Five silica samples (four precipitated silicas provided by commercial suppliers and one with the MCM-41 structure) have been studied by infrared spectroscopy and by a homemade thermogravimetry-infrared spectrum (TG-IR) setup. The silanol amount, accessibility to water, and different alcohols. and the affinity to water of these various silicas were compared and quantified. TG-IR Measurements allowed the precise determination of the integrated molar absorption coefficient of the (nu + delta)OH band, epsilon((nu + delta)OH) = (0.16 +/- 0.01) cm mu mol(-1). It is independent of the sample origin and the concentration of silanol groups on silicas. For the precipitated dried samples evacuated at room temperature, the silanol concentration C(OH) varies between 3.6 and 7.0 mmol g(-1). It is 5.3 mmol g(-1) in the case of the MCM-41 sample. Exchange experiments with D(2)O followed by back-exchanges with different alcohols (methanol, propan-2-ol, 2-methyl-propan-2-ol, and 3-ethyl-pentan-3-ol) have been followed by infrared spectroscopy. All of the silanols of the MCM-41 sample are accessible to water and alcohol molecules. By contrast, about 20% of the silanols in precipitated samples are not exchanged by D(2)O (internal silanols). Accessibility decreases with alcohol size; the main effect is relative to methanol. Taking into account the sample specific surface areas and the silanol accessibility to D(2)O, the surface silanol density of precipitated silicas is close to 8 OH per nm(2), at maximum coverage. At variance, the silanol surface density of the MCM silica is much lower, 4 OH per nm(2). The TG-IR setup has also been used to determine the amount of water adsorbed oil silicas through the intensity of the delta H(2)O band. It varies linearly with the concentration of adsorbed water, whatever the silica sample. The integrated molar absorption coefficient of two hands, epsilon(delta H2O) = (1.53 +/- 0.03) cm mu mol(-1) and epsilon(()nu + delta)H2O = (0.22 +/- 0.01) cm mu mol(-1), have been determined. The number of H(2)O molecules adsorbed per nm(2) has been compared oil the five samples under an equilibrium pressure of 13 hPa at room temperature. Taking into account the number of silanols accessible to D(2)O for each sample, the silica-water affinity has been defined by the H(2)O/(SiOH(surf)) ratio. it is close to 0.8-0.9 for the precipitated samples but lower (0.7) in the case of the MCM one. This result is explained by the more important amount of isolated silanol groups presented by this sample.