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As water diffuses into silica glass, it reacts with the silica network to generate hydroxyl groups that cause a volume swelling of the glass. We discuss this effect quantitatively for cases in which hydroxyl groups were produced either by gamma‐irradiation of hydrogen‐saturated silica glass or by high‐temperature diffusion of water into silica glass. From volume swelling measurements, the partial molar volume of hydroxyl groups for both treatments is determined to be 7.5 cm3/mol. Since two moles of SiOH are generated for each mole of water reacting with the glass, the reaction volume, ΔV¯, is 15.0 cm3/mol. [ABSTRACT FROM AUTHOR]