Long-Term Adsorption Kinetics of Asphaltenes at the Oil-Water Interface: A Random Sequential Adsorption Perspective

Previous studies indicated that asphaltenes adsorbed as monomers on oil-water interfaces and the early stage kinetics of the process was controlled by diffusion and hence dependent on oil viscosity. By measuring interfacial tension (IFT) as a function of surface coverage during droplet expansions in pendant drop experiments, it was also concluded that the IFT data could be interpreted with a Langmuir equation of state (EoS), which was independent of oil viscosity, time of adsorption, and bulk asphaltenes concentration. The surface excess coverage was calculated to be similar to 0.3 nm(2)/molecule, which suggested adsorption in face-on configuration of asphaltenes monomers at the interface and average PAR core per molecule of about 6 for the asphaltenes investigated, consistent with the Yen-Mullins model. The current study focuses on the kinetics of asphaltenes adsorption at longer times and higher interfacial coverage. Long-term IFT data have been measured by the pendant drop method for different asphaltenes concentrations and for different bulk viscosities of the oil phase (0.5-28 cP). The data indicate that when coverage reaches 35-40%, the adsorption rates slow down considerably compared to the diffusion-controlled rates at the very early stages. The surface pressure increase rate (or IFT decrease rate) at these higher coverages is now independent of oil viscosity but dependent upon both surface pressure itself and asphaltene monomer concentration. The long-term asymptotic behavior of surface coverage is found to be consistent with the predictions from surface diffusion-mediated random sequential adsorption (RSA) theory which indicates a linear dependency of surface coverage on 1/root t and an asymptotic limit very close to 2D random close packing of polydispersed disks (85%). From these observations RSA theory parameters were extracted that enabled description of adsorption kinetics for the range of conditions above surface coverage of 35%.