In situ solid-state NMR spectroscopy was employed to study the kinetics of hydrogen/deuterium exchange and scrambling as well as (13)C scrambling reactions of labeled propane over Al(2)O(3)-promoted sulfated zirconia (SZA) catalyst under mild conditions (30-102 degrees C). Three competitive pathways of isotope redistribution were observed during the course of the reaction: (1) a regioselective H/D exchange between acidic protons of the solid surface and the deuterons of the methyl group of propane-1,1,1,3,3,3-d(6), monitored by in situ (1)H MAS NMR; (2) an intramolecular H/D scrambling between methyl deuterons and protons of the methylene group, without exchange with the catalyst surface, monitored by in situ (2)H MAS NMR; (3) a intramolecular (13)C scrambling, by skeletal rearrangement process, favored at higher temperatures, monitored by in situ (13)C MAS NMR. The activation energy of (13)C scrambling was estimated to be very close to that of (2)H scrambling, suggesting that these two processes imply a common transition state, responsible for both vicinal hydride migration and protonated cyclopropane formation. All pathways are consistent with a classical carbenium ion-type mechanism.