Characteristics of the electroosmotic flow of electrolyte systems for nonaqueous capillary electrophoresis

Nonaqueous capillary electrophoresis (NACE) is a powerful tool for the analysis of surface-active substances, which represent a broad class of analytes containing cationic and anionic species, such as surfactants, phosphoric acid esters, and amines. In order to conduct an efficient method development in NACE, the influence of the electrolyte composition on the electroosmotic flow (EOF) of organic separation systems was systematically investigated. Background electrolytes and background chromophores appropriate for direct and indirect UV-detection were considered, as the majority of surface-active substances do not absorb UV-light. It was found that theoretical models developed to describe the EOF in aqueous electrolyte systems are insufficient for organic electrolyte systems. Experimental data on electroosmosis in a variety of organic solvents and mixtures of methanol and acetonitrile applying different background chromophores and basic or acidic additives are given. Differences between them are discussed with relation to the physicochemical properties of the organic solvents.     

高效液相色谱-质谱联用分析无患子中的表面活性物质

 应用高效液相色谱和大气压电离质谱联用技术 ,分离分析了无患子果皮中的表面活性成分。根据质谱结果确定其相对分子质量 ,根据源内的碰撞诱导解离 (CID)技术产生的碎片初步推测表面活性物质的结构 ,发现了数个未见文献报道的组分。     

典型表面活性物质在汞、镉汞齐和铅汞齐电极上的吸附行为

本文采用DD-1型电镀参数测试仪,测定了汞、镉汞齐和铅汞齐电极在1MKCl的基底溶液中,四下基碘化铵等十二种典型有机表面活性物质在三种电极上的脱附电位。由于镉汞齐和铅汞齐电极的阳极溶解电位比较负,未观测到F^-、Cl^-、Br^-离子的吸附现象。I^-离子及同一有机表面活性物质在三种电极上的吸附活性顺序为:Hg>Pb(Hg)>Cd(Hg)。测试结果表明:同浓度的同一种表面活性物质,在三种电极上的脱附峰电位值之差小于10mV。反映了镉汞齐和铅汞齐电极在脱附峰电位时的表面性质接近于纯汞。     

Pertraction of strontium in bulk liquid membrane systems using crown ether as a carrier

The rate of pertraction of Sr²⁺ by 18-crown-6 (18-C-6) ether and picric acid in bulk liquid membrane systems containing various surface-active substances depends not only on the concentration of 18-C-6 and picric acid but also on the presence of various surface-active substances.     

Influence of mass transfer at the monomer-water interface on polymerization emulsion

A quasi-spontaneous process of mass transfer takes place at the interface of a monomer and water in the presence of surface-active substances soluble in both phases as a result of their diffusion through the interfacial boundary. This process is accompanied by the formation of a microemulsion whose particle size depends on the emulsifier concentration and its molecular structure. While investigating various nonionic surface-active substances as emulsifiers in the emulsion polymerization of vinyl acetate, it was established that polymerization occurs in droplets of the monomer microemulsion in water, which are formed as a result of mass transfer at the interface.     

Characterization of surface-active substances during a semi-field experiment on a phytoplankton bloom

The determination of surface-active substances (SAS) during the evolution of a phytoplankton bloom in a model plankton ecosystem was done by electrochemical methods. The separation and characterization of the organic material present were also done on XAD-8 resin columns. It was found that large amounts of the SAS, predominantly of the humic (fulvic) type, were present from the beginning of the experiment and partly masked the effects of organic substances released by phytoplankton. Although the transformation of the organic matter (consumption and/or excretion) was obvious, no general trend in the amount or type of surface-active matter was observed during the experiment.     

Effects of some non-ionic surface-active substances on potential-time curves of the reduction of hexaisothiocyanatochromate (III) on the mercury electrode

The effects of some non-ionic surface-active substances on the potential-time curves of the reduction of hexaisothiocyanatochromate (III) on the mercury electrode have been investigated, and explained in terms of the blocking effect of adsorbed surface-active substance which is in equilibrium with that in the bulk of the solution by the apparent adsorption isotherm of Langmuir type. The relation obtained experimentally between the concentration of the surface-active substance and the transition time of the reduction of hexaisothiocyanatochromate(III) was consistent with the relation expected theoretically. It was confirrmed that the reduction of hexaisothiocyanatochromate(III) on the mercury electrode proceeds by a bridging mechanism.     

Stabilizing Potential of Solid-Contact Sensors Selective towards Surface-Active Substances

Electrochemical and operation parameters of solid-contact sensors with silver and graphite current leads selective towards surface-active substances (SAS) are studied. Graphite has advantage as an electronic conductor. Parameters of solid-contact SAS electrodes with graphite (response time, potential drift, lifetime) are more stable, and the electrodes have a lower SAS detection limit.     

