phase transition in adsorption systems exhibiting a hysteresis loop is presented as an alternative to methods such as multiple histogram reweighting, gauge cell method and thermodynamic integration. This method is based on the NVT-grand canonical Monte Carlo mid-density scheme to determine the coexistence chemical potential and coexistence densities of an adsorption system. We illustrate this new scheme with argon and methane adsorption in a number of model solids having slit and cylindrical pores. This method does not have a strong basis on thermodynamic ground, but it does provide a simple heuristic approach that is simpler to understand physically.

Monte Carlo simulation of the gas-phase volumetric adsorption system: effects of dosing volume size, incremental dosing amount, pore shape and size, and temperature

We model the volumetric method commonly used in the measurement of gas-phase adsorption isotherms by using Monte Carlo (MC) simulation to study slit pore adsorption in a finite volume. Although the method has been used for a very long time, modeling of the operation by a Monte Carlo scheme to account properly for the exchange of mass between the solid and the finite dosing volume has not been widely studied in the literature. This paper presents the MC simulation of the system composed of the solid subsystem and the gas phase surrounding it. We show that not only the size of the dosing volume and the incremental dosing amount but also the pore shape, pore size, and temperature have significant effects on the unstable region of the phase diagram, especially when the system is going through a first-order transition. This study extends and augments the recent work of Puibasset et al. (1) by showing that the shape of the adsorbent walls and the incremental dosing amount can affect the chemical potential in the adsorption system.

The interplay between molecular layering and clustering in adsorption of gases on graphitized thermal carbon black--spill-over phenomenon and the important role of strong sites.

We analyse in detail our experimental data, our simulation results and data from the literature, for the adsorption of argon, nitrogen, carbon dioxide, methanol, ammonia and water on graphitized carbon black (GTCB), and show that there are two mechanisms of adsorption at play, and that their interplay governs how different gases adsorb on the surface by either: (1) molecular layering on the basal plane or (2) clustering around very strong sites on the adsorbent whose affinity is much greater than that of the basal plane or the functional groups. Depending on the concentration of the very strong sites or the functional groups, the temperature and the relative strength of the three interactions, (a) fluid-strong sites (fine crevices and functional group) (F-SS), (b) fluid-basal plane (FB) and (c) fluid-fluid (FF), the uptake of adsorbate tends to be dominated by one mechanism. However, there are conditions (temperature and adsorbate) where two mechanisms can both govern the uptake. For simple gases, like argon, nitrogen and carbon dioxide, adsorption proceeds by molecular layering on the basal plane of graphene, but for water which represents an extreme case of a polar molecule, clustering around the strong sites or the functional groups at the edges of the graphene layers is the major mechanism of adsorption and there is little or no adsorption on the basal planes because the F-SS and FF interactions are far stronger than the FB interaction. For adsorptives with lower polarity, exemplified by methanol or ammonia, the adsorption mechanism switches from clustering to layering in the order: ammonia, methanol; and we suggest that the bridging between these two mechanisms is a molecular spill-over phenomenon, which has not been previously proposed in the literature in the context of physical adsorption.

Solid deformation induced by the adsorption of methane and methanol under sub- and supercritical conditions

Carbonaceous materials with some degree of flexibility in their physical structure can expand or contract under the influence of the forces exerted by adsorbed molecules. To gain insight into how adsorption of non-polar and polar fluids could deform a carbon solid, we present GCMC simulations of sub- and supercritical adsorption of methane and methanol in slit-shaped pores whose walls are made of graphene layers. Our extensive simulation study shows that there is a strong correlation between solvation pressure and solid deformation, and that the expansion or contraction of the pore strongly depends on adsorbate loading, temperature and pore size.

Microscopic analysis of adsorption in slit-like pores: layer fluctuations of particle number, layer isosteric heat and histogram of particle number

A number of measures are proposed as a microscopic means to analyse adsorption of gas on a surface and in slit pores under subcritical and supercritical conditions. Layer fluctuation of particle number provides us with information on where most of the mass interchange occurs, which can then be used as an indicator of the position of the interface separating the adsorbed phase and gas phase. The layer compressibility can be used to compare the adsorbed phase density with that of the bulk liquid. The layer isosteric heat provides an indication of the relative contribution of each layer to the overall isosteric heat. Finally, a histogram of particle number as a function of fluid–fluid particle energy is utilised to yield valuable information about the energetic structure of the adsorbed phase, for example (1) the number of neighbouring particles and (2) the evolution of the arrangement of particles.

