Diffuse reflectance infrared Fourier transform spectroscopy as a tool to characterise water in adsorption/confinement situations.

We present experimental data acquired by diffuse reflectance infrared spectroscopy in the mid-IR (4000-400 cm(-1)), on micrometric-sized mineral grain powders. The spectral evolution of the OH-stretching band is followed when the adsorbed water film is thinned under dry conditions, from high to low hydration states. The IR bands are found to be characteristic of the degree of adsorption/confinement of the liquid water. The OH-stretching band is shifted toward shorter wavenumbers than in bulk water, showing that a significant portion of adsorbed water has a higher intermolecular bonding energy. Complementary treatment of the kinetics of water desorption, varying with the surface forces in the water film, confirms the relationships of these bands with the constrained water state. We distinguish different water types obeying liquid-liquid interactions (free and capillary water) or dominated by solid-water interactions (confined and adsorbed water). Part of this study is devoted to mesoporous silica MCM-41, of interest due to the restricted geometries of its mesopores (4.7 nm) favouring the confined water state. The methodology allows us to distinguish bulk and adsorbed/confined water, using spectral analysis coupled with an understanding of the dynamic behaviour of the desorption process.