Vibrationally highly excited molecules react extremely fast with atoms and probably with radicals. The phenomenon can be utilized for selectively enhancing the rate of reactions of specific bonds. On the basis of quasiclassical trajectory calculations, the paper analyzes mechanistic details of a prototype reaction, H + HF(v). At vibrational quantum numbers v above 2, the reaction exhibits capture-type behavior, that is, the reactive cross section diverges as the relative translational energy of the partners decreases, both for the abstraction and for the exchange channel. The mechanism of the reaction for both channels is different at low and at high translational energy. At low vibrational energy, the reaction is activated, which is switched to capture-type at high excitation. The reason is an attractive potential that acts on the attacking H atom when the HF molecule is stretched. In contrast to the 6-SEC potential surface of Mielke et al., the switch cannot be observed on the Stark-Werner potential surface, due to a small artificial barrier at high H-HF separation, preventing the reactants from obeying the attractive potential and also proving the importance of the latter. The exchange reaction can be observed even when the total energy available for the partners is below the exchange barrier, because at low translational energies the product F atom of a successful abstraction step can re-abstract that H atom from the intermediate product H-2 molecule that was originally the attacker.