A comparison of electrochemical and electrokinetic parameters determined for cellophane membranes in contact with NaCl and NaNO3 solutions

Electrochemical and electrokinetic characterizations of cellophane membrane samples have been carried out by measuring membrane potential, salt diffusion, and tangential streaming potential, which allow the determination of different characteristic membrane parameters. Experiments were made with the membrane samples in contact with NaCl and NaNO(3) solutions at different concentrations and under different external conditions (concentration gradients), in order to obtain differences in transport and membrane characteristic parameters, depending on the electrolyte considered. Salt permeability across the membrane, which was obtained from diffusion measurements, is about twice as high for NaCl solutions as for NaNO(3) solutions, which is attributed to the different sizes of the electrolytes. Membrane potential measurements keeping the concentration ratio constant (C(1)/C(2)=2) were used to determine both the effective fixed charge concentration in the membrane, X(f), and the average value of transport numbers, t(i); taking into account these values, concentration dependence of membrane potential under a different external condition (C(1)=cte=0.01 M, 5 x 10(-3)< or =C(M)< or =5 x 10(-2)) was predicted. Results show that cellophane membrane behaves as a weak cation-exchange membrane and its permselectivity to cations is practically independent of the electrolyte considered. From electrokinetic results, assuming a Langmuir-type adsorption of anions on the cellophane surface, the number of accessible sites per surface unit was obtained, which is higher for Cl(-) than for NO(3)(-), in agreement with the small radii of chlorine ions; however, no significant differences in the specific adsorption free energy were found (DeltaG(Nacl)=-22.0 x 10(3) J/mol) and (DeltaG(NaNO(3))=-23.2 x 10(3) J/mol).     

Vinyltrimethylsilane (VTMS) as a probe of chemical reactivity of a TiCN diffusion barrier-covered silicon surface

This paper presents the first molecular level investigation of chemical reactivity of a surface of an amorphous diffusion barrier film deposited on a Si(100)-2 x 1 single crystal. Vinyltrimethylsilane (VTMS) is chosen as a probe molecule because of its chemical properties and because of its role as a ligand in a common copper deposition precursor, hexafluoroacetylacetonato-copper-vinyltrimethylsilane, (hfac)Cu(VTMS). The surface chemistry of vinyltrimethylsilane on titanium carbonitride-covered Si(100)-2 x 1 has been investigated using multiple internal reflection Fourier transform infrared spectroscopy (MIR-FTIR), Auger electron spectroscopy (AES), thermal desorption mass spectrometry, and computational analysis. On a film with nominal surface stoichiometry TiC(x)N(y) (x approximately y approximately 1) preannealed to 800 K, VTMS adsorbs molecularly at cryogenic temperatures even at submonolayer coverages; the major pathway for its temperature-programmed evolution is desorption. Adsorption at room temperature leads to chemisorption via a double-bond attachment. A set of computational models was designed to investigate the possible adsorption sites for a VTMS molecule on a TiCN-covered Si(100)-2 x 1 surface. A comparison of the computational predictions for a variety of possible adsorption sites with the results of thermal desorption and infrared measurements suggests that approximately 90% of the adsorbed VTMS is chemisorbed along the Ti-C bond while approximately 10% is chemisorbed on a Ti corner atom, the minority site of the surface. The Ti-N bond is not participating in the chemisorption process.     

Computer Simulation Study on Adsorption and Conformation of Polymer Chains Driven by External Force

In this work, Monte Carlo simulations are used to study the critical adsorption behaviors of flexible polymer chains under the action of an external driving force F parallel to an attractive flat surface. The critical adsorption temperature T_c decreases linearly with increasing F,indicating that the driving force suppresses the adsorption of polymer. The conformation of polymer is also affected by the driving force.However, the effect of F is dependent on the competition between the driving force and temperature. Under strong force or at low temperature,the polymer is stretched along the direction of the force, while under weak force or at high temperature, the polymer is not stretched. When the force is comparable to the temperature, the polymer may be stretched perpendicular to the driving force, and below T_c, we observe conformational transitions from parallel to perpendicular and again to parallel by decreasing the temperature. We found that the perpendicular stretched conformation leads the polymer chain to synchronously move along the direction of the driving force. Moreover, the conformational transitions are attributed to the competition and cooperation between the driving force and the temperature.     

