Adsorption von Polyvinylalkohol an der Grenzfläche Paraffin-Wasser. I. Grenzflächenspannung als Funktion der Zeit und der Konzentration

Ohne Zusammenfassung     

Adsorption of nonionic surfactants on cellulose surfaces: adsorbed amounts and kinetics

Kinetic and equilibrium aspects of three different poly(ethylene oxide) alkylethers (C12E5, C12E7, C14E7) near a flat cellulose surface are studied. The equilibrium adsorption isotherms look very similar for these surfactants, each showing three different regions with increasing surfactant concentration. At low surfactant content both the headgroup and the tail contribute to the adsorption. At higher surface concentrations, lateral attraction becomes prominent and leads to the formation of aggregates on the surface. The general shape of the isotherms and the magnitude of the adsorption resemble mostly those for hydrophilic surfaces, but both the ethylene oxide and the aliphatic segments determine affinity for the surface. The adsorption and desorption kinetics are strongly dependent on surfactant composition. At bulk concentrations below the CMC, the initial adsorption rate is attachment-controlled. Above the CMC, the micellar diffusion coefficient and the micellar dissociation rate play a crucial role. For the most hydrophilic surfactant, C12E7, both parameters are relatively large. In this case, the initial adsorption rate increases with increasing surfactant concentration, also above the CMC. For C12E5 and C14E7 there is no micellar contribution to the initial adsorption rate. The initial desorption kinetics are governed by monomer detachment from the surface aggregates. The desorption rate constants scale with the CMC, indicating an analogy between the surface aggregates and those formed in solution.     

An Improved Method for Calculating Zeta-Potentials from Measurements of the Electrokinetic Sonic Amplitude

The surface electric properties of the commercially available silica, Monospher 1000 (Fa. Merck), have been studied by conductivity and ESA (electrokinetic sonic amplitude) experiments. It could be shown that accounting for the contribution of the stagnant layer to surface conductivity is indispensable in the interpretation of electrokinetic data at low ionic strength. A general method has been put forward which allows to take into account the total, experimentally accessible surface conductivity in the evaluation of ESA data of moderately concentrated suspensions. This includes additional conductivity measurements which serve for the independent estimation of the total relative surface conductivity. The resulting zeta-potentials are clearly higher than those obtained after neglecting the contribution of the stagnant layer to surface conductivity. In addition, the ionic mobilities of potassium and magnesium in the hydrodynamically stagnant layer have been investigated in some detail. It has been found that the ionic mobility of potassium is of the same order of magnitude as in the bulk solution while the mobility of magnesium is significantly reduced. Copyright 2000 Academic Press.     

A theory of exciton dynamics with a percolation threshold

Mode-coupling methods are used to obtain an integral equation for the exciton diffusion constant in isotopically mixed crystals. Numerical solutions are obtained for nearest neighbor hopping in one- and two-dimensional square lattices. These solutions exhibit percolation thresholds.Supported by NSF Grant CHE78-09704.     

Protein partition and ion copartition in aqueous-apolar two-liquid-phase systems

A thermodynamic treatment of protein partitioning in an aqueous-organic two-phase system is presented. The phenomenological analysis interprets the copartitioning of electrolytes. The analysis is supported by experimental results. Solubilization of cytochrome c in trioctylmethylammonium chloride reverse micelles is accompanied by the expulsion and inclusion of electrolytes (HCl) for pH levels below, and respectively above the pH of maximal solubilization. Maximal solubilization occurs when no copartitioning is required. The observations are discussed in terms of the change in Donnan exclusion due to double-layer overlap.     

Self-avoiding walks on randomly diluted lattices

We discuss how the introduction of quenched impurities changes the exponents of a self-avoiding walk on a lattice. We find that , the exponent for the number of walks, does not change. On the other hand the exponent for the mean square end to end distance does change. This is caused by a singular normalization atp=p _c , which is necessary to compensate for the allowed number of walks on the diluted lattice.     

Faradaic depolarization in the electrokinetics of the metal-electrolyte solution interface

Streaming potentials (E(str)) have been measured in a flat thin-layer cell with gold and aluminum surfaces. The conventional relation between E(str) and the zeta-potential is shown to be applicable only as long as charge transfer reactions at the metal-electrolyte solution interface are insignificant in terms of the ensuing contribution to the overall cell conductivity. Owing to the irreversibility of the reduction/oxidation of water at most metal surfaces, streaming potentials can be obtained over a very broad range of pressure gradients for metallic substrates in electrolytes such as KNO3. The situation changes drastically in the presence of a reversible redox couple like Fe(CN)(6)3-/Fe(CN)(6)4-. Even small streaming potentials are then greatly diminished due to the extensive conduction that results from the bipolar electrolysis at the metal surface. For gold and aluminum in the presence of various electroinactive and electroactive electrolytes, the measured values for E(str) are shown to be consistent with their conventional voltammetric characteristics.     

DLVO and steric contributions to bacterial deposition in media of different ionic strengths

The deposition of eight bacterial strains on Teflon and glass in aqueous media with ionic strengths varying between 0.0001 and 1 M was measured and interpreted. Two types of interactions were considered: (1) those described by the DLVO theory, which comprise van der Waals attraction and electrostatic repulsion (bacteria and surfaces are both negatively charged); and (2) steric interactions between the outer cell surface macromolecules and the substrata. As a trend, at low ionic strength (<0.001 M), deposition is inhibited by DLVO-type electrostatic repulsion, but at high ionic strength (≥0.1 M) it is dominated by steric interactions. The ionic strength at which the transition from the DLVO-controlled to the sterically controlled deposition occurs, is determined by the extension of the macromolecules into the surrounding medium, which varied between 5 and 100 nm among the bacterial strains studied. The steric interactions either promote deposition by bridging or inhibit it by steric repulsion. Between Teflon and hydrophobic bacteria, bridging is generally observed. The surface of one bacterial strain contains amphiphilic macromolecules that form bridges with Teflon but induce steric repulsion on glass. The presence of highly polar anionic polysaccharide coatings on the cell impedes attachment on both glass and Teflon. For practice, the general conclusion is that the deposition of most bacteria is: (1) strongly inhibited by DLVO-type electrostatic repulsion in aqueous environments of low ionic strength such as rain water, streams and lakes; (2) controlled by DLVO and/or steric interactions in systems as domestic waste waters and saliva; and (3) determined by steric interactions only in more saline environments as milk, urine, blood and sea water.     

Molecular interpretation of electrokinetic potentials

A discussion is given of the electrokinetic, or ζ-potential in terms of the slip process and the composition of the electric double layer. Electrokinetically, only the outer parts of double layers are active. The existence of a stagnant part is generally observed for aqueous solutions adjacent to solid surfaces. It is claimed that this stagnancy is caused by the spontaneous structuring of fluids near solid surfaces. Hence, it is a ubiquitous phenomenon and the thickness of the stagnant layer does not significantly depend on the wettability and the surface charge of the surfaces.