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The binding of organic contaminants to dissolved humic acids reduces the free concentration of the contaminants in the environment and also may cause changes to the solution properties of humic acids. Surfactants are a special class of contaminants that are introduced into the environment either through wastewater or by site-specific contamination. The amphiphilic nature of both surfactants and humic acids can easily lead to their mutual attraction and consequently affect the solution behavior of the humics. Binding of an anionic surfactant (sodium dodecyl sulfate, SDS) and two cationic surfactants (dodecyl- and cetylpyridinium chloride, DPC and CPC) to purified Aldrich humic acid (PAHA) is studied at pH values of 5, 7, and 10 in solutions with a 0.025 M ionic strength (I). Monomer concentrations of the surfactants are measured with a surfactant-selective electrode. At I = 0.025 M, no significant binding is observed between the anionic surfactant (SDS) and PAHA, whereas the two cationic surfactants (DPC, CPC) bind strongly to PAHA over the pH range investigated. The binding is due both to electrostatic and hydrophobic attraction. The initial affinity increases with increasing pH (i.e., negative charge of PAHA) and tail length of the surfactant. Binding reaches a pseudo-plateau value (2-5 mmol/g) when the charge associated with PAHA is neutralized by that of the bound surfactant molecules. The pseudo-plateau values for DPC and CPC are very similar and depend on the solution pH. The cationic surfactant-PAHA complexes precipitate when the charge neutralization point is reached. This occurs at approximately 10% of the critical micelle concentration or CMC. This type of phase separation commonly occurs during surfactant binding to oppositely charged polyelectrolytes. For CPC, the precipitation is complete, but in the case of DPC, a noticeable fraction of PAHA remains in solution. At very low CPC concentrations (less than 0.1% of the CMC), CPC binding to PAHA is cooperative. The investigated range of concentrations for DPC was too limited to reach a similar conclusion. The results of this study demonstrate that the fate of humic acids will be strongly affected by the presence of low cationic surfactant concentrations in aqueous environmental systems.

Dilute emulsions of dodecane in water were prepared under constant flow rate conditions with binary surfactant systems. The droplet size distribution was measured as a function of the mixed surfactant composition in solution. The systems studied were (a) the mixture of anionic sodium dodecyl sulfate (SDS) with nonionic hexa(ethyleneglycol) mono n-dodecylether (C12E6) and (b) the mixture of cationic dodecyl pyridinium chloride (DPC) with C12E6. At a constant concentration of SDS or DPC surfactant in solution (below the CMC) the mean emulsion droplet size decreases with the increase in the amount of C12E6 added to the solution. However, a sharp break of this droplet size occurs at a critical concentration and beyond this point the mean droplet size did not significantly change upon further increase of the C12E6. This point was found to corresponded to the CMC of the mixed surfactant systems (as previously determined from microcalorimetry measurements) and this result suggested the mixed adsorption layer on the emulsion droplet was similar to the surfactant composition on the mixed micelles. The emulsion droplet size as a function of composition at the interface was also studied. The mean emulsion droplet size in SDS-C12E6 solution was found to be lower than that in DPC-C12E6 system at the equivalent mole fraction of ionic surfactant at interface. This was explained by the stronger interactions between sulphate and polyoxyethylene head groups at the interface, which facilitate the droplet break-up. Counterion binding parameter (beta) was also determined from zeta-potential of dodecane droplets under the same conditions and it was found that (beta) was independent of the type of the head group and the mole fraction of ionic surfactant at interface.

To clarify the effect of the surfactant head group on the emulsification process, dilute dodecane in water emulsions were prepared in a small flow-through cell with three surfactants which had the same hydrocarbon tail length but different head groups. The different surfactants types were (a) a nonionic, hexa(ethyleneglycol) mono n-dodecyl ether (C12E6), (b) an anionic, sodium dodecyl sulfate (SDS), and (c) a cationic, n-dodecyl pyridinium chloride (DPC), and the emulsions were prepared under the same conditions. From dynamic light scattering measurements, it was shown that the mean steady state droplet size of the emulsions (obtained after 20 min dispersion) could be related to the interfacial tension at concentrations in the region of the cmc. This result was in agreement with laminar and turbulent viscous flow theory. However, the particle size versus surface tension data for the different surfactant systems did not fall on a single line. This behavior suggested that the surfactant played a secondary role in defining the droplet size (in addition to reducing the interfacial tension) possibly through diffusion and relaxation, during deformation of the interface. In addition, it was found that the values of the equilibrium "surfactant packing densities" of the different surfactants at the oil/water interface were almost equal near the cmc, but the mean droplet size and the interfacial tension at the cmc decreased following the order DPC>SDS>C12E6 .

