The problem of clustering of quenched-in vacancies into various types of extended defects is considered. A master equation for the evolution of the concentration of clusters of various sizes is written down with general transition rates. It is shown that this model represents a continuous time non-stationary Markoff process. A particular choice of transition rates corresponding to the formation of vacancy loops and stacking fault tetrahedra is considered in some detail. It is shown that this choice of transition rates allows us to obtain the solution for the concentration of the single vacancy units, and hence yields some information on the nucleation time. Further, the transition matrix becomes stationary and doubly stochastic due to the short time constant of the concentration of single vacancy units. This in turn leads to an unphysical stationary state. Finally we show how the rate equations for the irradiated situation can be written down and derive the phenomenological rate equations that are conventionally used. © 1977 Indian Academy of Sciences.