Numerical investigation into the effects of ordered particle packing and slip flow on the performance of chromatography

The pressure drop and the plate height of chromatography columns packed with particles in the face‐centered cubic, the body‐centered cubic and the simple cubic configurations are calculated by a volume averaging method model. It is found that the Kozeny‐Carman equation provides a reasonable prediction of the pressure drop when particles are in the face‐centered cubic configuration, but overestimates the pressure drop when particles are in the body‐centered cubic and the simple cubic configurations. The face‐centered cubic configuration has the advantage to provide a smaller longitudinal dispersion coefficient than the body‐centered cubic, the simple cubic, and the random configurations. The pressure drop and the plate height for slip flow through particles in the face‐centered cubic configuration are lower than that for no‐slip flow. The values of the smallest reduced plate height of columns packed with particles in the face‐centered cubic configuration for no‐slip flow and slip flow are about 0.084 and 0.059, respectively. The plate height of the ordered particle packing structures is smaller and the effect of slip flow on the plate height is less remarkable than results reported in literature.     

Comparative Study of Flow Characteristics Inside Plasma Torch with Different Nozzle Configurations

A numerical analysis of the influence of different nozzle configurations on the plasma flow characteristics inside D.C plasma torches is presented to provide an advanced nozzle design basis for plasma spraying torches. The assumption of steady-state, axis-symmetric, local thermodynamic equilibrium, and optically thin plasma is adopted in a two-dimensional modeling of plasma flow inside the plasma torch. The PHOENICS software is used for solving the governing equations, i.e. the conservation equations of mass, momentum, and energy along with the equations describing the K-epsilon model of turbulence. The calculated arc voltages are consistent with the experimental results when arc current, gas inflow rate, and working gas are the same as the experimental parameters. Temperature, axial velocity contours inside plasma torches, profiles along the torch axis and profiles at the outlet section are presented to show the plasma flow characteristics. Comparisons are made among those torches. The results show that torches with different anode nozzle configurations produce different characteristics of plasma flows, which suggest some important ideas for the advanced nozzle design for plasma spraying. In order to validate the model and to show its level of predictivity, a comparison of the model with experimental results encountered in the literature is presented in the last part.     

Hydrophobicity within the three-dimensional Mercedes-Benz model: potential of mean force

We use the three-dimensional Mercedes-Benz model for water and Monte Carlo simulations to study the structure and thermodynamics of the hydrophobic interaction. Radial distribution functions are used to classify different cases of the interaction, namely, contact configurations, solvent separated configurations, and desolvation configurations. The temperature dependence of these cases is shown to be in qualitative agreement with atomistic models of water. In particular, while the energy for the formation of contact configurations is favored by entropy, its strengthening with increasing temperature is accounted for by enthalpy. This is consistent with our simulated heat capacity. An important feature of the model is that it can be used to account for well-converged thermodynamics quantities, e.g., the heat capacity of transfer. Microscopic mechanisms for the temperature dependence of the hydrophobic interaction are discussed at the molecular level based on the conceptual simplicity of the model.     

The omega function for the lithium atom

The omega model is reviewed in the case of a three-electron function and the omega function determined for the lithium atom ground state by using a procedure based on Brillouin' theorem. The resulting function is analyzed in terms of natural configurations, and the correlation coefficient determined as a function of the distance to the nucleus. It is found that the omega function is essentially equivalent to two configurations built up with the occupied NO' and that the model introduces mainly correlation at large distance. These results contrast with those obtained for the beryllium atom using the same model.     

