Application of density functional theory to analysis of energetic heterogeneity and pore size distribution of activated carbons

A new approach based on the nonlocal density functional theory to determine pore size distribution (PSD) of activated carbons and energetic heterogeneity of the pore wall is proposed. The energetic heterogeneity is modeled with an energy distribution function (EDF), describing the distribution of solid-fluid potential well depth (this distribution is a Dirac delta function for an energetic homogeneous surface). The approach allows simultaneous determining of the PSD (assuming slit shape) and EDF from nitrogen or argon isotherms at their respective boiling points by using a set of local isotherms calculated for a range of pore widths and solid-fluid potential well depths. It is found that the structure of the pore wall surface significantly differs from that of graphitized carbon black. This could be attributed to defects in the crystalline structure of the surface, active oxide centers, finite size of the pore walls (in either wall thickness or pore length), and so forth. Those factors depend on the precursor and the process of carbonization and activation and hence provide a fingerprint for each adsorbent. The approach allows very accurate correlation of the experimental adsorption isotherm and leads to PSDs that are simpler and more realistic than those obtained with the original nonlocal density functional theory.

Heterogeneous model for gas transport in carbon molecular sieves

A dual resistance model with distribution of either barrier or pore diffusional activation energy is proposed in this work for gas transport in carbon molecular sieve (CMS) micropores. This is a novel approach in which the equilibrium is homogeneous, but the kinetics is heterogeneous. The model seems to provide a possible explanation for the concentration dependence of the thermodynamically corrected barrier and pore diffusion coefficients observed in previous studies from this laboratory on gas diffusion in CMS.(1.2) The energy distribution is assumed to follow the gamma distribution function. It is shown that the energy distribution model can fully capture the behavior described by the empirical model established in earlier studies to account for the concentration dependence of thermodynamically corrected barrier and pore diffusion coefficients. A methodology is proposed for extracting energy distribution parameters, and it is further shown that the extracted energy distribution parameters can effectively predict integral uptake and column breakthrough profiles over a wide range of operating pressures.

Swash-aquifer interaction in the vicinity of the water table exit point on a sandy beach

The coupling of sandy beach aquifers with the swash zone in the vicinity of the water table exit point is investigated through simultaneous measurements of the instantaneous shoreline (swash front) location, pore pressures and the water table exit point. The field observations reveal new insights into swash-aquifer coupling not previously gleaned from measurements of pore pressure only. In particular, for the case where the exit point is seaward of the observation point, the pore pressure response is correlated with the distance between the exit point and the shoreline in that when the distance is large the rate of pressure drop is fast and when the distance is small the rate decreases. The observations expose limitations in a simple model describing exit point dynamics which is based only on the force balance on a particle of water at the sand surface and neglects subsurface pressures. A new modified form of the model is shown to significantly improve the model-data comparison through a parameterization of the effects of capillarity into the aquifer storage coefficient. The model enables sufficiently accurate predictions of the exit point to determine when the swash uprush propagates over a saturated or a partially saturated sand surface, potentially an important factor in the morphological evolution of the beach face. Observations of the shoreward propagation of the swash-induced pore pressure waves ahead of the runup limit shows that the magnitude of the pressure fluctuation decays exponentially and that there is a linear increase in time lags, behavior similar to that of tidally induced water table waves. The location of the exit point and the intermittency of wave runup events is also shown to be significant in terms of the shore-normal energy distribution. Seaward of the mean exit point location, peak energies are small because of the saturated sand surface within the seepage face acting as a "rigid lid'' and limiting pressure fluctuations. Landward of the mean exit point the peak energies grow before decreasing landward of the maximum shoreline position.

Estimation of concentration-dependent diffusion coefficient in drying process from the space-averaged concentration versus time with experimental data

The estimation of a concentration-dependent diffusion coefficient in a drying process is known as an inverse coefficient problem. The solution is sought wherein the space-average concentration is known as function of time (mass loss monitoring). The problem is stated as the minimization of a functional and gradient-based algorithms are used to solve it. Many numerical and experimental examples that demonstrate the effectiveness of the proposed approach are presented. Thin slab drying was carried out in an isothermal drying chamber built in our laboratory. The diffusion coefficients of fructose obtained with the present method are compared with existing literature results.

Ion-trapping, microsomal binding, and unbound drug distribution in the hepatic retention of basic drugs

This study investigated the relative contribution of ion-trapping, microsomal binding, and distribution of unbound drug as determinants in the hepatic retention of basic drugs in the isolated perfused rat liver. The ionophore monensin was used to abolish the vesicular proton gradient and thus allow an estimation of ion-trapping by acidic hepatic vesicles of cationic drugs. In vitro microsomal studies were used to independently estimate microsomal binding and metabolism. Hepatic vesicular ion-trapping, intrinsic elimination clearance, permeability-surface area product, and intracellular binding were derived using a physiologically based pharmacokinetic model. Modeling showed that the ion-trapping was significantly lower after monensin treatment for atenolol and propranolol, but not for antipyrine. However, no changes induced by monensin treatment were observed in intrinsic clearance, permeability, or binding for the three model drugs. Monensin did not affect binding or metabolic activity in vitro for the drugs. The observed ion-trapping was similar to theoretical values estimated using the pHs and fractional volumes of the acidic vesicles and the pK(a) values of drugs. Lipophilicity and pK(a) determined hepatic drug retention: a drug with low pK(a) and low lipophilicity (e.g., antipyrine) distributes as unbound drug, a drug with high pK(a) and low lipophilicity (e.g., atenolol) by ion-trapping, and a drug with a high pK(a) and high lipophilicity (e.g., propranolol) is retained by ion-trapping and intracellular binding. In conclusion, monensin inhibits the ion-trapping of high pK(a) basic drugs, leading to a reduction in hepatic retention but with no effect on hepatic drug extraction.