Transport modeling of membrane extraction of chlorinated hydrocarbon from water for ion mobility spectrometry

Membrane-extraction Ion Mobility Spectrometry (ME-IMS) is a feasible technique for the continuous monitoring of chlorinated hydrocarbons in water. This work studies theoretically the time-dependent characteristics of sampling and detection of trichloroethylene (TCE). The sampling is configured so that aqueous contaminants permeate through a hollow polydimethylsiloxane (PDMS) membrane and are carried away by a transport gas flowing through the membrane tube into IMS analyzer. The theoretical study is based on a two-dimensional transient fluid flow and mass transport model. The model describes the TCE mixing in the water, permeation through the membrane layer, and convective diffusion in the air flow inside membrane tube. The effect of various transport gas flow rates on temporal profiles of IMS signal intensity is investigated. The results show that fast time response and high transport yield can be achieved for ME-IMS by controlling the flow rate in the extraction membrane tube. These modeled time-response profiles are important for determining duty cycles of field-deployable sensors for monitoring chlorinated hydrocarbons in water.     

Diffusion and solubility of mineral oils through ethylene-vinyl acetate copolymer

This paper reports a study of mineral oil diffusion through a filled ethylene-vinyl acetate crosslinked polymer, together with some comparisons with aliphatic linear hydrocarbons. Permeation was monitored by classical gravimetric measurements leading to values of solubility and diffusion coefficient at several temperatures ranging from 20 to 120 °C. Diffusion coefficients display a change in activation energy at at ca. 70 °C for mineral oils but not for simple hydrocarbons. The values obtained were discussed regarding available structure-diffusivity relationships and diffusion models derived from free volume theory. A relationship between penetrant evaporation temperature and its diffusivity was observed and tentatively justified.     

Sorption Equilibria and Kinetics of Hydrocarbons onto Activated Carbon Samples Having Different Micropore Size Distributions

This paper deals with the prediction of adsorption equilibrium and kinetics of hydrocarbons onto activated carbon samples having different micropore size distribution (MPSD). The microporous structure of activated carbon is characterised by the distribution of slit-shaped micropores, which is assumed to be the sole source of surface heterogeneity. The interaction between adsorbate molecule and pore walls is described by the Lennard-Jones potential theory. Different adsorbates have access to different pore size range of activated carbon due to the size exclusion, a phenomenon could have a significant influence on both multicomponent equilibria and kinetics. Activated carbons with three different MPSDs are studied with ethane and propane as the two model adsorbates. The Heterogeneous Macropore Surface Diffusion model (HMSD) is employed to simulate adsorption kinetics. The simulation results show that the MPSD is an important factor affecting both the multicomponent equilibria and kinetics.     

Comparison of carrier-facilitated copper(II) ion transport mechanisms in a supported liquid membrane and in a plasticized cellulose triacetate membrane

Transport of copper ions through a plasticized cellulose triacetate membrane containing lauric acid as carrier and tris(2-ethylhexyl)phosphate (TEHP) as plasticizer has been investigated. A comparative study of transport mechanism across such a membrane and a supported liquid membrane (SLM) containing the same carrier in THEP has been made. In both cases, transport mechanisms were controlled by the diffusion of 1:2 metal/carrier complex in the membrane and of copper ions through the aqueous diffusion layer at the source/membrane interface. Diffusion coefficient in the cellulose triacetate membrane, after normalization, was found to be 22 times lower than in the corresponding SLM.     

Cd(II) and Pb(II) extraction and transport modeling in SLM and PIM systems using Kelex 100 as carrier

The extraction and transport of Cd(II) and Pb(II) in two different membrane systems (SLM and PIM) using Kelex 100 as carrier was studied, proposing the corresponding chemical models of transport. A two-species transport model is proposed for Cd(II), according to solvent extraction (SX) data. Experimental SLM permeabilities are 9.7×10⁻⁵ m s⁻¹, while measured PIM permeabilities are 5×10⁻⁵ m s⁻¹. Values for the aqueous boundary layer thickness and for the diffusion coefficient of the metal cation-carrier complexes in the membrane phase were calculated from numerical fitting of experimental data using the proposed transport models. A highly selective Pb(II) separation was achieved in PIM systems based on the nature of the chemical equilibria involved in Cd(II) and Pb(II) membrane transport.     