Coupling between transport phenomena and conformational transitions: Isothermal water transport and “asymmetric osmotic pressure” across a “membrane phase” promoted by a helix-coil transition

A membrane system is described consisting of an aqueous concentrated solution of poly-L-lysine bounded by two rigid conventional membranes permeable to water and to small ions but impervious to the polymer. When a large and steady pH difference is maintained between two external isoosmotic solutions α and β, a vertical volume flow may be observed from the acid solution to the basic solution across the membrane. The flow may give rise to a pressure difference between the basic and the acid solution corresponding to a non-equilibrium steady state of the system. These effects, first reported by Liquori et al. [1] are extensively analyzed from a thermodynamic point of view.It is shown that the pH gradient across the membrane maintains a conformational gradient of poly-L-lysine which is known to undergo a pH regulated helix-coil transition. The latter gradient in turn determines a gradient of chemical potential of water within the membrane phase acting as the main driving force of the volume flow.Using the flux equations of irreversible thermodynamics in connection with a model of helix-coil transition proposed by the author [3,4] compact equations are derived for the isobaric volume flow across the membrane phase and the steady state osmotic pressure in agreement with the experimental results.Possible implications of this study in connection with active transport phenomena across biological membranes are discussed.     

Fundamentals of electroporative delivery of drugs and genes

Electrooptical and conductometrical relaxation methods have given a new insight in the molecular mechanisms of the electroporative delivery of drug-like dyes and genes (DNA) to cells and tissues. Key findings are: (1) Membrane electroporation (ME) and hence the electroporative transmembrane transport of macromolecules are facilitated by a higher curvature of the membrane as well as by a gradient of the ionic strength across charged membranes, affecting the spontaneous curvature. (2) The degree of pore formation as the primary field response increases continuously without a threshold field strength, whereas secondary phenomena, such as a dramatic increase in the membrane permeability to drug-like dyes and DNA (also called electropermeabilization), indicate threshold field strength ranges. (3) The transfer of DNA by ME requires surface adsorption and surface insertion of the permeant molecule or part of it. The diffusion coefficient for the translocation of DNA (M(r) approximately 3.5 x 10(6)) through the electroporated membrane is Dm = 6.7 x 10(-13) cm2 s-1 and Dm for the drug-like dye Serva Blue G (M(r) approximately 854) is Dm = 2.0 x 10(-12) cm2 s-1. The slow electroporative transport of both DNA and drugs across the electroporated membrane reflects highly interactive (electro-) diffusion, involving many small pores coalesced into large, but transiently occluded pores (DNA). The data on mouse B-cells and yeast cells provide directly the flow and permeability coefficients of Serva blue G and plasmid DNA at different electroporation protocols. The physico-chemical theory of ME and electroporative transport in terms of time-dependent flow coefficients has been developed to such a degree that analytical expressions are available to handle curvature and ionic strength effects on ME and transport. The theory presents further useful tools for the optimization of the ME techniques in biotechnology and medicine, in particular in the new field of electroporative delivery of drugs (electrochemotherapy) and of DNA transfer and gene therapy.     

