Thinning of wetting films formed from aqueous solutions of non-ionic surfactant

We investigated the thinning of wetting films formed from aqueous solution of non-ionic triblock copolymer Pluronic F127 on the surface of silica using a home-made thin film balance and time-resolved ellipsometry. Imaging ellipsometry was used to visualize the film structures at subsequent stages of their development. The results unambiguously show that the time required for the formation of steady films strongly depends on the electrolyte concentration. When increasing the latter from 10(-4) to 0.1 M, this time typically increases with several orders of magnitude, from a few minutes to several hours. Moreover, for sufficiently large amounts of salt, two characteristic relaxation regimes can be clearly identified. After initial quick thinning, further thinning slows down enormously. These typical kinetic regimes are thought to result from the coupled dependencies of the bulk and interfacial properties of F127 on salt concentration. Possible explanations of the phenomenon are discussed.     

Salting-out of isopropyl alcohol from aqueous solutions with potassium nitrate

The solubility of components and critical phenomena in a ternary system constituted by potassium nitrate, water, and isopropyl alcohol were studied by the visual-polythermic method in the temperature range 25–90°C. The formation temperature of the critical node of the monotectic equilibrium (critical solution—solid phase) and the solution compositions corresponding to the critical solubility points at different temperatures were determined. Isothermal solubility diagrams of the system were constructed, the previously suggested scheme of the topological transformation of the phase diagrams of ternary stratifying systems constituted by a salt and a binary solvent was confirmed, and the distribution coefficients of isopropyl alcohol at different temperatures were calculated.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 12, 2004, pp. 1945–1949.Original Russian Text Copyright © 2004 by Sinegubova, Ilin, Cherkasov, Kurskii, Tkachenko.     

Cloud point extraction of aloe anthraquinones based on non-ionic surfactant aqueous two-phase system

Non-ionic surfactant-based aqueous two-phase system had been investigated to extract aloe anthraquinones. It had the advantage of using a single auxiliary chemical to induce phase separation above cloud point at a low concentration. Non-ionic surfactant Triton X-114 was chosen for its excellent phase-separating ability and low cloud point. The main factors affecting the cloud point extraction were discussed such as equilibrium temperature and time, concentrations of surfactant and inorganic electrolytes, pH, etc. Under the optimised conditions, the highest extraction yield 96.93% was obtained. The reverse extraction of anthraquinones from surfactant-rich phase was achieved with a recovery of 70.35% by adjusting pH. Compared with conventional purification methods, this CPE technique can be completed in one operation; besides, it is a low-cost method and an environment friendly one.     

Pressurized liquid extraction of active ingredients (ginsenosides) from medicinal plants using non-ionic surfactant solutions

The feasibility of employing aqueous non-ionic surfactant solutions as an alternative solvent system in pressurized liquid extraction (PLE) is demonstrated for the first time using the roots of American ginseng as model solid samples. When compared to the use of pure water or methanol, the presence of a common non-ionic surfactant (Triton X-100) in water at a concentration above its critical micelle concentration was shown to enhance the amount of pharmacologically active ingredients (ginsenosides) extracted from ginseng roots. The advantages of using aqueous non-surfactant solutions were also demonstrated by comparing extraction performances between ultrasonic-assisted extraction and PLE methods. Furthermore, the combination of PLE and cloud point extraction was shown to be a new and effective approach for the rapid sample preconcentration of herbal materials prior to analysis by high-performance liquid chromatography.     

Electrochemical nitration of naphthalene in the presence of nitrite ion in aqueous non-ionic surfactant solutions

The nitration of naphthalene (NapH) at a Pt electrode in aqueous NaNO₂ solutions both in the absence and presence of a non-ionic surfactant, Brij®35 (polyoxyethylene (23) dodecanol), has been studied. The electrochemical behaviour of the reactants NapH and NaNO₂ and a mixture of the two was investigated by cyclic voltammetry (CV) to determine the optimal electrolysis conditions. The peak current of NapH decreases with increasing NaNO₂ concentration, indicating that the oxidation product of the NO₂⁻ ion interacts with the NapH radical cation (NapH⁺). Controlled potential electrolysis (CPE) was carried out and the products were analysed by HPLC. The main products detected in the micellar medium were 1-nitronaphthalene, 2-nitronaphthalene, 1,2-naphthoquinone, and 1,4-naphthoquinone. In the absence of Brij 35, the naphthoquinones were produced but no nitration products were obtained. In both cases, unknown products are inferred by mass balance, which are believed to be derived from the oxidation of 1,1′-binaphthyl (BinapH) formed by NapH⁺ coupling in both micellar and aqueous media. A mechanism of nitration by the attack of NO₂ to NapH⁺ is proposed. The higher selectivity for formation of 2-nitronaphthalene in comparison to non-aqueous homogeneous media is attributed to the effect of the micellar microenvironment.     

