title: Fluorescence evidence that a phase transition causes the induction time in the reduction in dynamic tension during surfactant adsorption to a clean air/water interface and a kinetic-diffusive transport model for the phase-induced induction.
abstract: An aqueous soluble surfactant adsorbing from solution onto an initially clean air/water interface often exhibits an induction period in the surface tension relaxation in which, as the adsorption begins, the tension remains near the clean interface value for an extended period of time before decreasing rapidly to the equilibrium value. In this study, using a model nonionic soluble surfactant, C14E6(CH3(CH2)13-(OCH2CH2)6-OH), we present direct fluorescence evidence that this induction is due to a first-order phase transition from a gaseous (G) to a liquid expanded (LE) phase that the assembling monolayer undergoes at constant surface pressure. An open channel flow cell is initially filled with water, and onto its air/water interface is spread an insoluble amphiphilic dye that fluoresces upon irradiation in the LE phase and whose fluorescence is quenched in the G phase. An aqueous solution of C14E(6) is then allowed to flow through the channel. We observe the immediate appearance of bright islands of the LE phase growing in a dark (G) background, confirming the presence of the G/LE phase transition. These islands eventually occupy the entire surface, after which the interface remains uniformly bright. We correlate this phase transition to the induction period by simultaneously measuring the tension of the interface of the open channel, and verifying that as the islands grow the tension remains at the clean value until the bright LE phase occupies the entire surface, whereupon the tension rapidly decreases. We further develop a phase transition surfactant transport model for the induction period in which surfactant diffuses toward and kinetically adsorbs onto the surface, and then rapidly equilibrates between the G and LE phases. For our model surfactant C14E6, we independently measure the surface concentration of the nucleating LE phase, the LE phase surfactant equation of state, the kinetic rate constants for adsorption into the LE phase, and the bulk diffusion coefficient. Using these measurements, we predict induction times for adsorption onto a clean surface without convection. We also measure these induction times in tension relaxation for adsorption onto a pendant bubble using axisymmetric shape analysis, and demonstrate agreement with the simulations with no adjustable constants.
authors.affiliation: Department of Chemical Engineering, City College of the City University of New York, New York, New York 10031, USA.
authors.forename: Rajeev
authors.initials: R
authors.lastname: Subramanyam
authors.forename: Charles
authors.initials: C
authors.lastname: Maldarelli