Hydrodynamic Surface Flow and the Swelling Effect of C2 and C4 Alkenes through Anhydrous Ag+-Doped Perfluorocarbon Type Ion-Exchange Membranes

The transport mechanism was investigated for n-butane, 1-butene, ethane, and ethene through anhydrous Ag+-doped PSM at various upstream gas pressures. 1-Butene and ethene molecules can be adsorbed and form multilayers on the Ag+ sites in the membrane. Their adsorption behavior can be described by the BET n-layer adsorption theory. These adsorbed alkene molecules can also swell the surrounding polymer chains to a certain extent, causing resistance to the migration of these alkene multilayer molecules to decrease as the concentration of the adsorbed alkenes increases. The permeation behavior of 1-butene and ethene is mainly controlled by the hydrodynamic surface flow mechanism, and their fluxes are much higher than those of alkanes, especially at high upstream gas pressures. This leads to the high ideal selectivity of 1-butene/n-butane and ethene/ethane at relatively high pressure. It is also shown that the more C atoms present in the hydrocarbon molecules, the higher will be the permselectivity of alkenes relative to their corresponding saturated alkanes, which will be expected in the anhydrous Ag+-doped PSM. Copyright 1999 Academic Press.     

Hydrogen adsorption on the indium-rich indium phosphide (001) surface: a novel way to produce bridging In-H-In bonds

The indium phosphide (001) surface provides a unique chemical environment for studying the reactivity of hydrogen toward the electron-deficient group IIIA element, indium. Hydrogen adsorption on the In-rich delta(2 x 4) reconstruction produced a neutral, covalently bound bridging indium hydride. Using vibrational spectroscopy and ab initio cluster calculations, two types of bridging hydrides were identified, a (mu-H)In(2) and a (mu-H)(2)In(3) "butterfly-like" structure. These structures were formed owing to the large thermodynamic driving force for adsorption of H atoms on solid-state indium dimers.     

Insights into the effect of combustion-generated carbon nanoparticles on biological membranes: a computer simulation study

Classical molecular dynamics simulations of atomistic models of combustion-generated carbon nanoparticles and lipid bilayers have been performed to explore their possible structural, dynamical, and thermodynamic effects on biological membranes. The DREIDING generic force field is used for the carbonaceous nanoparticles of different morphologies, as produced from combustion sources, and the united atom model was employed for the dimyristoylphosphatidylcholine (DMPC) bilayer. It is observed that particle shape and structure have significant effects on solvation, mobility, adsorption, and permeation behavior of the particles. While combustion-generated carbon nanoparticles with an aspect ratio close to unity prefer to stay near the membrane center, precursors with other shapes mostly reside within the hydrocarbon tail region of the membrane. Carbon nanoparticles are not trapped in a local region even inside the membranes but move freely with a speed depending on their molecular weight. The adsorption of the particles on the surface of the biological membrane is comparable to thermal fluctuations because the weak segregation effect by water molecules is the main driving force to the adsorption behavior. The bigger the precursors are, the stronger they are bound to the membrane surface. The presence of combustion-generated nanoparticles inside the membrane perturbs local lipid density by pushing the neighboring lipid molecules away from the nanoparticles. This, coupled with thermal fluctuations, can induce an instantaneous membrane pore to allow water protrusion. From the umbrella sampling method, the potential of mean force for the permeation of carbona nanoparticles into the bilayer was also obtained. Surprisingly, elongated particles have a free energy barrier an order of magnitude smaller compared with more round ones. In addition, the round carbon nanoparticles showed strong hysteresis due to the local trapping of water molecules. Although the carbon soot precursors studied in this work are not the well-known carbon nanoparticles such as fullerenes or carbon nanotubes, the qualitative features of this study may be applicable to them as well.     

Stationary electrodiffusion–adsorption processes in membranes including diffuse double layer effects: A network approach

Ion transport across membranes with surface charge due to ion adsorption, including the diffuse double layer effects, is analysed using the network simulation method. The membrane system under study is a multilayer one constituted by a membrane and two diffusion boundary layers on both sides of the membrane. The ion transport processes are described by the Nernst–Planck and Poisson equations not only in the membrane–solution interfaces, but also in the membrane bulk and in the two diffusion boundary layers. The membrane has a negative surface charge due to an anion adsorption process. The structure of the equilibrium diffuse double layers and the steady-state current–voltage characteristic have been analysed for the case of an adsorption process described by a Langmuir-type adsorption isotherm. The evolution of the electric potential difference across the membrane system in the equilibrium state of the system as a function of the bathing concentrations, have been also analysed.     

