Geometry-Controlled Dynamic Tensiometry Resolves Intrinsic Surfactant Adsorption Kinetics
At short times, interfacial tension depends on experimental geometry because surfactant transport to the interface depends on the mass-transfer conditions.A predictive description therefore requires more than a dynamic tension curve or a fitted adsorption constant: interfacial thermodynamics, diffusion, and adsorption kinetics must be identified separately. Here, we combine equilibrium and diffusion measurements with a microfluidic EDGE tensiometer that provides a nearly stationary interface and controlled micrometer-scale transport. Equilibrium properties and diffusion are determined independently, leaving adsorption kinetics as the key unknown. Dynamic tension is then calculated using a nonequilibrium thermodynamic description, without assuming instantaneous equilibrium between the adsorbed layer and the subsurface solution. For the nonionic surfactant C$_{10}$E$_{8}$, equilibrium thermodynamics and transport are independently constrained, and a single intrinsic adsorption rate constant describes several concentrations. We extend the framework to SDS by including electrostatic interactions and subsurface-concentration dynamics, capturing transient depletion and replenishment. Once thermodynamic, transport, and kinetic parameters are identified, the model predicts dynamic interfacial tension beyond the geometry and conditions used to determine them. The microfluidic EDGE tensiometer thus provides both a reliable short-time tensiometry method and a quantitative framework for identifying the physical mechanisms governing surfactant mass transfer at interfaces.