Probing the Nature and the Structure of Pores in Silica Xerogels by Water Sorption: The Tetramethyl Orthosilicate‐Hydrogen Chloride/Fluoride System

A series of silica xerogels were synthesized in a closed system by hydrolyzing tetramethyl orthosilicate (TMOS) with various concentrations of hydrochloric acid solution but without the addition of alcohol. The molar ratio of H₂O to TMOS was fixed at 4.96. The gels were characterized by water and nitrogen sorption measurements. The gelation time peaked at 50 to 80 h with 5 × 10⁻² to 10⁻¹M HCl, apparently a consequence of the isoelectric point of silica. Surface area, pore size, and sorption capacity were, however, at a minimum for samples prepared with 5 × 10⁻² to 10⁻¹M HCl. The BET c constant and hence the net heats of sorption were at a maximum for these samples. Although water sorption of all the samples prepared with HCl exhibited moderate Type I isotherms, the concavity of the isotherms to the P/P₀ axis increased with increasing concentrations of HCl up to 10⁻¹M in accordance with the decreased pore size and increased heat of sorption. Addition of F⁻ ions (HF or NaF) in the presence of 10⁻¹M HCl steadily decreased the gelation time. Addition of F⁻ in the absence of HCl, however, caused rapid gelation and an increase in pore size, nitrogen BET surface area, and hydrophobicity. Consequently, the shape of water isotherms gradually converted to Type IV and/or Type V. Adsorption and desorption measurements on differently activated gels exhibited various types of hystereses as a result of development of hydrophobie sites at as low as 200°C, inelastic distortion induced by adsorption, and chemical reaction and aging of gels when exposed to water vapor.