No abstract

No abstract

No abstract

The evaporation rate of water molecules across three kinds of interfaces (air/water interface (1), air/surfactant solution interface (2), and air/water interface covered by insoluble monolayer (3)) was examined using a remodeled thermogravimetric balance. There was no difference in both the evaporation rate and the activation energy for the first two interfaces for three types of surfactant solutions below and above the critical micelle concentration (cmc). This means that the molecular surface area from the Gibbs surface excess has nothing to do with the evaporation rate. In the third case, the insoluble monolayer of 1-heptadecanol decreased the evaporation rate and increased the activation energy, indicating a clear difference between an insoluble monolayer and an adsorbed film of soluble surfactant. This difference was substantiated by BAM images, too. The images of three surfactant solution interfaces were similar to that of just the water surface, while distinct structures of molecular assemblies were observed for the insoluble monolayer. The concentration profile of water molecules in an air/liquid interfacial region was derived by Fix's second law. The profile indicates that a definite layer just beneath the air/liquid interface of the surfactant solution is made mostly of water molecules and that the layer thickness is a few times the root-mean-square displacement %@mt;sys@%%@rl;;@%2%@ital@%Dt%@rsf@%%@rlx@%%@mx@% of the water molecules. The thickness was found to be more than a few nanometers, as estimated from several relaxation times derived from the other kinetics than evaporation of amphiphilic molecules in aqueous systems and a maximum evaporation rate of purified water.

Several pieces of experimental evidence of condensation of soluble surfactant molecules, cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS), into the air/water surface region from the bulk solution are presented at different added salt concentrations in order to substantiate that the concentrated molecules do not locate just at the air/solution interface. The insoluble monolayer just at the air/subphase interface for the two surfactants could be studied by surface pressure (π) versus molecular surface area (A), surface potential (ΔV) versus the area (A), infrared absorption of the surface region, and BAM (Brewster angle microscope) image. From surface tension versus concentration curves for the two surfactant solutions, the apparent molecular surface area and the cmc values were determined at different added salt concentrations, and the degree of counterion binding to micelle was found to be 0.70 and 0.73 for CTAB and SDS, respectively. Further examination was made on infrared absorption from the surface region of the surfactant solutions and on BAM images of the surface planes in order to examine the difference between the insoluble monolayer and the condensation in the surface region. Finally, the new concept of bilayer or bilamellar aggregate for soluble surfactant solutions is presented together with the former experimental evidence, which is consistent with several interfacial phenomena of the surfactant solutions.

The surface potential (DeltaV) of the air/sodium chloride solution interface was measured by using an ionizing (241)Am electrode method at 298.2 K. The surface potential steeply increased from 0 up to 15 mV with increasing concentration, then gradually increased up to 20 mV between 1 and 10 mmol dm(-3), and finally stayed almost constant at 20 mV up to the concentration of 20 mmol dm(-3). This result means that sodium ions concentrate more just near the air/solution interface, whereas chloride ions concentrate more far below the interface above the bulk region of electroneutrality. The dipole moment was derived from the surface potential value, from which the width of the interfacial layer was estimated as a function of the magnitude of electric charge. As for the sodium dodecyl sulfate solution, on the other hand, the surface potential steeply decreased from 0 down to -80 mV with increasing concentration from 0 to 0.01 mmol dm(-3), then rapidly increased up to -50 mV between 0.1 and 3 mmol dm(-3), then linearly increased up to 0 mV with increasing concentration from 3 mmol dm(-3) up to the CMC, 8 mmol dm(-3), then quite rapidly decreased again down to -82 mV from the CMC to 10 mmol dm(-3), and finally stayed almost constant at -82 mV up to the concentration of 20 mmol dm(-3). The above variations of the surface potential cannot be elucidated by the conventional surface excess, and therefore, the new concept of surface adsorption was presented for a simple salt and a typical anionic surfactant.

No abstract

No abstract