Cover: There are two competing RAFT polymerization theories: Intermediate Radical Termination (IRT) and Slow Fragmentation (SF). Using direct integration methods and the QSSA (quasi steady state approximation) the full MWD, that contains essential information for mechanism discrimination, can be calculated. Further details can be found in the article by I. Zapata-González, E. Saldívar-Guerra,* and J. Ortiz-Cisneros on page 370. Contents www.mts-journal.deThe full molecular weight distribution (FMWD) in RAFT polymerization is solved by direct integration for the slow fragmentation (SF) and the intermediate radical termination (IRT) models using the steady state approximation when possible. A marked bimodality is found for the FMWD of the SF model only, which suggests radical trapping experiments and GPC measurements to discriminate among models.

Cover: There are two competing RAFT polymerization theories: Intermediate Radical Termination (IRT) and Slow Fragmentation (SF). Using direct integration methods and the QSSA (quasi steady state approximation) the full MWD, that contains essential information for mechanism discrimination, can be calculated. Further details can be found in the article by I. Zapata‐González, E. Saldívar‐Guerra,* and J. Ortiz‐Cisneros .

In this work the molecular weight distribution (MWD) of several atom transfer radical polymerization (ATRP) techniques has been derived and solved using the Reduced Stiffness by Quasi Steady State Approximation (RSQSSA) methodology. The Quasi Steady State Approximation has been validated on the living radicals for normal, Simultaneous Reversible and Normal Initiation and Activators Regenerated by Electron Transfer (ARGET), and it is shown that the information lost due to its application is negligible. According to these results, RSQSSA shows the best performance in terms of wall-clock time and required memory in comparison to implicit techniques and Predici. In the case of the ARGET technique, the model predictions show good agreement with experimental data. Finally, an analysis on the impact of the slow and fast activation of the initiator on the MWD using ARGET has been carried out, indicating that the optimal initiator to control the MWD should exhibit activation-deactivation rates very similar to those of the polymeric equilibrium.