Experiments were performed, irradiating UO2 colloids of 3 nm diameter by a 5 MeV alpha beam of a cyclotron. Both the dissolution rate of these colloids and the production rate of hydrogen peroxide have been measured. The experimentally measured corrosion rate of these colloids is very similar to the corrosion rates measured for bulk UO2 samples, indicating on the one hand that similar reaction mechanism prevail and on the other hand that the UO2 colloids are well representative for bulk UO2. The results were compared with two current models for radiolytical dissolution of spent fuel. Additionally a new coupling between water radiolysis reactions and spent fuel dissolution has been established. The coupling is not anymore based on rate constants for direct reaction of oxidants with UO2, but on the electrochemical coupling of anodic dissolution reactions with cathodic reduction of molecular and radical radiolysis products. The model not only describes well the experimental data, it also allows to predict both the establishment of corrosion potentials and of fractional reaction orders with respect to oxidant concentrations. Model results can also be compared with experimental data (corrosion potential ...) using UO2 as an electrode.