Polyoxyethylene Type Research Articles

A Review on the Environmental Behavior of the Polyoxyethylene Type Nonionic Surfactants Adjuvants in Pesticides

A Review on the Environmental Behavior of the Polyoxyethylene Type Nonionic Surfactants Adjuvants in Pesticides

Pressure-Induced Transition of Bilayers in a Nonionic Surfactant Solution.

Pressure effects on the bilayers of polyoxyethylene type nonionic surfactant in water have been investigated by means of small- and wide-angle X-ray scattering. It has been found that the Krafft transition from the micellar phase to the lamellar gel phase (Lβ) is induced by pressure. By further pressurizing, the lamellar structural parameters, such as the repeat distance d and Caillé parameter η, discontinuously decrease after taking a maximum. All the SAXS and WAXS results revealed that the Lβ phase is transformed into the higher-ordered lamellar crystal phase (Lc). On the basis of these observations, we have made the T-C and T-P phase diagrams.

Vesicle formations at critical vesicle concentration in a polyoxyethylene type nonionic surfactant system

In a nonionic polyoxyethylene type surfactant CiEj aqueous solution below the Krafft temperature, multilamellar vesicles which have a hollow including excess water are formed (Kawabata et al., 2009). In this study, we surveyed the critical vesicle concentration, CVC, and the formation of the vesicles by means of fluorescence microscopy and light scattering. We have found that disk-like layers are formed below the CVC, and they are transformed to vesicles via a coexisting region of vesicles and disks with increasing surfactant concentration. Furthermore, by varying temperature, the transformations are induced reversibly. These phenomena could be interpreted by taking into account the elastic energy of unilamellar vesicle formation.

Effect of Polyoxyethylene Type Nonionic Surfactant and Polar Lipophilic Oil on Solubilization of Mixed Surfactant Microemulsion Systems

In the present report, the water solubilization capacity of water-in-oil microemulsion systems comprising mixed surfactants, that is, anionic sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and nonionic(s) [viz., polyoxyethylene (2) stearyl ether (Brij-72), polyoxyethylene (10) stearyl ether (Brij-76), polyoxyethylene (20) stearyl ether (Brij-78), polyoxyethylene (2) oleyl ether (Brij-92), polyoxyethylene (10) oleyl ether (Brij-97), and polyoxyethylene (20) oleyl ether (Brij-98)] was investigated in polar lipophilic oils [viz., ethyl myristate (EM), isopropyl myristate (IPM), and isopropyl palmitate (IPP)] with varying mole fractions of nonionic surfactant (Xnonionic) at a fixed surfactant concentration and 303 K. A maximum (i.e., synergism) in water solubilization (ω0,max) was observed at an optimal value of mole fraction of nonionic surfactant (Xnonionic,max). The solubilization efficiency parameter (SP*water) and the free energy of dissolution (ΔG0s) were evaluated for these mixed systems. All of the physicochemical parameters for solubilization (viz., ω0,max, Xnonionic,max, and SP*water) were found to be dependent on both nonionic surfactants and oils. A minimum in ΔG0s was observed at corresponding Xnonionic,max, where a maximum in SP*water was evidenced. The IPP-based system was found to be most efficient, whereas the EM-based system was least efficient. An attempt was made to correlate the interdependence of physicochemical (ω0,max or SP*water) and thermodynamic (ΔG0s) parameters.

Interfacial composition and characterization of a quaternary water-in-oil mixed surfactant (cationic of different alkyl chain lengths + polyoxyethylene type nonionic) microemulsions in absence and presence of inorganic salts

In this contribution, phase behavior and the Schulman's cosurfactant titration of a quaternary water-in-oil microemulsion, formed from equimolar cationic [alkyltrimethylammonium bromide (CnTAB)] and nonionic [polyoxyethylene (20) cetyl ether (C16E20)] surfactants, n-pentanol (Pn) and n-heptane or isopropyl myristate, have been studied along with the variation in alkyl chain length of the cationic surfactant, Cn (n=12, 14, 16 and 18) at a fixed water content (ω=25) and temperature (303K). The synergies in single-phase microemulsion zone, interfacial composition and the spontaneity of formation of mixed surfactant microemulsions have been observed with increase in Cn (n=12→18). Further, the effect of the variation of Cn (n=12→18) on the interface vis-à-vis interdroplet interaction, morphology and the dynamics of confined water of these systems have been examined by means of viscosity, dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FTIR) measurements. The increase in the Cn (n=12→18) leads to shrink the droplet size as well as increase in the droplet numbers. Subsequently, the change in droplet size affects the states of water organization (bulk and bound) inside the pool. Additionally, the influence of different inorganic salts [normal salt (NaCl), precursor salt for nanoparticle synthesis (NiCl2, FeCl3), water structure affective salt (KF, KI)] on the transfer process of Pn (oil→ interface) at equimolar composition (of both surfactants) has been investigated. FTIR measurement (via D2O probing) indicates that the presence of salts significantly modifies the water structure in confined environment.