Adsorption behaviour of sugars versus their activity in single and multicomponent liquid solutions

In this work the activity of three carbohydrates (sucrose, glucose and fructose) in highly concentrated aqueous solutions was studied along with its effect on the adsorption behaviour of the investigated compounds. Activities of individual sugars in aqueous solutions of single solute as well as in binary mixtures were quantified on the basis of solubility properties. Solid–liquid equilibria of sugars were correlated with the NRTL (nonrandom, two liquid) model of activity coefficient formulation. Activities of individual sugars were incorporated into the single component adsorption isotherm model, which reproduced accurately the course of the adsorption equilibria of sugars in aqueous solutions obtained experimentally in previous work using an ion-exchange resin. Activities of sugars determined in binary solute systems along with the single component isotherms were used to predict competitive adsorption equilibria. To calculate adsorbed phase concentrations of individual sugars in binary mixtures the adsorbed solution theory was adopted. The isotherm shapes calculated were compared to the data of competitive adsorption from the former study and found to be able to describe these experimental results.     

Kinetic considerations of ion selectivity coefficients of ion-selective electrodes based on neutral carriers

Ion selectivity coefficients of ion-selective electrodes based on neutral carriers are described by means of a mixed potential model of ion transport reactions at the aqueous solution/ion-sensitive membrane interface. The decrease in ion selectivity can be explained by the deviations from the equilibrium conditions, which arise from the ionic partial current across the interface, but the proposed correspondence of the exchange current density of ion transfer reactions with the ion selectivity coefficients is rationalized only for certain conditions of the kinetic parameters. The ion selectivity for liquid membrane transport is discussed starting from three different rate-determining steps. It is shown that the potentiometric selectivities of ion-selective electrodes and the transport selectivities are correlated when the ionic transfer across the aqueous solution/ membrane interface is fast compared with the complex ion transport through the membrane. The significance of a kinetic approach for the design of neutral carriers for ion-selective electrodes is stressed.     

Modulation of drug transport properties by multicomponent diffusion in surfactant aqueous solutions

Diffusion coefficients of drug compounds are crucial parameters used for modeling transport processes. Interestingly, diffusion of a solute can be generated not only by its own concentration gradient but also by concentration gradients of other solutes. This phenomenon is known as multicomponent diffusion. A multicomponent diffusion study on drug-surfactant-water ternary mixtures is reported here. Specifically, high-precision Rayleigh interferometry was used to determine multicomponent diffusion coefficients for the hydrocortisone-tyloxapol-water system at 25 degrees C. For comparison, diffusion measurements by dynamic light scattering were also performed. In addition, drug solubility was measured as a function of tyloxapol concentration, and drug-surfactant thermodynamic interactions using the two-phase partitioning model were characterized. The diffusion results are in agreement with a proposed coupled multicomponent diffusion model for ternary mixtures relevant to nonionic drug and surfactant molecules. Theoretical examination of diffusion-based drug transport in the presence of concentration gradients of micelles shows that drug fluxes and drug concentration profiles are significantly affected by coupled multicomponent diffusion. This work provides guidance for the development of accurate models of diffusion-based controlled release in multicomponent systems and for the applications of micelle concentration gradients to the modulation of diffusion-based drug transport.     

Spreading of surfactant solutions over thin aqueous layers: influence of solubility and micelles disintegration

A moving circular wave front forms after a small droplet of aqueous surfactant solution is deposited on a thin aqueous layer. The time evolution of the radius of the moving front was monitored. Surfactants of different solubility were used at concentrations above CMC. It is shown that the time evolution of the moving front proceeds in two stages: a rapid first stage, which is followed by a slower second stage. It is shown that the time evolution of the moving front substantially depends on the surfactant solubility. An exact solution for the evolution of the moving front was deduced for the case of insoluble surfactants. A qualitative theory was developed to account for the influence of the solubility on the front motion. Our experimental observations are in a good agreement with the theory predictions.     

Oxygen/nitrogen separation by polycarbonate/Co(SalPr) complex membranes

An oxygen carrier, cobalt di-(salicylal)-3,3′-diimino-di-n-propylamine (Co(SalPr)), was added into a polycarbonate membrane for improving its oxygen/nitrogen selectivity. Both the oxygen permeability and oxygen/nitrogen selectivity increased when only 3 wt% of Co(SalPr) was added. The permeability kept increasing but the selectivity decreased when more than 3 wt% of Co(SalPr) was added. The oxygen to nitrogen solubility ratio decreased when 3 wt% of Co(SalPr) was added. Further increase in Co(SalPr) content led to an increase in oxygen/nitrogen solubility ratio. It was astonishing to know that the effect of Co(SalPr) content on the oxygen/nitrogen solubility ratio was totally opposite to that on the oxygen/nitrogen selectivity. A membrane gas transport model which combines the dual mobility model with pore model was adopted to explain the above phenomenon. The specific volume measurement implied that the pore diffusion was responsible for this behavior. The contribution of sorption-diffusion type transport was also investigated by examining the transport behavior of the 3 wt% Co(SalPr) containing membrane through which the pore diffusion is relatively low. The effect of upstream pressure on the oxygen permeability and solubility implied that the diffusivity of Henry's mode was much higher than that of Langmuir's mode. It was also found that the effects of upstream pressure and operating temperature on the oxygen/nitrogen selectivity were both in accordance with those on the Henry's mode solubility ratio. The above information suggested that in addition to the pore diffusion the ratio of Henry's mode diffusion dominated the O₂/N₂ separation instead of the overall O₂ to N₂ solubility ratio.     