Rapid determination of surface-active substances by fast-scan differential-pulse voltammetry

Fast-scan differential-pulse voltammograms of air-saturated acetate buffer and mercury nitrate solutions are presented. The current-voltage curves obtained are markedly influenced by surface-active substances (SAS). The peak potential of the voltammogram shifts to more positive potentials with increasing concentration of the SAS. This effect can be utilized for analytical purposes.     

Voltammetry of lead cations on a new type of silver composite electrode in the presence of other cations

A new type of silver composite electrode was examined, prepared from silver, graphite powder, and methacrylate resin. The effects of the presence of various cations (cadmium, copper, bismuth, thallium), anions (chlorides), surface-active substances (Triton X-100), and oxygen on the anodic-stripping voltammetric determination of lead were studied. It was found that the effect of underpotential deposition at the composite electrode differs from that produced at a metallic silver electrode, mainly at low concentrations of the deposited metal. The use of this type of silver composite electrode in differential pulse anodic-stripping voltammetry enables direct determination of lead in natural water samples without elimination of surface-active substances (LOD about 3 g L^–1).     

Methodische Hinweise und Fehlerm?glichkeiten bei der Untersuchung membranfiltrierter w?\riger L?sungen

Zusammenfassung Es wird auf eine bisher nicht beachtete Fehlermöglichkeit bei der analytischen Untersuchung und Weiterverwendung von membranfiltrierten Lösungen hingewiesen. Die üblichen Membranfilter enthalten zur Hydrophilisierung bestimmte Mengen anionaktiver Tenside, die sich nur in wechselndem Ausma\e vor dem Gebrauch eluieren lassen. Bei der Untersuchung von membranfiltrierten Flu\-, Grund- und Trinkwasserproben findet man dadurch zu hohe Tensidkonzentrationen und bei der Austestung und Verwendung sterilfiltrierter Wirkstofflösungen u. a. können betrÄchtliche Störungen eintreten. Von Fall zu Fall ist darum eine sorgfÄltige Versuchskontrolle hinsichtlich einer spezifischen Tensidwirkung nötig.

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Summary Reference is made to a source of error so far unknown in analytical examinations of aqueous membrane-filtered solutions. Membrane filters usually contain a certain amount of anionic surface-active substances for hydrophilizing purposes. These substances are only partly eliminated before the use of the filter. Therefore, in samples of membrane-filtered river, underground and tap water concentrations are found higher than the actual detergent content. There may also be interferences with the testing of bio-active substances, for instance of antibiotics. Advice is given to control carefully the possible specific effect of surface-active substances during these experiments.

     

Effect of anionic surfactant and short-chain alcohol mixtures on adsorption at quartz/water and water/air interfaces and the wettability of quartz

Measurements of the advancing contact angles for aqueous solutions of sodium dodecyl sulfate (SDDS) or sodium hexadecyl sulfonate (SHS) in mixtures with methanol, ethanol, or propanol on a quartz surface were carried out. On the basis of the obtained results and Young and Gibbs equations the critical surface tension of quartz wetting, the composition of the surface layer at the quartz-water interface, and the activity coefficients of the anionic surfactants and alcohols in this layer as well as the work of adhesion of aqueous solutions of anionic surfactant and alcohol mixtures to the quartz surface were determined. The analysis of the contact angle data showed that the wettability of quartz changed visibly only in the range of alcohol and anionic surfactant concentration at which these surface-active agents were present in the solution in the monomeric form. The analysis also showed that there was a linear dependence between the adhesion and the surface tension of aqueous solutions of anionic surfactant and alcohol mixtures. This dependence can be described by linear equations for which the constants depend on the anionic surfactant and alcohol concentrations. The slope of all linear dependence between adhesion and surface tension was positive. The critical surface tension of quartz wetting determined from this dependence by extrapolating the adhesion tension to the value equal to the surface tension (for contact angle equal zero) depends on the assumption whether the concentration of anionic surfactant or alcohol was constant. Its average value is equal to 29.95mN/m and it is considerably lower than the quartz surface tension. The positive slope of the adhesion-surface tension curves was explained by the possibility of the presence of liquid vapor film beyond the solution drop which settled on the quartz surface and the adsorption of surface-active agents at the quartz/monolayer water film-water interface. This conclusion was confirmed by the work of adhesion of aqueous solutions of anionic surfactants and short-chain alcohol mixtures to the quartz surface determined on the basis of the contact angle data and molar fraction of anionic surfactants and alcohols and their activity coefficient in the surface layer.     

Thin liquid films as a model to study surfactant layers on the alveolar surface

Thin liquid films composed of usual surface-active substances have well-developed theory and variety of applications for a long time. Recently the accumulated knowledge on thin liquid films composed of lipid–protein mixture, lung surfactant, or its constituents has been successfully applied to a number of problems in biology and medicine, e.g. as a new and adequate model system for studying the structure, stability, molecular interactions and lateral mobility in the surfactant layer on the alveolar surface.     

