Identification and quantification of soil water components in kaolin by thermogravimetric and kinetic analysis

Different types of soil water, such as bound water and capillary water, have distinct effects on the physicochemical and engineering properties of soils, particularly unsaturated clayey soils. Therefore, it is crucial to develop an accurate and physically meaningful experimental method for identifying and quantifying these components. This study pioneers the use of a multi-step kinetic model to identify and quantify different soil water components across a wide range of relative humidity (RH) using thermogravimetric analysis (TGA) data. To validate the determined kinetic parameters (i.e., activation energy, preexponential factor, and reaction model) and the identification and quantification results of soil water components, TGA with multiple heating rates, nitrogen adsorption method, cation exchange capacity measurement, and nuclear magnetic resonance (NMR) were performed on kaolin samples equilibrated under various RH conditions. These experimental results cross-validate the superior performance of the kinetic model in determining soil water components and predicting the thermal desorption behaviors of soil water. Based on the cross-validation results, the soil water components obtained from the kinetic analysis are further identified as tightly-bound, loosely-bound, and capillary water, which exhibit variations consistent with empirical soil water isotherm models. The T₂ cutoff value between bound and capillary water is determined to be 1.79 ms based on TGA and NMR results. The determined thermal kinetic parameters of different soil water components can exhibit their distinct retention mechanisms. The method and results in this study provide a new perspective on identifying different soil water components, as well as understanding the mechanism of soil-water interactions in unsaturated soils.