Abstract: | A method for the direct computation of the chain length distribution in a bulk polymerization is developed, based on the discretization procedure introduced by Kumar and Ramkrishna (Chem. Eng. Sci. 1996 , 51, 1311) in the context of particle size distribution. The overall distribution of chain lengths is partitioned into a finite number of classes which are supposed to be concentrated at some appropriate pivotal chain lengths. Several of the involved reactions lead to the formation of chain whose length differs from the pivotal values. Rules have been introduced in order to share chains between two contiguous classes, which have been designed so as to preserve two well‐defined properties of the distribution, such as, for example, two of its moments. The method has been applied to a polymerization system including propagation, bimolecular terminations and two different chain branching mechanisms: chain transfer to polymer and crosslinking. In addition, complex systems such as one with chain length‐dependent kinetic constants or a two‐dimensional distribution of chain length and number of branches have been considered. |