A model has been developed that can simulate in some detail the chemistry of the glass dissolution process. To test the performance of the model, calculations were carried out to predict the dissolution behaviour of a commercial borosilicate glass. The model could reproduce accurately the behaviour of major elements released from the glass, although in the case of silica, ‘sorption’ at the glass surface was required in order to achieve good agreement with experimental data. Secondary reaction products sepiolite, montmorillonite, analcime and goethite were predicted to form. Further calculations were carried out to simulate the release of radioelements (caesium, strontium, uranium, plutonium) from within the dissolving glass. The precipitation of insoluble solids was the only mechanism included in the model to retain the radioelements at the glass surface. For plutonium, there was good agreement between model predictions and available experimental data. For caesium and strontium, the model underestimated the amount of retention at the glass surface and additional retention mechanisms, such as coprecipitation or ion exchange reactions involving newly-formed clay-type minerals at the glass surface must be invoked to explain experimental observation.