The role of extra-framework Al (EFAL) species on industrially important reactions such as alkane cracking has been extensively discussed and debated. It has long been known that water treatments influence the framework aluminum sites and, in some cases, can modify activity. What is less understood, however, is the direct relationship between the structural modifications and reactivity of important reactions such as alkane cracking and isomerization. The collective understanding of the multiple roles that water plays in the modification of zeolites and influence on reaction rates is continuously evolving. Extra-lattice Al species in close proximity to a framework Brønsted acid sites (BAS) have been proposed to modify the energies associated with surface intermediates and kinetically relevant transition states, which results in an enhancement in the rates of alkane cracking reactions. However, the kinetic role of water on the migration of these extra-framework alumina species to generate highly active sites is less understood and is the focus of this study. Water is introduced in controlled pulses to ZSM-5 zeolites with various Si/Al ratios and EFAL densities, with responses in n-hexane cracking activity used to investigate the generation of new active sites. A pulse technique allows decoupling of water dosing, lattice rearrangement, and drying, thereby enabling the quantification of activation energies associated with the generation of new active sites without losses in crystallinity or total BAS density. Further, by subtraction of the contributions to the reaction rate associated with isolated BAS, the reaction rate associated with the newly created sites is estimated. The results show that the energy barrier required for cracking on highly active sites is much lower than that observed on traditional Brønsted sites (75 vs 110 kJ/mol). The temperature dependence for the generation of these new sites reveals a 44 kJ/mol activation energy for the kinetically relevant step associated with their generation in the presence of water vapor, which to the best of our knowledge has not been previously quantified. It is reported that, while water vapor is essential for the generation of these new active sites, it also binds to these sites and strongly inhibits the cracking rate. These findings clarify some of the conflicting reports regarding the role of water in activity enhancement.