Membrane permeation of testosterone from either solutions, particle dispersions, or particle-stabilized emulsions

We derive a unified model that accounts for the variation in extent and rate of membrane permeation by a permeating species with the type of donor compartment formulation (aqueous and oil solutions, particle dispersions, and oil-in-water and water-in-oil emulsions stabilized by particles) initially containing the permeant. The model is also applicable to either closed-loop or open-flow configurations of the receiver compartment of the permeation cell. Predictions of the model are compared with measured extents and rates of permeation of testosterone across an 80 μm thick polydimethylsiloxane (PDMS) membrane from donor compartments initially containing testosterone dissolved in either aqueous or isopropylmyristate (IPM) solutions, aqueous or IPM dispersions of silica nanoparticles or IPM-in-water or water-in-IPM emulsions stabilized by silica nanoparticles. Using a single set of input parameters, the model successfully accounts for the wide variations in permeation behavior observed for the different donor formulation types with either closed-loop or open flow configurations of the permeation cell receiver compartment.     

The determination of the viscosity coefficients of nematic liquid crystals

This paper considers the flow generated by driving a sample of nematic liquid crystal through a rectangular capillary by application of a small pressure gradient in the presence of a large aligning magnetic field. A theoretical calculation based on the continuum theory of nematics is presented which makes some allowance for non-uniform alignment induced by flow, and allows a more accurate determination of the viscosities corresponding to the three principal configurations in the plane of shear.     

Evaluation of partition measurements in liquid-liquid segmented flow

The different configurations possible for an FIA extraction system for partition measurements have been tested and the corresponding evaluation formulae based on determinations at different phase flow ratios, verified. Increased flexibility results from the possibility of using samples dissolved in either aqueous or organic phase. Choosing the best configuration in every case makes it possible to extend the range of measurable conditional partition constants without excessive losses in precision.     

Autocatalysis and bistability in the reaction between nitric acid and thiocyanate

The reaction between nitric acid and thiocyanate has been studied both in batch and flow configurations. The batch reaction is autocatalytic with an induction period which is decreased by the addition of HNO₂. At the nitric acid concentrations employed (1–10 M), a red NOSCNH⁺ intermediate is formed. The reaction in a flow reactor exhibits bistability. A model involving competitive reactions of SCN^? and NOSCNH⁺ with NO₂ is suggested, and computer simulations with this model give good agreement with both the batch and flow experiments.     

Synthesis of Ozone at Atmospheric Pressure by a Quenched Induction-Coupled Plasma Torch

The technical feasibility of using an induction-coupled plasma (ICP) torch to synthesize ozone at atmospheric pressure is explored. Ozone concentrations up to ~250 ppm were achieved using a thermal plasma reactor system based on an ICP torch operating at 2.5 MHz and ~11 kVA with an argon/oxygen mixture as the plasma-forming gas. The corresponding production rate and yield were ~20 g ozone/hr and ~2g ozone/kWh, respectively. A gaseous oxygen quench formed ozone by rapid mixing of molecular oxygen with atomic oxygen produced by the torch. The ozone concentration in the reaction chamber was measured by Fourier Transform infrared (FTIR) spectroscopy over a wide range of experimental conditions and configurations. The geometry of the quench gas flow, the quench flow velocity, and the quench flow rate played important roles in determining the ozone concentration. The ozone concentration was sensitive to the torch RF power, but was insensitive to the torch gas flow rates. These observations are interpreted within the framework of a simple model of ozone synthesis.     

Design of an Interference‐Free Cholesterol Amperometric Biosensor Based on the Electrosynthesis of Polymeric Films of Diaminonaphthalene Isomers

Different cholesterol amperometric biosensors were developed based on entrapment of cholesterol esterase and/or cholesterol oxidase in polymer films of diaminonaphthalene isomers, electrochemically synthesised from aqueous solutions of the monomers and enzymes in phosphate buffer at neutral pH. These conditions permit the growth of films with extraordinary selective properties which allow the preparation of interference‐free biosensors for application in biological media without the response being affected by the presence of either endogenous species (ascorbic and uric acid) or exogenous species like 4‐acetamidophenol. These selective properties were evaluated for the different monolayer and bilayer configurations proposed in function of the film permeation factor. All the steps involved in the preparation of the biosensors and determination of free or total cholesterol were carried out in a flow system. A comparative study was made of the analytical properties of each of the configurations developed and their application to the flow‐injection determination of cholesterol in a synthetic serum.     

