The class of volatiles, which possess low saturated vapor pressures, appreciable solubilities in water, and well pronounced surface activities, have gained wide applications in diverse areas of industry, cosmetics, and medicine. One way to qualitatively characterize their mass transfer between vapor and aqueous solutions is to measure the relaxation of the interfacial tension, σ, with time, t, under different nonequilibrium initial conditions. This approach is applied in the present work for geraniol and menthol. By means of combining σ(t) data with the respective equilibrium surface tension isotherms, the instantaneous values of the fragrance adsorption, Γ(t), have been determined. Quantitative characterization of the geraniol and menthol mass transfers in the case of adsorption from vapor to aqueous drops is achieved by using a mixed barrier-diffusion model. The obtained values of the rates of adsorption and desorption are compared with those reported in the literature for benzyl acetate, linalool, and citronellol. In the case of evaporation of the volatiles from their saturated aqueous solutions to the ambient atmosphere, the mass transfer is found to be driven both by mixed barrier-diffusion and by convection-enhanced mechanisms – depending on the air humidity. The quantitative description of the evaporation of volatile molecules is modelled theoretically by adsorption rate constants. In order to achieve the reported model representations, complex numerical calculations are implemented. On the other hand, having in mind the cases when one wishes to avoid extensive computational work, we developed a simple semiempirical model suitable for all five studied fragrances. This simplified approach is convenient for the express comparison and characterization of the evaporation rates. The obtained physicochemical parameters related to the evaporation and condensation of volatiles are important for the rigorous modeling of their complex mixed solutions of practical interest. The semiempirical model could be used for the quantitative classification of volatile molecules with respect to their ability to evaporate.

Subject of this work is to investigate the kinetics of mass transfer of volatile amphiphiles from their vapors to aqueous drops, and from the saturated aqueous drop solutions to air. The used amphiphiles are benzyl acetate, linalool, and citronellol, all of which have low saturated vapor pressures, appreciable solubility in water, and well pronounced surface activity. The adequate theoretical processing of the equilibrium surface tension, σ, isotherms is applied to construct the two-dimensional equation of state, which relates σ to the adsorption, Γ, at the interface. The measured surface tension relaxations with time t in the regimes of adsorption from vapor and evaporation from drop combined with the equations of state provide quantitative information on the change of adsorption because of the volatile amphiphile mass transfer across the surface. The theoretical analysis of the diffusion and barrier mechanisms in the case of adsorption from vapor to the aqueous drop shows that the mixed barrier-diffusion control in the vapor and diffusion control in the drop describe experimental data. The obtained values of the adsorption rate constants are six orders of magnitude larger than those for hexane and cyclohexane reported in the literature. The regime of evaporation from aqueous amphiphile solution drop follows the convection-enhanced adsorption mechanism with desorption rate constant in the vapor affected by the simultaneous water evaporation and amphiphile desorption. The water evaporation suppresses the evaporation of linalool and accelerates desorption of benzyl acetate and citronellol. From viewpoint of applications, the obtained physicochemical parameters of the studied three fragrances can help for better understanding of their performance in shampoo systems and perfumes. From theoretical viewpoint, the result show that by introducing an effective amphiphile desorption rate constant it is possible to quantify the complex volatile amphiphile desorption accompanied with the water evaporation.