Towards detergency in liquid CO2 – A surfactant formulation for particle release in an apolar medium

In this paper we propose, characterize and test a surfactant formulation, consisting of a branched polyoxyethylene type commercial non-ionic surfactant (Igepal CA520), n-hexane and water, for use in CO2 dry-cleaning to enhance the removal of particulate soil. In the formulation lamellar mesophases Lα coexist in an L2 microemulsion (reverse micellar) phase. We hypothesize that enhanced soil removal would be possible due to the adsorption of lamellar liquid crystalline phases at the fabric–soil interface, the presence of water pools, the improvement of the solvent quality of liquid CO2 by the presence of n-hexane, and the enhanced viscosity due to the presence of the lamellar mesophases. We have characterized the formulation by optical microscopy with crossed polarizers, confocal microscopy, dynamic light scattering and shear viscometry to determine the phase behaviour, the size of the reverse micelles and the flow behaviour. AFM force measurements in n-hexane show that large adhesion forces between a model soil particle (silica) and fabric surface (cellulose) in water-saturated hexane can be reduced by the action of the surfactant mesophases. In the presence of the surfactant formulation the interaction forces were found to be decreased from ∼15nN to 0.5nN. The formulation, applied as a pre-treatment on standard soil test monitors and followed by washing in liquid CO2, showed a five times better soil removal ability than the control.

Interfacial composition, thermodynamic properties and structural parameters of water-in-oil microemulsions stabilized by 1-pentanol and mixed anionic + polyoxyethylene type nonionic surfactants

The interfacial composition \( \left( {n_a^i} \right) \), thermodynamic properties and structural parameters of the stable water/(SDS + Brij-58 or Brij-78)/1-pentanol/heptane (or decane or isopropyl myristate) have been evaluated under various physicochemical environments by the dilution method. The results showed \( n_a^i \) values increase with increasing water content (ω = [water]/[surfactant]) for all the systems, whereas reverse trend was observed for (SDS/Brij-58)/heptane-derived system. The spontaneity of the transfer process of 1-pentanol from bulk oil to the interface \( \left[ { - \Delta G_t^0} \right] \) decreases with increase in ω for all the systems. The effective binding between 1-pentanol and surfactant(s) at the interface follows the order: SDS/Brij-78/IPM < SDS/Brij-58/IPM < SDS/Brij-78/Hp(or, Dc) < SDS/Brij-58/Hp(or, Dc), which corroborates well with the degree of spontaneity of the transfer process. The Gibbs free energy change \( \left( {\Delta G_t^0} \right) \), standard enthalpy change \( \left( {\Delta H_t^0} \right) \) and standard entropy change \( \left( {\Delta S_t^0} \right) \) have been found to be dependent on ω, type of nonionic surfactant and its content (Xnonionic), oil and temperature, because of the interdependence of the partition equilibrium of Pn between bulk oil and the interface, and strong adsorption of both surfactants at the interface. Synergism in \( \Delta G_t^0 \) and \( \left[ {{{\left( { - \Delta C_P^0} \right)}_t}} \right] \) (standard specific heat change) is evidenced at equimolar composition of SDS and Brij-58 in both oils at all temperatures and advocates more favorable applications for the synthesis of nanoparticles and the modulation of enzyme activity. The radius of water pool (Rw) was very sensitive to the increment of water content and tuned up by the addition of Brijs, which followed the order with decreasing size: IPM < Dc < Hp.