Configurational effects on polystyrene rejection from microporous membranes

Dilute solutions of polystyrene in chloroform were filtered through track-etched mica membranes. The pores of each membrane were smaller than the mean unperturbed dimension of the polymer molecules. Three configurations of polystyrene were used: linear, comb-branched, and star-branched. The data for the linear polystyrenes show that the reflection coefficient σ decreases with solvent flow rate per pore q in a manner independent of molecular weight. At low flow rates the rejection is quantitatively described by 1 ? σ ～ q^1.69. Comparisons among the three configurations show that as the extent of branching increases, σ increases at given solvent flow rate. It is concluded that filtration studies with well-defined porous membranes can provide a relative measure of deformability among various configurations of polymeric species.     

Dynamic Properties of Local Structures in Aqueous Model Systems

A method for describing structural and dynamic inhomogeneity in aqueous model systems is proposed. The method is based on the construction of ranked distributions of measured quantities (lifetime of hydrogen bonds and local configurations of water molecules). Asymptotic estimates were obtained for the lifetimes of hydrogen bonds and local configurations of hydrogenbonded water molecules selected by a dynamic criterion for hydrogen bonds.     

Impact of Taylor‐Aris diffusivity on analyte and system zone dispersion in CZE assessed by computer simulation and experimental validation

Application of pressure‐driven laminar flow has an impact on zone and boundary dispersion in open tubular CE. The GENTRANS dynamic simulator for electrophoresis was extended with Taylor‐Aris diffusivity which accounts for dispersion due to the parabolic flow profile associated with pressure‐driven flow. Effective diffusivity of analyte and system zones as functions of the capillary diameter and the amount of flow in comparison to molecular diffusion alone were studied for configurations with concomitant action of imposed hydrodynamic flow and electroosmosis. For selected examples under realistic experimental conditions, simulation data are compared with those monitored experimentally using modular CE setups featuring both capacitively coupled contactless conductivity and UV absorbance detection along a 50 μm id fused‐silica capillary of 90 cm total length. The data presented indicate that inclusion of flow profile based Taylor‐Aris diffusivity provides realistic simulation data for analyte and system peaks, particularly those monitored in CE with conductivity detection.     

Configurational probabilities for symmetric dimers on a lattice: an analytical approximation with exact limits at low and high densities

A new approach is developed for lattice density functional theory of interacting symmetric dimers at high temperatures. Equations of equilibrium for two-dimensional square and three-dimensional cubic lattices are derived for the complete set of configurations in the first three shells around the central dimer, and rules of truncation for higher shells are based on exact results from the mathematical theory of domino tilings. This provides exact limits for both low and high densities. The new model predicts contributions of particular configurations which are in agreement with Monte Carlo simulations over the whole range of densities, including agreement with pocket Monte Carlo simulations at high densities.     

Molecular dynamics simulations of LiCl association and NaCl association in water by means of ABEEM/MM

Constrained molecular dynamics simulations have been used to investigate the LiCl and NaCl ionic association in water in terms of atom-bond electronegativity equalization method fused into molecular mechanics (ABEEM/MM). The simulations make use of the seven-site fluctuating charge and flexible ABEEM-7P water model, based on which an ion-water interaction potential has been constructed. The mean force and the potential of mean force for LiCl and NaCl in water, the charge distributions, as well as the structural and dynamical properties of contact ion pair dissociation have been investigated. The results are reasonable and informative. For LiCl ion pair in water, the solvent-separated ion pair configurations are more stable than contact ion pair configurations. The calculated PMF for NaCl in water indicates that contact ion pair and solvent-separated ion pair configurations are of comparable stability.     

