Kinetics of transfer of volatile amphiphiles (fragrances) from vapors to aqueous drops and vice versa: Interplay of diffusion and barrier mechanisms

TL;DR

This study investigates the kinetics of volatile amphiphile transfer between vapors, aqueous drops, and air, revealing the mechanisms and rate constants involved, with implications for fragrance applications.

Contribution

It introduces a comprehensive theoretical framework combining surface tension isotherms and kinetic analysis to quantify amphiphile transfer mechanisms and rate constants.

Findings

Mixed barrier-diffusion control in vapor phase

Diffusion control in aqueous drops

Enhanced adsorption rate constants compared to hydrocarbons

Abstract

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. The adequate theoretical processing of the equilibrium surface tension isotherms is applied to construct the two-dimensional equation of state, which relates the surface tension to the adsorption at the interface. The measured surface tension relaxations with time 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.