Search

This review incorporates a large number of chromatographic systems modified by the surfactants. A large number of solvent systems and stationary phases are summarized in this paper. Three different kinds of surfactants (anionic, cationic, and nonionic) are used as modifiers for stationary phases as well as solvent systems. Surfactants are used at all the three different concentration levels (below, above, and at critical micelle concentration) where surfactants behave differently. Modifications of both stationary phases and solvent systems by surfactants produced a new generation of chromatographic systems. Microemulsion solvent systems are also incorporated in this paper. Microemulsion thin-layer chromatography is a new approach in the field of chromatography.

The thermodynamics of clouding in an anionic surfactant, sodium dodecyl sulfate (SDS) and quaternary phosphonium bromides systems in the presence of glycerol are reported. The standard Gibbs energy change of solubilization (ΔsG°) for all of the additives was found to be negative. The standard enthalpy change (ΔsH°) and the standard entropy change (TΔsS°) values were found to be negative as well as positive depending upon the type and nature of the additive. The results were explained on the basis of their nature, effect on the water structure, and solubilization of these additives either in the micellar or aqueous phase.

The energetics of clouding in anionic surfactant (SDBS) and tetrabutylammonium bromide system in the presence of additives, such as ureas, amino acids and sugars is reported. The change of standard Gibbs energy of solubilization (ΔG o ) for all of the additives was found to be negative. The values of change of standard enthalpy (ΔH o ) and that of standard entropy (TΔS o ) values were found to depend on the type and chemistry of the additive. The results were explained on the basis including chemistry of additives, their effect on water structure, and solubilization of additives either in the micellar or in aqueous phases.

Mixing behavior of anionic surfactant sodium dodecyl sulfate (SDS) with cationic hydrotropes aniline hydrochloride (AH), o-toluidine hydrochloride (o-TH), and p-toluidine hydrochloride (p-TH) have been studied using conductivity at different temperatures. Critical micelle concentration for different mixing mole fractions, their ideal values, and different interaction parameters have been estimated. All the parameters show nonideal behavior with synergistic interactions. Thermodynamic parameters are also calculated for these systems.

Effects of three organic solvents, viz. methyl cellosolve, acetonitrile, and formamide, on the micellization process of Gemini surfactant pentamethylene-1,5-bis(tetradecyldimethylammonium bromide) aqueous solutions, with the volume percentages of the organic solvents up to 50%, have been investigated conductometrically. The studies were made at different temperatures and the data were used to find out different micellization parameters. From the study, it was observed that, although an increment in the amount of the organic solvents delays the micellization, the increase in the critical micelle concentration (cmc) is comparatively less below 20%(v/v) showing the predominance of water character in the bulk phase at lower compositions of the organic solvents. Applying equilibrium model for micelle formation, various thermodynamic parameters were also calculated from the temperature dependence of the cmc values and the results show that the micellization process becomes less spontaneous as the volume % of th...

The thermodynamic parameters of an aqueous anionic surfactant, tetrabutylammonium dodecyl sulfate (TBADS), are calculated in the presence of various additives (viz., quaternary bromides, alcohols, and amines) at the cloud point (CP) of the TBADS−additive system. As the clouding components release their solvated water, they separate out from the solution. Therefore, the CP of an amphiphile can be considered the limit of its solubility. The standard Gibbs energy change of solubilization (ΔsG°) for all of the additives is found to be negative. The standard enthalpy change (ΔsH°) and the standard entropy change (TΔsS°) values are found to be negative as well as positive depending upon the type and nature of the additive. The results are explained on the basis of their nature, effect on the water structure, and solubilization of these additives either in the micellar or aqueous phase.

In this paper, we are reporting the influence of addition of aromatic acids (anthranilic and benzoic acid) and their sodium salts on the micellar morphological changes in three cationic gemini surfactant solutions, viz. 5 mM tetramethylene-1,4-bis(N-hexadecyl-N,N-dimethylammonium bromide), 10 mM pentamethylene-1,5-bis(N-hexadecyl-N,N-dimethylammonium bromide), and 10 mM hexamethylene-1,6-bis(N,-hexadecyl-N,N-dimethylammonium bromide). The solubilization site of the counterions (obtained from the additives) near the micellar surface are inferred by 1H NMR. The behavior is explained in the light of binding of counterions to the micelle as well as the nature of the functional group attached to the additive.

The effect of addition of sodium anthranilate to 5 mM micellar solutions of gemini surfactant 1,4-bis(N-hexadecyl-N,N-dimethylammonium)butane dibromide is investigated by 1H NMR. The solubilization site of anthranilate anion near the micellar surface is inferred. In the micelles, the An− ions intercalate among the surfactant headgroups producing morphological changes.

Analysis of a variety of surfactant aggregation processes (monomer-to-micelle, spherical micelle-to-rod shaped micelle – s → r – transition, micellar growth and clouding phenomenon) in aqueous ureas or thioureas presented here shows a different picture that differs from the earlier literature reports (i.e., urea postpones the surfactant aggregation). Evidence has been collected on the basis of critical micelle concentration (cmc, obtained from conductometry), [1-pentanol] needed for s → r transition (obtained from viscometry), aggregation number (obtained from small angle neutron scattering) and cloud point (CP) measurements. All of these effects are attributed to urea-assisted aggregation up to certain concentration, which depends upon the nature and presence of number of methylene groups in a particular urea. The results are explained on the basis of influence of the additive on solvent water, adsorption on headgroup and hydrocarbon tail and size of the additive. The results may find application in understanding the mechanism of protein denaturation/renaturation by the presence of different additives.

Clouding phenomenon in aqueous micellar solutions of an anionic surfactant tetra-n-butylammonium dodecylsulfate (TBADS) has been observed as a function of surfactant concentration. Small-angle neutron scattering (SANS) experiments in these systems show clustering of micelles as the temperature approaches the cloud point (CP). The individual micelles and the clusters of micelles coexist at CP. The clustering of micelles depends on the surfactant concentration and temperature. It is proposed that clustering is due to depletion of H-bonded water present around the butyl chains at the micellar surface. This is associated with entropy gain which is considered to be the major thermodynamic factor related to micellar aggregation. The structures (clusters) that emerge depend on the relative lengths of the alkyl chains of the counterion and can be tuned by the temperature.