Andalusite–staurolite–biotite hornfels metamorphosed beneath the mafic layered rocks of the Bushveld Complex, South Africa, preserves a detailed record of the relative timing of porphyroblast growth and metamorphic reactions. The sequence inferred from microstructures shows considerable overlap of the period of growth of porphyroblasts of staurolite, cordierite, biotite and andalusite, and the persistence over a similar interval of the reactant porphyroblastic phase chloritoid. This is inconsistent with calculations of equilibrium phase relations, and implies that disequilibrium processes controlled the prograde reaction sequence, despite the slow heating rates involved (1 °C per 10 000 yr). The early appearance of cordierite by a metastable reaction and its subsequent disappearance indicates that delayed nucleation of porphyroblastic phases, rather than simply sluggish reaction, is required to account for the sequence of growth. The predicted reactions for the first appearance of andalusite and staurolite have low entropy of reaction, and do not occur until they have been overtaken in terms of reaction affinity by high-entropy devolatilisation reactions involving the breakdown of chlorite. Once the porphyroblasts have nucleated, metastable chloritoid-breakdown reactions also contribute to their growth. The implied magnitude of the critical overstepping for andalusite nucleation is around 5 kJ mole−1 (equivalent to 40 °C for the chlorite-breakdown reaction), and that for other phases is expected to decrease in the order andalusite>staurolite>cordierite. Coupling between nucleation rate, crystal growth rates and the resulting grain size distribution suggests that the rate constants of natural reactions are at least an order of magnitude lower than those measured in the laboratory. Pseudomorphs after chloritoid and cordierite conserve volume but not Al or other species of low mobility, suggesting a breakdown mechanism controlled by an interface process such as the slow dissolution of the refractory porphyroblast phase, rather than by a transport step.