Pervaporation properties of crosslinked poly(dimethylsiloxane) membranes for the removal of hydrocarbons from water

The pervaporation (PV) performance of crosslinked poly(dimethylsiloxane) dimethylmethacrylate (PDMSDMMA) membranes for an aqueous solution of various hydrocarbons was studied using sorption–diffusion theory. Three chlorinated hydrocarbons (chloroform, trichloroethylene, and tetrachloromethane) and three aromatic hydrocarbons (benzene, chlorobenzene, and toluene) were used as the permeants. When aqueous solutions of 0.05 wt % hydrocarbon were permeated through the crosslinked PDMSDMMA membranes, they showed high hydrocarbon/water selectivity and permeability during PV. The hydrocarbon/water selectivity of the crosslinked PDMSDMMA membranes was significantly dependent upon the permeants; in particular, chloroform removed the hydrocarbons most efficiently in this study. The results of the temperature dependence of the PV performance and hydrocarbon absorption into the membrane revealed that the difference in hydrocarbon/water selectivity for various aqueous solutions of hydrocarbons during PV depended significantly on the molar volume and diameter of the hydrocarbons. The permeation and removal mechanism of hydrocarbons from water through crosslinked PDMSDMMA membranes can be explained by a qualitative model based on the diffusion jump model. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2079–2090, 2006     

Water transfer in emulsified liquid membrane processes

Water transfer through the organic phase of a water-in-oil emulsion (liquid membrane) is investigated as a function of emulsion composition, water activity, temperature and agitation in a two-compartment cell. It is shown that the rate of transfer increases with the difference of water activities in the two aqueous phases and depends on the nature and the concentration of the surfactant. A decrease of the organic phase viscosity and an increase in temperature increase the transfer rate. A mathematical model is proposed which is based on the assumption of water—surfactant associations and carrier-mediated water transport. This model qualitatively explains the experimental results.     

Calculations of the solubility of gases in mixed nonaqueous solvents within the framework of the theory of molecular association

A method for calculating the solubility of gases in mixed nonaqueous solvents was suggested. The method was based on the theory of molecular association and the simple lattice model. It allowed the solubility of gases in mixed nonaqueous solvents to be calculated only using molecular association parameters and the mutual exchange energy ω_AB determined from the data on phase equilibria in mixed solvents.     

O2/n2-separation by polymer-bound cobalt complexes

Facilitated or complexation-mediated transport of oxygen in the solid membrane containing a fixed carrier was described, by using the polymer-bound cobalt Schiff's base chelate (CoS) and cobaltporphyrin (CoP). α³ β-Substituted cobaltporphyrin derivatives were synthesized: The oxygen-binding reaction to cobalt was affected by the cavity structure on porphyrin, i.e., unbulky amido-substituted groups such as acetylamido- and acrylamido-substituents enhanced oxygen-binding and -dissociation rate constant or provided an oxygen-binding pathway. Oxygen transport through the membranes of these polymer-bound CoP derivatives was selectively augmented due to the rapid and reversible oxygen-binding. Diffusion constants via the fixed CoPs correlated to the characteristics of oxygen-binding reaction.     

Modelling of mass transfer in facilitated supported liquid membrane transport of copper(II) using MOC-55 TD in Iberfluid

The transport of copper(II) through a supported liquid membrane using MOC-55 TD (oxime derivative), dissolved in Iberfluid, as a carrier has been studied. A physico-chemical model is derived to describe the transport mechanism which consists of: diffusion process through the feed aqueous diffusion layer, fast interfacial chemical reaction and diffusion through the membrane. The experimental data can be explained by mathematical equations describing the rate of transport. The mass transfer coefficient was calculated from the described model as 2.8×10⁻³ cm s⁻¹, the thickness of the aqueous boundary layer as 2.6×10⁻³ cm⁻¹ and the membrane diffusion coefficient of the copper-containing species as 1.2×10⁻⁸ cm² s⁻¹.     