Application of non-ionic surfactant in the microwave-assisted extraction of alkaloids from Rhizoma Coptidis

The feasibility of employing non-ionic surfactant oligoethylene glycol monoalkyl ether (Genapol X-080) as an alternative and effective solvent for the microwave-assisted extraction of alkaloids from Rhizoma Coptidis was demonstrated. When compared with commonly used solvents, 5% Genapol X-080 enhanced the extraction efficiency. Under optimal conditions, i.e. 5% acidified Genapol X-080 (v/v), microwave-assisted extraction for 10 min at 100 °C, the extraction recovery of alkaloids reached 92.8% in a one-step extraction. The efficiency of cloud-point preconcentration of three alkaloids was in the range 93.6-94.7% with relative standard deviation lower than 3.3% by the proposed procedure. Furthermore, the combination of microwave-assisted extraction and cloud-point extraction was shown to be a green, rapid and effective approach for alkaloids preconcentration of Rhizoma Coptidis samples.     

Adsorption of non-ionic and cationic polymers on silica from their mixed aqueous solutions

The adsorption of polyvinylpyrrolidone (PVP) and poly(dimethyldiallylammonium chloride) (PDC) on silica from their mixed aqueous solutions has been investigated as a function of PVP concentration in the presence of PDC. The adsorption of PVP is almost unchanged with the feed concentration of PVP, while the adsorption of PDC decreases with increasing PVP concentration, especially at high concentrations of PDC. The conformation of PVP in the adsorbed layer on silica is relatively flat at low concentrations of PDC, but is extended in solution at high concentrations of PDC. The stability of the silica dispersion is low and the ζ potential is relatively small at low concentrations of PDC, whereas a stable dispersion is obtained at high concentrations of PDC and the ζ potential is large. Thus the stability of the dispersion is well correlated with the electrostatic repulsion and steric repulsion forces operating at the particles.     

Thermodynamics of aqueous carbohydrate surfactant solutions

The paper deals with the application of the micelle formation theory, developed by Nagarajan and Ruckenstein [R. Nagarajan, E. Ruckenstein, Langmuir 7 (1991) 2934–2969] and Nagarajan [R. Nagarajan, in: K. Esumi (Ed.), Structure–Performance Relationships in Surfactants, Dekker, New York, 1997, pp. 1–81; R. Nagarajan, Adv. Colloid Interface Sci. 26 (1986) 205-264] to various n-alkyl-β-d-glucopyranoside surfactants, differing in the surfactant tail length (n-octyl-β-d-glucopyranoside C₈G₁, n-decyl-β-d-glucopyranoside C₁₀G₁ and dodecyl-β-d-glucopyranoside C₁₂G₁). The model predicts that the carbohydrate surfactant molecules assemble for energetic reasons in spherical bilayer vesicles. The critical micellar concentration as function of the temperature shows a minimum value. The formed micellar aggregates exhibit a broad distribution of sizes. It is demonstrated in this study that the thermodynamic theory in combination with phase separation thermodynamics can be used successfully to described the phase separation, which occurs for the system C₁₀G₁+water and C₁₂G₁+water at low surfactant concentrations.     

Solvent extraction of some metals from aqueous solutions

The results for the extractions of divalent (manganese, cobalt, zinc and cadmium) and trivalent (gallium and indium) metals and hexavalent uranium from aqueous solutions by various extractants such as organophosphorus compounds (tributyl phosphate, trioctylphosphine oxide, di-(2-ethylhexyl)phosphoric acid and 2-ethylhexyl 2-ethylhexylphosphonic acid), sulfur-containing compound (dihexyl sulfoxide), high-molecular weight amines (trioctylamine and trioctylmethylammonium chloride) and 7-alkylated hydroxyquinoline (7-(5,5,7,7-tetramethyl-1-octen-3-yl)-8-hydroxyquinoline are discussed in the viewpoint of separation chemistry.     