Zn adsorption on Pd(111): ZnO and PdZn alloy formation

The adsorption and thermal desorption of Zn and ZnO on Pd(111) was studied in the temperature range between 300 and 1300 K with TDS, LEED, and CO adsorption measurements. At temperatures below 400 K, multilayer growth of Zn metal on the Pd(111) surface takes place. At a coverage of 0.75 ML of Zn, a p(2 x 2)-3Zn LEED structure is observed. Increasing the coverage to 3 ML results in a (1 x 1) LEED pattern arising from an ordered Zn multilayer on Pd(111). Thermal desorption of the Zn multilayer state leads to two distinct Zn desorption peaks: a low-temperature desorption peak (400-650 K) arising from upper Zn layers and a second peak (800-1300 K) originating from the residual 1 ML Zn overlayer, which is more strongly bound to the Pd(111) surface and blocks CO adsorption completely. Above 650 K, this Zn adlayer diffuses into the subsurface region and the surface is depleted in Zn, as can be deduced from an increased amount of CO adsorption sites. Deposition of >3 ML of Zn at 750 K leads to the formation of a well-ordered Pd-Zn alloy exhibiting a (6 x 4 square root 3/3)rect. LEED structure. CO adsorption measurements on this surface alloy indicate a high Pd surface concentration and a strong reduction of the CO adsorption energy. Deposition of Zn at T > 373 K in 10(-6) mbar of O2 leads to the formation of an epitaxial (6 x 6) ZnO overlayer on Pd(111). Dissociative desorption of ZnO from this overlayer occurs quantitatively both with respect to Zn and O2 above 750 K, providing a reliable calibration for both ZnO, Zn, and oxygen coverage.     

A non-equilibrium thermodynamics approach to model mass and heat transport for water pervaporation through a zeolite membrane

Pervaporation through zeolite membranes involves local heat effects and combined heat and mass transport. The current state-of-the-art Maxwell–Stefan (M–S) models do not take these effects into account. In this study, transport equations for the coupled heat and mass transport through a zeolite membrane are derived from the framework of non-equilibrium thermodynamics (NET). Moreover, the assumption of equilibrium between the adjacent bulk phases at the feed and permeate sides of the zeolite layer is abandoned in favor of local equilibrium. The equations have been used to model pervaporation of water through a 2 m thick NaA type zeolite membrane, deposited on an asymmetric -alumina support, at a feed temperature of 348 K. Assuming a flux of 10 kg m⁻² h⁻¹(0.15 mol m⁻² s⁻¹), the transport through the zeolite layer, as well as the liquid feed side boundary layer and the support layers is modeled. The activity, fugacity, and temperature profiles are calculated with and without taking coupling effects and surfaces into account. The profiles show distinct differences between the two cases. Including the surface effects leads to discontinuities in the activity and temperature at the membrane interfaces. A significantly higher temperature drop of 1.3 K is calculated across the zeolite, compared to 0.4 K when surface and coupling effects are not accounted for. The calculated decrease in temperature over the zeolite layer is dominated by the surfaces. This could indicate that temperature polarization is, to a large extent, a surface effect. The heat flux induces an extra driving force for mass transport, reducing the activity difference over the membrane. A positive jump in activity is observed at the interfaces, revealing the mass transport across the interfaces is governed by the coupling with the heat flux. The support layers contribute significantly to the total mass transport resistance.     

Anisotropic diffusion of n-butane and n-decane on a stepped metal surface

The diffusion of single n-butane and n-decane molecules on a model stepped surface, Pt655, and on a corresponding flat surface, Pt111, is investigated using molecular-dynamics simulations and anisotropic united atom model. The surface step on Pt655 causes the alkane molecules to adsorb on the lower terrace in all-trans conformations with their long molecular axes adjacent and parallel to the step edge, and to diffuse anisotropically along the surface step via a constant wiggly motion without rotation or marked deviation from the parallel adsorption configuration. At relatively high temperatures, the alkane molecules can temporarily break away from the step edge but cannot migrate across the step edge in either the downstair or upstair direction. In comparison with the diffusion on Pt111, the diffusivity of n-decane is reduced by the surface step but its diffusion barrier is hardly affected. In the case of the shorter n-butane, however, the surface step significantly reduces the diffusion energy barrier and gives rise to higher diffusion coefficients at lower temperatures. Important implications of the simulation results are discussed.     