超离子导体CaF2中的Ca2+亚晶格和F-亚晶格

CaF_2在熔化以前为超离子导体相。一些实验和理论的研究表明,在超离子导体相中,Ca~(2+)仍维持原有的面心立方骨架,而F~-则在Ca~(2+)骨架中运动。早期的分子动力学模拟结果表明Ca~(2+)的均方根位移仅约0.3A,而F~-的扩散系数可达2.6×10~(-5)cm·s~(-1),已是熔盐扩散系数量级。近年来的中子散射实验表明在扩散离子和近邻离子间存在着某种动力学相关。为解释这些事实,新近Gillan的分子动力学模拟表明扩散离子伴随着F~-亚晶格变形,而Kaneko和Ueda的分子动力学模拟则表明扩散离子伴随着近邻离子在同一运动方向的相关运动。进一步的研究尚待进行。八十年代初,Nelson等人提出了描述晶体、非晶和液态中键取向的键球谐函数方法。     

Formation of HArF in solid Ar revisited: are mobile vacancies involved in the matrix-site conversion at 30 K?

The HArF molecule can occupy in solid Ar thermally unstable and stable configurations, and their microscopic structure is not understood at the moment. We present additional experimental results on the formation of two HArF configurations and analyze them with emphasis on possible reactions of the unstable configuration with matrix vacancies to form the stable configuration. We conclude that the existing computational scenarios do not describe fully the present experimental data. In order to explain qualitatively the experimental results, two tentative models are discussed. The first model is based on local mobility of matrix vacancies produced during photolysis and the second model considers isomerization of the HArF at Arn supermolecule. More importantly, the present results constitute the experimental basis for future theoretical studies.     

Effects of Monomer Flow Rate,Flow Configuration,and Reactor Geometry on the Rate of Plasma Polymerization

The effects of flow rate on the plasma polymerization of ethylene in an rf discharge were investigated using both a tubular and a bell-jar-type of reactor. Both reactors contained parallel plate internal electrodes. Experiments with the tubular reactor showed that both the total thickness of the deposit and its distribution in the axial direction were strong functions of the flow rate. At low flow rates the polymer thickness decreased in the flow direction, while at high flow rates the polymer thickness increased. Each of these observations is explained by a simple model of plasma polymerization. Using the bell-jar reactor, different monomer flow distribution configurations were tested to determine their effect on the distribution of polymer thickness. It was found that distribution or diffusion of the monomer inflow provided a more uniform film.     

Comparison of biosensors based on entrapment of cholesterol oxidase and cholesterol esterase in electropolymerized films of polypyrrole and diaminonaphthalene derivatives for amperometric determination of cholesterol

Cholesterol amperometric biosensors constructed with enzymes entrapped in electropolymerized layers of polypyrrole and poly-naphthalene derivative polymers are compared. The biosensors are based on entrapment of cholesterol oxidase and/or cholesterol esterase in monolayer or multilayer films electrochemically synthesised from pyrrole, 1,8-diaminonaphthalene (1,8-DAN), and 1,5-diaminonaphthalene (1,5-DAN) monomers. Seven configurations were assayed and compared, and different analytical properties were obtained depending on the kind of polymer and the arrangement of the layers. The selectivity properties were evaluated for the different monolayer and bilayer configurations proposed as a function of the film permeation factor. All the steps involved in the preparation of the biosensors and determination of cholesterol were carried out in a flow system. Sensitivity and selectivity depend greatly on hydrophobicity, permeability, compactness, thickness, and the kind of the polymer used. In some cases a protective outer layer of non-conducting poly(o-phenylenediamine) polymer improves the analytical characteristics of the biosensor. A comparative study was made of the analytical performance of each of the configurations developed. The biosensors were also applied to the flow-injection determination of cholesterol in a synthetic serum.     

Comparison of configurations of a four-column simulated moving bed process by multi-objective optimization

Configurations of a four-column simulated moving bed chromatographic process are investigated by multi-objective optimization. Various existing column configurations are compared through a multi-objective optimization problem. Furthermore, an approach based on an SMB superstructure is applied to find novel configurations which have been found to outperform the standard SMB configuration. An efficient numerical optimization technique is applied to the mathematical model of the SMB process. It has been confirmed that although the optimal configuration highly depends on the purity requirement, the superstructure approach is able to find the most efficient configuration without exploring various existing configurations.