Search

The aqueous catanionic system dodecyltrimethylammonium bromide (DTAB)–disodiumdodecanephosphonate (DSDP) was studied by potentiometry, conductivity, surface tension, spectrometry and dye solubilization. No precipitation of neutral salts was found in the entire range of compositions studied. Up to four transitions were detected. The first transition, at about 0.001 mol dm−3, was probably related to a state change in the adsorption monolayer at the air/water interface. The second, at about 0.0065 mol dm−3, was probably related to the formation of ion pairs. The third transition was the critical micelle concentration which was analyzed with the pseudophase separation model and regular solution theory. The interaction between DTAB and DSDP molecules in micelles was weaker than in other cationic–anionic surfactant mixed micelles. Large, probably rodlike, micelles formed at the fourth transition at higher surfactant concentration. No vesicles or lamellar liquid crystals were detected. The adsorbed monolayer at the air/water interface was also studied by means of regular solution theory. It was much richer in DTAB than the micelles and the intermicellar solution. The interaction between DTAB and DSDP molecules at the air/water interface was very low. The results were explained on the basis of steric factors.

The partial molar volume of dodecyltrimethylammonium hydroxide in water and aqueous NaOH solutions was measured. The addition of NaOH did not affect either the micellized or the unmicellized molecules. The expansion on micellization is much larger than in dodecyltrimethylammonium bromide systems, which reflects the stronger ionization of the hydroxide surfactant micelles, when compared with that of the bromide amphiphile.

The triangular phase diagram of the system dodecyltri-methylammonium hydroxide (DTAOH)–dodecanephosphonic acid (H2DP)–water was studied by several techniques. The DTAOH-rich zone could not be studied because DTAOH decomposed when it was dried. Pure H2DP only forms lamellar mesophases with water. The inclusion of DTAOH in the system produces the appearance of cubic and hexagonal mesophases. The gradual increase in DTAOH proportion lead to the gradual reduction in the existence of the lamellar mesophase domain, and increase of the hexagonal liquid crystal domain. At high DTAOH content, the lamellar mesophase disappeared. This behavior was explained by the gradual destruction of the hydrogen-bonded structure in the polar headgroup layer of liquid crystal aggregates. H2DP-rich anhydrous crystals were triclinic.

The solubilization of styrene in micelles of the catanionic surfactant dodecyltrimethylammonium hydroxide (DTAOH)–n-dodecane-phosphonic acid (DPA) was studied by UV–Vis. spectrometry, as a function of the DTAOH:DPA proportion in the surfactant mixture. The styrene molecules are adsorbed at the surface of the micelles, with the vinyl group closer to the hydrocarbon core than the aromatic ring, which is oriented to the water. In micelles with an excess of DTAOH, the dielectric constant of the water surrounding the micelles was strongly affected by the non-neutralized –N(CH3)+3 groups at the Stem layer. In micelles with an excess of DPA, the –PO3H2 groups which are not neutralized by –N(CH3)+3, remain almost unionized and hydrogen-bonded. The effect of the micellar surface on the surrounding water dielectric constant dropped sharply. The dielectric constant in the hydrogen-bonded polar layer is ∼65, rising to the value of pure water very close to the micellar surface.

Electrobalance evaporation rate measurements were used to measure solute weights in the aqueous catanionic system monododecyltri-methylammonium-n-dodecanephos-phonate. At very low concentration premicelles composed of ion pairs between 3.6 and 7 were found, which increased with concentration. Above the cmc the aggregates increased in size with concentration much more rapidly. Aggregates had 54 ion pairs at the higher studied concentration (6×10-3 mol dm-3). This value agrees with literature data of other similar systems. Since the system is probably polydisperse and the evaporation rate method gives number average weights, the true aggregation numbers are probably higher than those found. In this system the cmc did not indicate the starting point of aggregation, but a change in the aggregates structure and growing regime.

The air/water interface of the system n-dodecanephosphonic acid (H2DP)–water was studied by surface tension, ion-selective electrodes and evaporation in an electrobalance. The combination of surface tension and ion-selective electrodes measurements enables to study the adsorption of soluble surfactants above the cmc using the Gibbs’ equation. H2DP formed a nonideal monolayer at the air/water interface with Amolec=0.995 nm2 below the cmc. Above the cmc there was a reduction in adsorption giving Amolec=6.32 nm2, which remained almost constant in the explored concentration range. This adsorption reduction may be due to a change composition on micellization, or to a thermodynamic advantage of micellization on adsorption. The reduction in the evaporation rate of water was mainly due to the reduction of the water activity, caused by the presence of solutes in bulk. This is because the strong changes in the surface coverage did not have significant influence on the evaporation rate.

The influence of the surfactant charge on micellization was studied on sodium n-dodecane-phosphonates, varying the charge of the surfactant ion from 0 to 2. The effects on the cmc, hydrolysis, micelle composition, and micelle ionization degree were studied. The increase of one e unit in the charge of the surfactant species reduces the cmc by about one order of magnitude.

Several techniques were employed to study the aggregation ofn-Dodecanephosphonic Acid (DPA) in water. At 22°C, the solubillity of DPA increases, probably due to the formation of small premicellar aggregates. The CMC is (5.4±2.4) ×10−4 mol·dm−3 and the solubility reaches the CMC value at 26°C. At 30°C and at a concentration of about 9×10−3 mol·dm−3, a lamellar mesophase appears. Both micelles and liquid crystal lamellae are almost uncharged. Their polar heads have strong hydrogen bonds between them. The ionization of DPA molecules in micelles and mesophase structures is strongly reduced in comparison with monomerically dissolved molecules.

The aggregation of dodecyltrimethylammonium hydroxide (DTAOH) in aqueous NaOH solutions was studied as a function of NaOH concentration. As in NaOH-free DTAOH aqueous solutions, the surfactant underwent a stepwise aggregation mechanism. Changes in the structure of aggregates produced an increase of the concentration at which premicellar aggregates could solubilize hydrophobic dyes and also in the concentration at which hydroxide inons join the aggregates.

The aggregation of aqueous dodecylphosphonic acid (DPA) and dodecyltrimethylammonium hydroxide (DTAOH) mixtures was studied by several methods. The behavior of DPA-rich mixtures is close to that of pure DPA. This is probably due to the preservation of the hydrogen-bonded structure of the micellar headgroup layer. The behavior is almost ideal. Betweeny DPA =0.5 and 0.33 (y DPA being the mole fraction of DPA in the surfactant mixture), the hydrogen-bonded structure of the micellar headgroup layer is destroyed. A sort of “micellar azeotrope” is formed, and the maximum of non-ideal interaction between the two surfactants is attained aty DPA =0.4. Fory DPA

The aggregation of dodecyltrimethylammonium hydroxide (DTAOH) aqueous solutions has been studied by several methods. It is stepwise and four critical points were found. AtC T=(2.51±0.10)×10−4 mol · dm−3 the surface excess becomes zero, atC T=(1.300±0.041)×10−3 mol · dm−3 small aggregates from, which grow with concentration. AtC T=(1.108±0.010)×10−2 mol · dm−3 true micelles form (CMC) and at (3.02±0.28)×10−2 mol · dm−3 the structure of micelles probably changes affecting their properties. The DTAOH micelles are highly ionized (α=0.8) at the CMC, and decreases to reach very small values when the total concentration increases.