Equilibrium and kinetics of water adsorption in carbon molecular sieve: theory and experiment

Measurements of water adsorption equilibrium and kinetics in Takeda carbon molecular sieve (CMS) were undertaken in an effort to characterize fundamental mechanisms of adsorption and transport. Adsorption equilibrium revealed a type III isotherm that was characterized by cooperative multimolecular sorption theory. Water adsorption was found to be reversible and did not display hysteresis upon desorption over the conditions studied. Adsorption kinetics measurements revealed that a Fickian diffusion mechanism governed the uptake of water and that the rate of adsorption decreased with increasing relative pressure. Previous investigations have attributed the observed decreasing trend in the rate of adsorption to blocking of micropores. Here, it is proposed that the decrease is attributed to the thermodynamic correction to Fick's law which is formulated on the basis of the chemical potential as the driving force for transport. The thermodynamically corrected formulation accounted for observations of transport of water and other molecules in CMS.     

K-stabilized high-oxygen-coverage states on Rh(110): a low-pressure pathway to formation of surface oxide

Using scanning tunneling microscopy, low-energy electron diffraction, and X-ray photoelectron spectroscopy, we studied the evolution of the structure and chemical state of a Rh(110) surface, modified by K adlayers and exposed to high O2 doses at elevated temperatures. We find that oxygen coadsorption on the K-covered Rh(110) leads to massive reconstruction of the Rh(110) surface. Stable reconstructed (10 x 2) and (8 x 2) segmented phases with a local coverage of more than two oxygen atoms per surface Rh atom were observed. Formation of surface oxide, which coexists with the (10 x 2) and (8 x 2) segmented adsorption phases, is evidenced at the highest O2 doses. The development of strongly reconstructed adsorption phases with oxide-like stoichiometry and surface oxide under UHV conditions is explained in terms of the stabilization of the (1 x 2) reconstruction and promotion of O2 dissociation by the K adatoms.     

Zeolitic imidazolate framework-8 as a reverse osmosis membrane for water desalination: insight from molecular simulation

A molecular simulation study is reported for water desalination in zeolitic imidazolate framework-8 (ZIF-8) membrane. The simulation demonstrates that water desalination occurs under external pressure, and Na(+) and Cl(-) ions cannot transport across the membrane due to the sieving effect of small apertures in ZIF-8. The flux of water permeating the membrane scales linearly with the external pressure, and exhibits an Arrhenius-type relation with temperature (activation energy of 24.4 kJ∕mol). Compared with bulk phase, water molecules in ZIF-8 membrane are less hydrogen-bonded and the lifetime of hydrogen-bonding is considerably longer, as attributed to the surface interactions and geometrical confinement. This simulation study suggests that ZIF-8 might be potentially used as a reverse osmosis membrane for water purification.     

Comparative study between a CMS membrane and a CMS adsorbent: Part II. Water vapor adsorption and surface chemistry

The adsorption/desorption equilibria of water vapor in a carbon molecular sieve (CMS) membrane and a commercial CMS adsorbent were determined, exhibiting S-shaped, type V isotherms. The fits of several models found in the literature to the experimental data were evaluated. The results obtained led to the development of a new model accounting for both adsorption and desorption and essentially based on the work of Lagorsse et al. (2005) [15]. Furthermore, the adsorption kinetics was also assessed for both materials and well described by a linear driving force model. The existence of hydrophilic groups responsible for water vapor adsorption in such carbonaceous materials has been related to the surface chemistry by means of X-ray microanalysis and by thermogravimetry. It was concluded from X-ray microanalyses that the carbon membrane presents a lower C/O ratio and is thus more sensitive towards water vapor exposure, as evidenced by the measured water adsorption at lower relative pressures. It was also observed that the diffusion rates are higher for the CMS membrane than for the CMS adsorbent.     