Micellization of sodium dodecyl sulfate and polyoxyethylene dodecyl ethers in solution

The effect of polyoxyethylene type nonionic surfactants (C12E n n = 3, 4, 5, 6, 7 and 8) on the aqueous solution of sodium dodecyl sulfate (SDS) in absence and presence of NaCl was examined using small-angle neutron scattering (SANS), dynamic light scattering (DLS), and viscosity measurements. Upon addition of C12E n , micellar size of SDS was found to increase significantly, and such micellar elongation was further enhanced in the presence of NaCl. Micellar growth is most significant in presence of shorter moieties of C12E n (e.g., n = 3, 4) as compared to higher ethereal oxygen content. The results of structural investigations with SANS and DLS to confirm this assumption are reported. The cloud point of C12E n has increased upon addition of SDS and decrease with NaCl, and a typical behavior is observed when both SDS and NaCl were present.

Microemulsions Formation on Water/Nonionic Surfactant/Peppermint Oil Mixtures

The water/nonionic surfactant/peppermint oil systems were studied in order to determine the one-phase microemulsion regions. The surfactants were of two types: hydroxylated (sugar esters) and ethoxylated (ethoxylated mono-di-glyceride and polyoxyethylene sorbitan monooleate). These surfactants were able to form microemulsions without the use of cosurfactants or cosolvents. The ternary phase behavior at 25, 37, and 45°C was explored to determine the effect of temperature on the amount of solubilized water in the microemulsions. For each system investigated, the total area of the one phase microemulsion region, AT, was estimated. Temperature insensitive microemulsions were observed in the sugar ester based systems. It was found that minor changes in the surfactant structure suffice to provoke a considerable change in the total monophasic area of the system. Hydrophilic sugar esters were able to solubilize higher quantities of water in peppermint oil compared to the polyoxyethylene type surfactants. These alcohol free microemulsions are promising for food, cosmetics and pharmaceutical applications.

Modelling of phase equilibria of glycol ethers mixtures using an association model

Vapor–liquid and liquid–liquid equilibria of glycol ethers (surfactant) mixtures with hydrocarbons, polar compounds and water are calculated using an association model, the Cubic-Plus-Association Equation of State. Parameters are estimated for several non-ionic surfactants of the polyoxyethylene type but mixture calculations are mostly presented for three compounds for which many data are available (2-methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol). The way pure compound vapor pressures and liquid densities are estimated, and the way parameter trends against the van der Waals volume, Kamlet–Taft parameters and, perhaps most importantly, mixture liquid–liquid equilibria data with alkanes are used for choosing optimum parameter sets is illustrated. Vapor–liquid, liquid–liquid equilibria and second virial coefficient data are used for model validation, including aqueous and other cross-associating mixtures. The influence on the results of the association schemes, type of data available, combining rules for cross-associating mixtures and interaction parameters are discussed also in connection to other cross-associating mixtures, previously studied with the model. Finally, the capabilities and limitations of the Cubic-Plus-Association Equation of State in representing this type of multi-functional chemicals, glycol ethers, are discussed.

The application of artificial neural networks in the prediction of microemulsion phase boundaries in PEG-8 caprylic/capric glycerides based systems

The objective of this study was to develop artificial neural network (ANN) model suitable to predict successfully the borders of the microemulsion region in the quaternary system PEG-8 caprylic/capric glycerides (Labrasol ®)/cosurfactant/isopropyl myristate/water, in order to minimise experimental effort. In our preliminary investigations of phase behaviour, two cosurfactants were used, PEG-40 hydrogenated castor oil (Cremophor ® RH 40) and polyglyceryl-6 isostearate (Plurol Isostearique ®). Microemulsion existance area in pseudo-ternary phase diagrams was determined using titration method at constant: (a) oil-to-water ratio ( α = 50%, w/w); (b) surfactant-to-cosurfactant ratio (Km) 4:6; (c) Km 5:5; or (d) Km 6:4. It was found that the phase behaviour of systems involving polyoxyethylene type of cosurfactant depends significantly on oil-to-surfactant/cosurfactant mixture mass ratio (O/SCoS) but it is Km-independent. The formation of microemulsions in Labrasol ®/polyglyceryl-6 isostearate based systems was a complex function of Km and O/SCoS and there was employed a Generalized Regression Neural Network (GRNN) with four layers as a predictive mathematical model, using data obtained from the phase behaviour study (the surfactant concentration in surfactant/cosurfactant mixture ( S, %, w/w), the oil concentration in the mixture with tensides ( O, %, w/w) as two input variables, and the water solubilization limit ( W max, %, w/w) as output data). After network training, six independent pairs of input/output data were used for network testing. The resulting GRNN was tested statistically and found to be of quality predictive power. This results confirmed that the trained GRNN could be effective in predicting the size of the microemulsion area providing valuable tool in formulation of this type of colloidal vehicles.

