Kinetic multi‐layer model of film formation, growth, and chemistry (KM‐FILM): Boundary layer processes, multi‐layer adsorption, bulk diffusion, and heterogeneous reactions
Pascale S. J. Lakey, Clara M. A. Eichler, Chunyi Wang, John C. Little, Manabu Shiraiwa
Abstract
Large surface area-to-volume ratios indoors cause heterogeneous interactions to be especially important. Semi-volatile organic compounds can deposit on impermeable indoor surfaces forming thin organic films. We developed a new model to simulate the initial film formation by treating gas-phase diffusion and turbulence through a surface boundary layer and multi-layer reversible adsorption on rough surfaces, as well as subsequent film growth by resolving bulk diffusion and chemical reactions in a film. The model was applied with consistent parameters to reproduce twenty-one sets of film formation measurements due to multi-layer adsorption of multiple phthalates onto different indoor-relevant surfaces, showing that the films should initially be patchy with the formation of pyramid-like structures on the surface. Sensitivity tests showed that highly turbulent conditions can lead to the film growing by more than a factor of two compared to low turbulence conditions. If surface films adopt an ultra-viscous state with bulk diffusion coefficients of less than 10−18 cm2 s−1, a significant decrease in film growth is expected. The presence of chemical reactions in the film has the potential to increase the rate of film growth by nearly a factor of two.