NMR Study of the Kinetics of Butane and Hexane Adsorption from Vapor Phase by Porous Glasses

The kinetics of butane and hexane sorption from vapor phase by porous glasses is studied by the pulsed NMR technique. The sorption process is revealed to proceed in two stages: monomolecular adsorption and capillary condensation. The rate of adsorption is limited by the rate of adsorbate transfer to the adsorbent surface, with the latter rate being described by the classical diffusion flux. It is shown that ultramicropores are filled simultaneously with the formation of a monolayer. The relative content of molecules in such pores is estimated. At the stage of monomolecular adsorption and at the initial stage of capillary condensation, when the adsorption proceeds from the vapor phase of butane-hexane or butane-deuterated hexane mixtures, butane molecules are predominantly sorbed and followed by their partial displacement by hexane molecules. The rate of the capillary condensation of butane from the mixture is 15–18-fold lower than that from the vapor phase of butane alone which is explained by a decrease in the gradient of chemical potential. It is shown that, when adsorption occurs from a nonequilibrium butane-hexane mixture, anomalous kinetic curves are observed because the driving force of adsorption changes in the course of establishing equilibrium in the liquid phase.     

Charged microbeads are not transported across the human stratum corneum in vitro by short high-voltage pulses

There have been several reports of particle transport due to high-voltage pulsing of human skin. Here, several different short, high-voltage pulsing protocols were used in vitro to study the possible transport of highly charged, fluorescent polystyrene particles (14 nm to 2.1 microns in diameter; surface charges of -4.05 x 10(3) e to -2.77 x 10(7) e) across the skin. Two different methods were used to trap and measure particles on the other side of the skin. The first used a polycarbonate membrane to trap the particles, determining the amount of transport by enumeration under a fluorescence microscope. The second used spectrofluorimetry to measure the amount of particles transported. After pulsing, particles were found in randomly distributed clusters on the surface of the skin. No detectable transport across the stratum corneum for any size particle was observed.     

Characterization of Zinc Ion Transport Via Dialysis Process

Treatment of metal ions' wastes is getting more interest due to the tight regulations for environmental protection. Dialysis, a membrane based process with the concentration difference as the driving force, may be used for separation of metal ions from wastewater. In this study membranes with different pore sizes including Accurel, Celgard, GVHP, PM30 and PTHK membranes were employed to characterise the transport of zinc ion in various (0.01, 0.1, 0.5, 1, 5 and 10 w/v percent) initial feed concentrations. The results show that low initial feed concentration causes less passage of ions through the membrane due to low driving force, i.e. concentration gradient across the membrane. This result is expected. However the effect of membrane pore size is somehow unexpected. It was found that the large pore size membranes provide less penetration of the metal ions through the membrane. This reproducible result has been explained based on the transport mechanism. Two types of mechanisms, i.e. extensive and intensive mechanisms, have been suggested for metal ion transport through different pore size membranes.     

氢气对正丁烷/空气混合物催化着火的热作用和化学作用

通过对正丁烷/氢气/空气混合物在Pt 催化表面的详细反应机理分析, 研究了氢气添加对正丁烷/空气混合物催化着火过程的影响. 研究发现, 在正丁烷/空气混合中添加氢气有助于正丁烷在更低的温度下实现催化着火, 而且不同的氢气添加量对混合物的着火温度和着火过程呈现不同的影响: 当氢气添加量较小时, 氢气的作用主要呈现为热影响; 而当氢气添加量较大时, 氢气的作用主要呈现为化学影响. 这些结果与实验结果是一致的. 本文进一步确定了发挥不同作用的氢气添加量的范围, 并分别对热作用和化学作用情况下的着火启动反应进行了动力学分析.