Application of the Stefan‐Maxwell Equations to determine limitations of Fick's law when modeling organic vapor transport in sand columns

The organic component of the vapor phase of a porous medium contaminated by an immiscible organic liquid can be significant enough to violate the condition of a dilute species diffusing in a bulk phase assumed by Fick's law. The Stefan‐Maxwell equations provide a more comprehensive model for quantifying steady state transport for a vapor phase composed of arbitrary proportions of its constituents. The application of both types of models to the analysis of column experiments demonstrates that use of a Fickian‐based transport model can lead to significant overestimates of soil tortuosity constants. Further, the physical displacement of naturally occurring gases (e.g., O 2 ), predicted by the Stefan‐Maxwell model but not by application of Fick's Law, can be attributed improperly to a sink term such as microbial degradation in a Fickian‐based transport model.