Sodium-rich glasses of the system Na2O-SiO2 are well known to be easily soluble in water. This is not true for silica-rich compositions. We have manufactured quenched glasses with silica contents between 65 and 80 wt.% SiO2 and followed the water interaction at 100°C by measuring mass and sample dimensions in intervals. Comparing the path of edge length, mass and volume to a general shrinking core model for cuboids we conclude that only compositions between 65 and 70 wt% SiO2 can be described well by a simple dissolution process. The logarithm of the dissolution rate constant varies linearly with the SiO2 content. At higher silica contents the mechanism changes towards leaching of sodium. We propose changing glass structures to be responsible for the change in mechanism.