HPTLC on inert pre-coated layers of cellulose and of silica 50000

Summary In a manner analogous to that for surface-active silica gel, HPTLC pre-coated plates for nano TLC have also been developed from two inactive sorbents. The two materials are microcrystalline cellulose and a synthetically produced, porous silica (Silica 50000) with a very low specific surface area. The chromatographic properties of these inert sorbents and of the new HPTLC pre-coated plates prepared therefrom are examined in relation to separations of amino acid mixtures and carbohydrate mixtures and are related to the chromatographic properties of the inactive sorbents and TLC precoated plates used hitherto. The figure 50000 characterizes the type of silica. The average pore diameter of this sorbent is about 5000 nm.     

Standardless Analysis of Multicomponent Mixtures of Substances by Time-Resolved Vibronic Spectroscopy

A new approach to the quantitative and qualitative standardless analysis of complex substances based on experimental time-dependent vibronic luminescence spectra (in the UV and visible regions) is proposed. The approach requires no preliminary calculation of absolute intensities for molecular models. It is shown that this analysis can be carried out for both individual substances and multicomponent mixtures, including unknown substances and mixtures of unknown composition. The concentration ranges of mixture components available for the analysis are evaluated, depending on the optical properties of mixtures.     

Alginic acid–silica hydrogel coatings for the protection of osmotic distillation membranes against wet-out by surface-active agents

The formulation of organic–inorganic polymer composites can be used to enhance selected properties, such as susceptibility to microbial attack, thermal stability, mechanical strength and water sorption capability. Accordingly, a series of alginic acid–silica hydrogel films was prepared for testing as protective coating materials for PTFE osmotic distillation membranes. Unprotected hydrophobic membranes are subject to wet-out when contacted by surface-active agents, such as oils and detergents. Films containing 5, 10, 15 and 20 wt.% silica, with and without the addition of glycerol for plasticisation, moisturisation and silica dispersion, were characterised using scanning electron microscopy, X-ray diffraction, differential scanning calorimetry, mechanical strength measurements, and water-swelling measurements. Composites prepared with glycerol addition had better thermal stability, mechanical strength and water sorption capability than those prepared without glycerol addition. Uncoated membranes and membranes coated with composites prepared with glycerol addition were tested for OD performance and resistance to surface-active agents using pure water, orange oil (limonene)–water mixtures, and sodium dodecylbenzene sulfonate detergent solutions. Uncoated membranes showed immediate hydrophobicity loss in the presence of orange oil and detergent. For coated membranes, no wet-out occurred over the 15 h duration of three consecutive 5 h OD trials using orange oil–water mixtures. In the case of detergent solutions, the coating afforded protection to the membrane for 4–5 h. In a separate trial, no wet-out occurred when the coated side of the membrane was placed in contact with 1.2 wt.% orange oil for 72 h.     

Liquid-liquid interfaces as potentiometric ion-sensors-I The n-butanol-water interface as indicating sensor for the potentiometric titration of some acids and bases

The property that liquid-liquid interfaces modify their electrical charge as a function of the composition of the two phases in contact has been used to detect the end-points in a series of acid-base titrations in the aqueous phase. Although the titration curves are not classical in shape, the equivalence points can be located if the solutions are not too dilute. Good results for concentrations down to 10(-3)N have been obtained. The electrode has a fast response. The influence of surface-active substances on the titration has also been investigated.     

Rheological and volumetric properties of aqueous solutions of anionic polymer surface-active substances

The kinematic viscosity and density of diluted aqueous solutions of polymer anionic surface-active substances (ASASes) is studied in the temperature range of 298.15 to 323.15 K. The intrinsic viscosities, Huggins constants, apparent activation energies of viscous flow, and partial molar volumes at infinite dilution are determined for these systems. IR spectra of the investigated ASASes are obtained. The conformations of ASAS macromolecules in solution are corrected, based on an analysis of experimental data.     

The stability of lyophobic and lyophilic sols

The problem of the nature of the stability of colloidal solutions and the mechanism of their coagulation by electrolytes has been examined. On the basis of an analysis of a general criterion for the stability of ionstabilized disperse systems and a comparison of the theoretical results with the experimental facts, it has been concluded that the actual coagulation process in lyophobic sols never takes place by a purely concentration mechanism. Neutralization effects, associated with adsorption phenomena, which take place in a colloidal system when electrolytes are added, are of considerable importance. When treated with nonionogenic surface-active substances, hydrophobic sols are converted into hydrophilic sols, which retain their stability even in moderately concentrated electrolyte solutions. This conversion is brought about as a result of the adsorption of molecules of the surface-active compounds, leading to the production of hydrophilic properties on the surface of the colloidal particles. It has been suggested that the coagulation of these lyophilic sols takes place as a result of the breakdown of the polymolecular solvate layers at the boundary of the colloidal-disperse phase.Paper read at the XX International Congress of Pure and Applied Chemistry, Moscow, July, 1965.