To study the influence of the chemical nature of headgroups and the type of counterion on the process of micellization in mixed surfactant systems, the cmc's of several binary mixtures of surfactants with the same length of hydrocarbon tail but with different headgroups have been determined as a function of the monomer composition using surface tension measurements. Based on these results, the interaction parameter between the surfactant species in mixed micelles has been determined using the pseudophase separation model. Experiments were carried out with (a) the nonionic/anionic C(12)E(6)/SDS ((hexa(ethyleneglycol) mono-n-dodecyl ether)/(sodium dodecyl sulfate)), (b) amphoteric/anionic DDAO/SDS ((dodecyldimethylamine oxide)/(sodium dodecyl sulfate)), and (c) amphoteric/nonionic C(12)E(6)/DDAO mixed surfactant systems. In the case of the mixed surfactant systems containing DDAO, experiments were carried out at pH 2 and pH 8 where the surfactant was in the cationic and nonionic form, respectively. It was shown that the mixtures of the nonionic surfactants with different kinds of headgroups exhibit almost ideal behavior, whereas for the nonionic/ionic surfactant mixtures, significant deviations from ideal behavior (attractive interactions) have been found, suggesting binding between the head groups. Molecular orbital calculations confirmed the existence of the strong specific interaction between (1) SDS and nonionic and cationic forms of DDAO and between (2) C(12)E(6) and the cationic form of DDAO. In the case for the C(12)E(6)/SDS system, an alternative mechanism for the stabilization of mixed micelles was suggested, which involved the lowering in the free energy of the hydration layer. Copyright 2000 Academic Press.

The association of diblock copolymers with oppositely charged, water-soluble poly(dimethylamino)ethyl methacrylate (AMA) and sodium polymethacrylate (SPM) blocks was studied in aqueous solution as a function of pH and the segment ratio of the two blocks. The size and the structure of these copolymer aggregates were characterized by dynamic light scattering, electrokinetic, and potentiometric measurements. The association process is mainly electrostatically driven. At pH values around the isoelectric point, unlimited aggregation or phase separation takes place. The position of this region depends on the segment ratio of the two blocks. If the pH is moved away from the isoelectric point, the net charge of the copolymer molecules leads to charged molecular assemblies. At pH values higher than 10 or lower than 4, i.e., one of the blocks is entirely uncharged, copolymer assemblies still exist. The solution behavior of the corresponding oppositely charged homopolyelectrolyte mixtures was also studied. The size of the charged homopolymer complexes is smaller than that for copolymers although the length of the homopolymer molecules is higher.

Contact angle, colloid stability and flotation measurements have been carried out for silica as a function of the concentration of cationic surfactants at different salt concentrations. The results are compared with surfactant adsorption and surface charge isotherms. The surfactants used are dodecyl and cetyl pyridinium chloride, and dodecyl trimethyl-ammonium bromide. Colloid instability, contact angles and flotation recovery all pass through a maximum at about the charge compensation point that corresponds for the present system to the iso-electric point and the (near) common intersection point of surfactant isotherms measured at a given pH and different ionic strength values. Before the charge compensation point the surfactant progressively neutralises the negative surface charge by head-on adsorption and simultaneously the surfactant tail causes an increase in hydrophobicity. Beyond the charge compensation point admicelles are formed, leading to a net positive particle charge and an increase in hydrophilicity. In the charge compensation point the maximum of hydrophobicity occurs together with the minimal net particle charge. Therefore, the minimum in the stability and the maximum in the flotation recovery are related to both the low particle charge and the relatively large particle hydrophobicity around the charge compensation point.