Thioether-mediated copper transport through liquid membranes with the aid of redox reaction

A thioether-mediated copper transport with the aid of redox reaction was studied in a polymer-supported liquid membrane and in a liquid surfactant membrane. A photochemical generation of the redox potential led to a photo-assisted copper separation and concentration system. Tetradentate thioethers 1 and 2 (L) selectively extracted copper ion into organic solution in the presence of a reducing agent, and served as a copper-selective carrier in a liquid membrane system. In the polymer-supported organic liquid membrane system, the thioether was dissolved in the membrane phase which separated the two aqueous solutions of different redox potentials. The copper ion was extracted into the membrane phase by formation of the [Cu^IL]⁺ ? X^? type complex on the reducing solution interface and permeated through the membrane toward the oxidizing solution interface, where the complex was decomposed to release the copper(II) species into the oxidizing aqueous solution. The nature of the system was studied in detail under various operational conditions (redox agents, pairing anion X^?, coexisting metals, etc.) and compared with that of the previously reported Bathocuproine-mediated system. The transport system was extended to the water-in-oil-in-water emulsion system (liquid surfactant membrane), and the selective concentration of copper ion from dilute external aqueous solutions into inner stripping solutions was achieved. Photo-induced redox reactions, triethanolamine—acriflavine—methyl viologen—hv and glucose—titanium oxide—hv, were successfully coupled to the systems, leading to a photo-assisted copper transport in the polymer-supported liquid membrane as well as in the liquid surfactant membrane. Tentative explanations were given on the nature of the membrane transport reactions.     

A study of kinetic molecular exchange processes in the medium frequency range by surface SHG on an oscillating bubble

The dilatational properties of fluid surfaces and interfaces have been comprehensively investigated in recent years. For example, an improved oscillating bubble device provided experimental results that allow for critical testing of established surface models, such as the Lucassen/van den Tempel (LvdT) model. The comparison of the LvdT model with the oscillating bubble experiments demonstrates a mismatch between the model parameters. For example, near the CMC or the limit of solubility the calculated parameters of surfactant solutions become unrealistically large. The deviation can be explained by the introduction of more detailed surface models, in particular by the modification of the effective thickness of the surface layer, its internal structure and the molecular exchange processes between these structures. For the verification of such processes an experimental setup was realized which allows for an independent determination of the instantaneous adsorption state at the surface of an oscillating bubble inside a surfactant solution. The setup utilizes the Second Harmonic Generation (SHG)--effect at the air-solution interface generated by the light of a pulsed LASER. The set-up is described in detail, and the results of a first experimental series are presented and discussed in this paper. As system, aqueous solutions of the fluortenside F381 were used.     

Synthesis and ion transport activity of oligoesters containing an environment-sensitive fluorophore

A series of oligoesters based on a rigid triphenyl-diyne core is described. The molecules were readily synthesized from key intermediates, and retained good solubility properties. One of the compounds displayed modest ion transport activity in vesicles, was capable of forming highly conducting single channels in planar bilayers and exhibited an irregular non-linear current-voltage response. All the reported molecules had minimal aqueous fluorescence while being highly fluorescent in less-polar media including lipid vesicles; their partitioning into the membrane could be monitored by a significant blue-shift and increase in fluorescence intensity, as well as a decreased extent of quenching in vesicles over that in water. The combined data indicated that the compounds are highly aggregated in aqueous solution, which limits their membrane partitioning and ion transport activity, in agreement with mechanisms proposed for other 'simple' oligoester channels.     

Adsorption of sodium octylbenzene-sulfonate at the liquid/air interface

The surface tensions of aqueous solutions containing sodium octylbenzenesulfonate were measured by means of a processor tensiometer at 20°, 25°, 30° and 35°C. A test for the layer model and thickness of the adsorbed phase is proposed. By means of a linear regression the surfactant area at liquid/air interface was calculated. Finally, the molar-and surface-related thermodynamic functions were discussed.     

Membrane drotaverine-selective electrodes based on tetraphenylborate derivatives: Electrochemical, adsorption, and transport properties and analytical application

The potentiometric response of ion-selective electrodes (ISEs) based on different lipophilic derivatives of tetraphenylborate to drotaverine hydrochloride was studied. The composition of a polymeric membrane was optimized to obtain the best electroanalytical properties of ISEs. The transport properties of selective membranes, the permeability and the flow of ions through the interface, were studied. Linear correlations between the solubility of ionophoric membrane components, membrane transport, and electroanalytical properties were revealed. The kinetic studies of ion-exchange adsorption showed that two limiting stages of transfer, namely, diffusion through the boundary layer and diffusion throug the membrane phase, occurred. Procedures for the potentiometric determination of drotaverine hydrochloride in pharmaceutical forms were proposed.