CEC-normalized clay-water sorption isotherm

A normalized clay‐water isotherm model based on BET theory and describing the sorption and desorption of the bound water in clays, sand‐clay mixtures, and shales is presented. Clay‐water sorption isotherms (sorption and desorption) of clayey materials are normalized by their cation exchange capacity (CEC) accounting for a correction factor depending on the type of counterion sorbed on the mineral surface in the so‐called Stern layer. With such normalizations, all the data collapse into two master curves, one for sorption and one for desorption, independent of the clay mineralogy, crystallographic considerations, and bound cation type; therefore, neglecting the true heterogeneity of water sorption/desorption in smectite. The two master curves show the general hysteretic behavior of the capillary pressure curve at low relative humidity (below 70%). The model is validated against several data sets obtained from the literature comprising a broad range of clay types and clay mineralogies. The CEC values, derived by inverting the sorption/adsorption curves using a Markov chain Monte Carlo approach, are consistent with the CEC associated with the clay mineralogy. Key Points The CEC can be used to normalize water retention curves The CEC itself needs to account for the type of cation sorbed on the clays An extended BET theory can reproduce the experimental data