The influence of cosurfactants and oils on the formation of pharmaceutical microemulsions based on PEG-8 caprylic/capric glycerides

In the present study the effect of type and concentration of a cosurfactant and oil on the ability of nonionic surfactant PEG-8 caprylic/capric glycerides (Labrasol ®) to solubilize both oil and water phases was evaluated. Seven different cosurfactants (polyglyceryl-6 dioleate (Plurol Oleique ®) (PO), polyglyceryl-6 isostearate (Plurol Isostearique ®) (PI), polyglyceryl-4 isostearate (Isolan ® GI 34) (IGI34), octoxynol-12 (and) polysorbate 20 (Solubilisant gamma ® 2421) (SG2421), octoxynol-12 (and) polysorbate 20 (and) PEG-40 hydrogenated castor oil (Solubilisant gamma ® 2429) (SG2429), PEG-40 hydrogenated castor oil (Cremophor ® RH 40) (CRH40) and diethyleneglycol monoethyl ether (Transcutol ®)) and six oils (isopropyl myristate, ethyl oleate, decyl oleate, medium chain triglycerides, mineral oil and olive oil) were used in phase behaviour studies of a quaternary system Labrasol ®/cosurfactant/oil/water. The amount of surfactant required to completely homogenize equal masses of oil and water to form a single phase microemulsion (termed as balanced microemulsion) (Smin, %w/w), the minimal concentration of the surfactant/cosurfactant blend required to produce a balanced microemulsion (SCoSmin, %w/w) as well as the maximum concentration of water solubilized in investigated surfactant/oil and surfactant/cosurfactant/oil mixtures ( W max, %w/w) were determined. The obtained results indicated that Labrasol ® showed a good efficiency in the presence of lower molecular volume fatty acid esters with a preferred chemical structure such as isopropyl myristate (Smin 56.14% (w/w); W max 12.28% (w/w)). Oils with high molecular volume (olive oil and mineral oil) do not result in microemulsion formation. Transcutol ® decreased the capacity of Labrasol ® for solubilization of oil and water phases. The tendency of Labrasol ® to solubilize both, water and oil phases, was favoured by polyglycerol-6 ester type of cosurfactants (PO and PI) while the influence of the polyglycerol-4 ester (IGI34) as well as of polyoxyethylene type of cosurfactants (CRH40, SG2421 and SG2429) on the surfactant efficiency, was not significant. Furthermore, the results revealed the significant influence of the surfactant/cosurfactant mass ratio ( K m) on synergistic effect between polyglyceryl-6 esters and Labrasol ® in the formation of microemulsions using isopropyl myristate as oil phase. Optimized microemulsion systems were stabilized with Labrasol ®/polyglyceryl-6 esters blend at K m 5:5 (SCoSmin, 27.5% (w/w) and W max, 71.43% (w/w) for PI; SCoSmin, 29.18% (w/w) and W max, 65.00% (w/w) for PO) and the electrical conductivity measurement results for optimized balanced microemulsions showed that their structures were highly conductive indicating a bicontinuous microstructure.

Effect of Nonionic Head Group Size on the Formation of Worm-Like Micelles in Mixed Nonionic/Cationic Surfactant Aqueous Systems

The phase behavior, microstructure and rheological properties of mixtures of polyoxyethylene type nonionic surfactants (C12EOn, n = 0–4) and alkyltrimethylammonium bromide cationic surfactants in water were investigated. Upon addition of C12EO3 to the aqueous cationic system at high surfactant concentration, both the interfacial curvature of aggregates and the effective cross-sectional area per surfactant molecule, aS, decrease, resulting in a hexagonal-lamellar liquid crystal phase transition. This effect becomes more pronounced as the alkyl chain-length of the cationic surfactant increases. At low surfactant concentration, addition of nonionic amphiphile to micellar solution above a particular concentration, C*, induces a rapid unidimensional micellar growth, and particularly in CTAB systems viscoelastic micellar solutions of entangled wormlike micelles are formed. With successive addition of the nonionic amphiphile ultimately a micellar to lamellar phase transformation occurs. Rheological measurements within the Wm-phase show that with decreasing EO chain-length, C* also decreases and viscosity increases more swiftly with increasing concentration of nonionic amphiphile, suggesting a rapid micellar growth. This is attributed to the decrease in aS, as predicted by a simple geometrical model.