On the phase transition in a monolayer adsorbed on graphite at temperatures below the 2D-critical temperature

Monte Carlo simulations in the grand ensemble and meso-canonical ensemble in which the adsorbent is connected to a finite reservoir have been used to study adsorption isotherms for monolayer argon adsorption on graphite at temperatures below the 2D-critical temperature in order to elucidate the microscopic details of the 2D-transitions: vapour–solid, vapour–liquid and liquid–solid. An S-shaped van der Waals (vdW) loop was found when a small square surface was used; however, for large square surfaces and rectangular surfaces the isotherms exhibit a vdW-type loop with a vertical segment which indicates the coexistence of two phases separated by a boundary that changes its shape with the loading. This coexistence occurs at the same chemical potential as determined by the mid-density scheme, developed by Do and co-workers (Z. Liu, L. Herrera, V.T. Nguyen, D.D. Do, and D. Nicholson, A Monte Carlo scheme based on mid-density in a hysteresis loop to determine equilibrium phase transition. Mol Simul. 37(11):932–939, 2011; Z. Liu, D.D. Do, and D. Nicholson, A thermodynamic study of the mid-density scheme to determine the equilibrium phase transition in cylindrical pores. Mol Simul. 38(3):189–199, 2011).

Application of kinetic Monte Carlo method to the vapour–liquid equilibria of associating fluids and their mixtures

Abstract Canonical kinetic Monte Carlo (C-kMC) simulations have been carried out to assess their feasibility and potential for calculating the vapour–liquid equilibria of various pure components with increasingly strong electrostatic interactions (carbon dioxide, methanol, ammonia and water) over a wide range of temperatures and for methanol/water mixtures at 298 K. The simulation results show that C-kMC is successful as a method for studying phase equilibria and thermodynamic properties. For all the examples investigated, the performance of the C-kMC method is at least as good as that of the conventional Monte Carlo (MC) methods and is efficient at low temperature where these fail. It also provides a route that is superior to the Widom method for the calculation of chemical potential. We recommend this method for this purpose and as an alternative to conventional MC for simulations of strongly associating fluids and at low temperatures.

A comparative study of the adsorption of water and methanol in zeolite BEA: a molecular simulation study

Grand canonical Monte Carlo simulations were carried out to study the equilibrium adsorption concentration of methanol and water in all-silica BEA zeolite and HBEA zeolites with different Si/Al ratios over a wide range of temperatures and loadings. These zeolites have oval-shaped channels with one side longer than the other. Water sorption into the hydrophobic BEA zeolite had a sharp transition with its sorption going from zero to near full capacity over a very small pressure range. Methanol sorption was much more gradual with respect to pressure. With the addition of hydrophilic sites for the HBEA zeolites by decreasing the Si/Al ratio, adsorption at lower pressures increased significantly for water and methanol. At higher loadings, water and methanol adsorption were found to behave in fundamentally different ways. Water structures in the zeolite channels formed hydrogen-bonded chains while maximising contact with the surfaces on the longer edges of the zeolite channels. Methanol molecules, in contrast, formed very few hydrogen bonds between themselves, with their hydroxyl groups primarily binding with surface of the shorter edge of the zeolite channels and their methyl groups located near the middle of the zeolite channels. The addition of hydrophilic groups in the HBEA zeolites strongly influenced positions of the methanol hydroxyl groups at high loadings, but did not have a significant effect on water structure.

Radiological studies of fetal alcohol spectrum disorders in humans and animal models: An updated comprehensive review.

Fetal Alcohol Spectrum Disorders encompass a wide range of birth defects in children born to mothers who consumed alcohol during pregnancy. Typical mental impairments in FASD include difficulties in life adaptation and learning and memory, deficits in attention, visuospatial skills, language and speech disabilities, mood disorders and motor disabilities. Multimodal imaging methods have enabled in vivo studies of the teratogenic effects of alcohol on the central nervous system, giving more insight into the FASD phenotype. This paper offers an up-to-date comprehensive review of radiological findings in the central nervous system in studies of prenatal alcohol exposure in both humans and translational animal models, including Magnetic Resonance Imaging, Computed Tomography, Positron Emission Tomography, Single Photon Emission Tomography and Ultrasonography.