Salting-out effects in aqueous ionic liquid solutions: cloud-point temperature shifts

The effects of the addition of three inorganic salts, namely, NaCl, Na(2)SO(4), and Na(3)PO(4), on the liquid-liquid (L-L) phase diagram of aqueous solutions containing the model ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [bmim][BF(4)], were investigated. All three inorganic salts trigger salting-out effects, leading to significant upward shifts of the L-L demixing temperatures of the systems. The magnitude of the shifts depends on both the water-structuring nature of the salt and its concentration; that is, the effects are correlated with the ionic strength of the solution and the Gibbs free energy of hydration of the inorganic salt. The pH effect and the occurrence of salt precipitation in concentrated solutions are also discussed.     

On the properties of surfactant aqueous solutions

Summary From studies of aqueous solutions of dodecylammoniumnitrate an association mechanism has been proposed involving multiequilibrium. In the concentration range considered we can differentiate between two aspects: ranges of marked qualitative and quantitative changes and formation of differently structured surfactant species.

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Zusammenfassung Aus der Untersuchung wäßriger Lösungen von Dodecylammoniumnitrat würde ein Assoziationsmechanismus abgeleitet, welcher ein Multiequilibrium beinhaltet. Im untersuchten Konzentrationsbereich können zwei Bereiche unterschieden werden: Bereiche mit ausgeprägten qualitativen und quantitativen Änderungen und Bereiche mit der Bildung von verschieden strukturierten oberflächenaktiven Spezies.

     

Wetting behavior of pulmonary surfactant aqueous solutions

The wetting properties of pulmonary surfactant aqueous solutions with respect to solid surfaces with different degree of hydrophobicity have been studied. The contact angles θ of drops from a pulmonary surfactant solution onto SiO₂-glass surfaces have been measured as a function of their degree of hydrophobicity θ _w. The completely hydrophilic SiO₂-glass surface is essentially hydrophobized by the animal-derived pulmonary surfactant Curosurf. The hydrophobization depends on the surfactant concentration—the contact angles increase with increasing the Curosurf concentration C _s in the low concentration range, but they remain almost constant in a wide range of C _s >90 μg/ml. Additions like NaCl and bovine serum albumin influence the θ-values. The contact angles θ naturally increase with increasing θ _w but this dependence is not linear—the curve steepens at larger θ _w values. The thickness h of the wetting thin liquid films from Curosurf aqueous solutions depends on the hydrophobicity θ _w of the solid surface and the h(θ _w) curves always pass a minimum. The h-values, as well as the h(θ _w) curve, are mainly determined by the steric and hydrophobic disjoining pressures, which depend on the orientations and conformations of the molecules adsorbed on the solid surface from the very complicated multi-component aqueous solutions.     

Equilibrium surface tension of aqueous surfactant solutions

Summary The applicability of the drop weight method for determining time dependent surface tension of surfactant solutions was experimentally proved.The presence of CO₂ and traces of lauryl alcohol and long chain homologs lower the surface tension of sodium dodecyl sulfate solutions in a measurable extent. The chemical purification of materials and recrystallizations are insatisfactory to obtain sufficient purity; the cleaning of the surface itself is needed by e.g. foaming. The equilibrium surface tension of pure surfactant solutions that is often required to interpret interfacial phenomena and to calculate theGibbs adsorption excess can be determined with reliable accuracy by linear extrapolation to zero time from measurements made in function of time up from 1 minute on moderately contaminated solutions.As a criterion of surface purity the time dependence of surface tension and the average life-time of thin liquid film are suggested.

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Zusammenfassung Die Tropfengewichtsmethode eignet sich auch zur Bestimmung der zeitabhängigen Oberflächenspannung wäßriger Tensidlösungen. Zur Entfernung von Verunreinigungen, die die Oberflächenspannung von Natriumdodecylsulfatlösungen herabsetzen, wie Spuren von Laurylalkohol und höheren Homologen, reichen weder chemische Methoden noch wiederholtes Umkristallisieren aus, sondern die Oberfläche selbst ist zu reinigen, z. B. durch Ausschäumen. Der Gleichgewichtswert der Oberflächenspannung läß sich mit hinreichender Genauigkeit berechnen, in dem man die an mäßig konzentrierten Lösungen über einer Minute Meßzeit gewonnenen Daten auft = 0 linear extrapoliert. Als praktisches Kriterium für die Reinheit der Oberfläche kann man sowohl die Zeitabhängigkeit der Oberflächenspannung, wie auch die mittlere Lebensdauer von dünnen Lösungsfilmen heranziehen.