The preparation of sterically stabilized polymer dispersions

The emulsion polymerizations of styrene (St) and butyl acrylate (BA) stabilized by nonionic polyoxyethylene type emulsifiers did not show the long stationary rate interval. This was discussed in terms of two opposing effects: 1) the decreased monomer concentration at the reaction loci due to the depletion of monomer droplets or depressed monomer droplet degradation and 2) the increased number of polymer particles with increasing conversion. The continuous particle nucleation is attributed to the continuous release of emulsifier from the emulsifier saturated monomer droplets and/or the presence of monomer swollen micelles (microdroplets). The limited particle flocculation operative at lower emulsifier concentrations increases the nonstationary-state polymerization. The particle agglomeration is accompanied by the increased reaction order x (Np vs. [E]x) above 0.6. The increased uniformity of monomer emulsion stabilized by Tween 20 by homogenization of monomer emulsion increased the final conversion and the polymerization rate as well. The polymerization rate vs. conversion curve of the homogenized emulsion characterized with broader stationary rate interval reminds the four rate intervals system typical for miniemulsion. The accumulation of polymer and nonionic emulsifier within the monomer phase preserves the monomer droplets up to high conversion. The decreased monomer droplet degradation rises the monomer-starved condition or the depressed transport of both monomer and emulsifier to the reaction loci.

Comparing Decyl-β-maltoside and Octaethyleneglycol Mono n-Decyl Ether in Mixed Micelles with Dodecyl Benzenesulfonate: 1. Formation of Mixed Micelles

In this study the mixed micelle behavior of an alkyl polyglycoside is compared to a surfactant of polyoxyethylene type, by means of surface tension measurements. The two nonionic surfactants are compared in mixed micelle systems together with an anionic surfactant. The surfactant mixtures are: decyl-β-maltoside (C10M) with dodecyl benzenesulfonate (C12BS) and octaethyleneglycol mono n-decyl ether (C10EO8) with C12BS. The mixture of C10M and C10EO8 is also studied. Critical micelle concentration (CMC) and the concentration at which the surface tension reduction is 20 mNm−1 (C20) are determined at different mixing ratios of the surfactant mixtures. By applying the nonideal mixed micelle theory, interaction parameters at CMC (βCMC) and C20 (βC20) are calculated for the surfactant mixtures. The results show that the C10M–C12BS mixture has a βCMC parameter of −2.1, whereas the βCMC parameter for the C10EO8–C12BS mixture is −3.3, indicating a weaker net attractive interaction between C10M and C12BS than between C10EO8 and C12BS. This is attributed to a small negative and positive charge of the respective nonionic surfactants. This is supported by a slightly negative βCMC parameter obtained for the surfactant mixture C10M–C10EO8, indicating a small net attractive interaction between the two nonionic surfactants.

Phase Behavior of Aqueous Mixtures of Some Polyethylene Glycol Decyl Ethers Revealed by DSC and FT-IR Measurements

Differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR) were used to investigate the phase behavior of aqueous binary mixtures of three polyoxyethylene type nonionic surfactants, penta-, hexa-, and octaethylene glycol decyl ethers (C10E5, C10E6, and C10E8, respectively) in the temperature range −40–70°C. Many thermotropic transitions among various phases assumed by these mixture systems, including mesomorphic phases, were detected in DSC thermograms, from which theT–Xphase diagrams were constructed with the aid of polarized optical microscopic observation to characterize the mesomorphic phases. It was revealed by FT-IR measurements that the phase compounds are formed in a solid phase between these surfactants and water molecules; the compositions of the compounds for the three surfactant species are expressed as C10E5· 10H2O, C10E6· 12H2O, and C10E8· 16H2O, respectively. The stoichiometry of the phase compounds clearly demonstrates that just two water molecules are bound per oxyethylene unit of polyoxyethylene (POE) chain of the surfactants in the solid phase, probably due to the hydrogen bonding. It was also found that the phase state of the mixture is reflected in the wavenumber of the absorption maximum associated with the OH stretching vibration, νOH, although no significant difference was appreciable in νOHamong mesomorphic phases. The νOHdecreased in the orderL(liquid phase) >H1(normal hexagonal phase) ≈V1(normal cubic phase) ≈Lα(lamellar phase) > solid phase, which indicates that the hydrogen bonding between water and the POE chain of the surfactants becomes stronger in the sequence liquid < mesophase < solid.