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Use of non-ionic surfactant solutions for the extraction and preconcentration of phenolic compounds in water prior to their HPLC-UV detection

A simple and rapid HPLC method with spectrophotometric detection to determine phenolic compounds in water, including the 11 priority phenolic pollutants, is described. As they are present in low concentrations, an extraction and preconcentration step is necessary prior to their determination. A methodology based on the cloud point phenomenon is applied using the non-ionic surfactant oligoethylene glycol monoalkyl ether (Genapol X-080) as extractant. The optimum conditions for the extraction and preconcentration of phenolic derivatives have been established and detection limits lower than 10 micrograms L-1 were obtained for all studied compounds. The method has been applied to their determination in sea water and depurated waste water samples.     

Rheological studies of aqueous alkylpolyglucoside surfactant solutions

Alkylpolyglucosides (C _Y G _X ) are industrial products of mixtures consisting of a hydrocarbon chain with Y carbon atoms linked to X sugar residues. Based on detailed analytical investigation of technical grade alkylpolyglucosides (C_8–10G _X , C_12–14G _X and C_8–16G _X )/water systems using high-performance liquid chromatography in combination with a special kind of mass spectroscopy their rheological behaviour is discussed and compared to the rheological behaviour of pure alkyl monoglycosides (C₈G₁ and C₁₀G₁) in water. The rheological properties that exhibit a dependence on the alkyl chain length, Y, and the degree of polymerisation, X, are investigated by rotation and oscillation experiments over an extended concentration range. The Maxwell model fits the frequency dependence of the dynamic functions fairly well. The viscosity shows an Arrhenius-like dependence on temperature. A comparison is drawn between the monoglucosides and the polyglucosides, which shows that the rheological properties are more sensitive to the a change in chain length than in the degree of polymerisation. Phase transitions, especially liquid-crystalline to isotropic solutions, phase split into two coexisting liquid phases, and could be followed using visual observation and rheology. Depending on the difference in the rheological properties of the corresponding phases, viscoelastic measurements showed these transitions clearly. Additionally, the changes in viscosities were measured after addition of a second surfactant. Received: 4 January 1999 Accepted in revised form: 12 April 1999     

Efficient separation of nitrite from aqueous solutions by grafting metalloporphyrin on Fe3O4 nanoparticles

A new sorbent comprising 3-aminopropyltriethoxy-silane-coated magnetic nanoparticles functionalized with organic moieties containing the cobalt(III) porphyrin complex Co (TCPP) [TCPP: 4,4′,4″,4″′-(21H,23H-porphine-5,10,15,20-tetrayl)tetrakis (benzoic acid)], was prepared, for nitrite removal from drinking water. Fe₃O₄ nanoparticles were synthesized by co-precipitation of Fe²⁺ and Fe³⁺, then surface of the Fe₃O₄ nanoparticles was modified with APTES and Co (TCPP). The sorbent was characterized using FTIR, TGA, XRD, SEM and TEM analysis. The batch experiments showed that the proposed sorbent can effectively be used to remove nitrite from water. Various parameters such as pH of the solution, contact time, sorbent dosage, concentration of desorbing reagent, and influence of other interfering anions have been investigated. Under optimal conditions for a nitrite concentration of 10 mg L^?1 (i.e., contact time 15 min, pH 5.5 and nanosorbents dosage 100 mg), the percentage of the extracted nitrite ions was 92.0. Nitrite sorbing material was regenerated with 10 mM NaOH up to 97.0 %. The regeneration studies also showed that nanosorbents are regenerable and can be used for a couple of times.     

Electrochemical behavior of anthraquinone in aqueous solution in presence of a non-ionic surfactant

Cyclic voltammetric behavior of anthraquinone in aqueous medium has been studied in presence of a non-ionic surfactant, Triton X-100 (TX-100) using sodium salt of anthraquinone-2-sulphonic acid (AQS) as the electro-active species. When cathodic potential is applied, the anthraquinone (AQ) group of AQS is reduced to its dianion. In the reverse scan, the oxidation of AQ²⁻ gives AQ. The electrochemical behavior shows a profound influence from the dissolved state of TX-100 in aqueous media. Spectrophotometric results indicate interaction between AQ and TX-100. A CEC (chemical–electrochemical–chemical) mechanism with the electrochemical reaction coupled with preceding interaction of AQS with TX-100 and following protonation reaction of reduced AQ has been proposed.