Effect of polyoxyethylene emulsifier composition on the course of emulsion polymerization of vinyl acetate

Three different emulsifier types from vinyl acetate monomer and methoxypolyoxyethylene (35: 65, 27: 73 and 19: 81wt: wt%) were prepared in the presence of benzoyl peroxide using a macroradical initiator technique. Fourier transform infrared spectroscopy and 1 H nuclear magnetic resonance were carried out to confirm the structure of the copolymers obtained (emulsifiers). The emulsion polymerization of vinyl acetate initiated by sodium persulphate as an initiator in the presence of non-ionic (polyoxyethylene (POE) type) emulsifier has been kinetically investigated. The rate of polymerization was found to be proportional to the 0.33, 0.40 and 0.44 power of the emulsifier concentration and to the 0.71, 0.79 and 0.87 power of the initiator concentration. The apparent activation energy was found to be 135, 56.5 and 38kJ mol -1 for 65 wt%, 73 wt% and 81 wt% POE, respectively. The particle size was observed to increase with increasing initiator concentration and to decrease with increasing emulsifier concentration. The reaction order with respect to the emulsifier concentration (number of particles versus emulsifier concentration) was found to be 0.10, 2.05 and 0.89 for 65 wt%, 73 wt% and 81 wt% POE, respectively.

Composition analysis of detergents of the polyoxyethylene type: comparison of thin-layer chromatography, reversed-phase chromatography and matrix-assisted laser desorption/ionization mass spectrometry

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) can be used to determine the distribution of single polymer species of non-ionic detergents of the polyoxyethylene type (Triton X-100 and 114, Tween 20 and Brij 35). Thin-layer chromatographic (TLC) and reversed-phase chromatographic (RPC) methods are presented which may separate single polymer species as verified by MALDI-MS. Comparison of chromatographic and MALDI-MS data show Poisson-like distributions for Triton X-100 without marked differences between different methods. Distribution parameters obtained with Triton X-100 charges from different suppliers are very similar. The RPC method used can be scaled up for preparation of pure detergent species.

Separation of nonionic surfactants of the polyoxyethylene type by capillary electrophoresis

Nonionic surfactants are widely used in commercial formulations as complex mixtures requiring efficient and selective separation methods. Capillary electrophoretic separations were carried out in electrolytes containing high amounts of organic solvents and anionic surfactants based on the formation of association complexes between analytes and anionic surfactants without micelle formation. Octyl- and nonylphenol polyethoxylates were separated as their ethoxylate homologues. Influences of the electrophoretic conditions like electrolyte concentration and pH, type and content of anionic surfactant and organic solvents were investigated.

Separation of ionic and neutral surfactants by capillary electrophoresis and high-performance liquid chromatography

Some of the most important anionic, cationic and non-ionic surfactants can be separated by CE; HPLC was used as a reference. A comparison of both methods with respect to separation efficiency, reproducibility and detection limits is presented. Linear alkylbenzenesulfonates were analyzed in river water, sewage sludge and laundry detergents. Chromatographic separations on RP-8 columns led to a resolution of alkyl homologues. In CE, determination of the sum was performed in a pure aqueous buffer. Using electrolytes containing acetonitrile, homologous separation could be obtained. The addition of α-cyclodextrin allowed the separation of isomers. Aliphatic anionics (alkylsulfonates and -sulfates) could be determined by HPLC with conductivity detection and CE with indirect UV detection. Various chromophores like salicylate or dodecylbenzenesulfonate and organic modifiers were compared. Sodium dodecyl sulfate could be analyzed in toothpaste. Important representatives of cationics (quaternary alkyl and benzalkyl ammonium compounds, pyridinium salts) were separated using direct and indirect UV detection. For electrophoretic separation, high content of organic solvents was necessary to obtain a sufficient peak resolution. The results of method development were applied to the analysis of cetylpyridinium chloride in mouth-was. Non-ionic surfactants of the polyoxyethylene type are separated into ethoxylate homologues by HPLC on aminosilica columns. CE separation was carried out in electrolytes containing high content of acetonitrile and SDS and is based on the formation of association complexes between the non-ionic analytes and anionic surfactants. Chromatograms and electropherograms may be considered as fingerprints of the substance for product control and to determine the average number of ethylene oxide units of unknown products.