The mechanism of the reaction of N₂O and ¹³CO over Fe-silicalite was investigated with the use of the temporal analysis of products (TAP) reactor and compared with that of the reaction of N₂O and C₃H₈ previously reported. Upon direct N₂O decomposition at 523-573 K, Fe-silicalite stored ca. 1018 atoms of oxygen per gram, with a ratio of 1 O atom per each 30-60 Fe atoms in the sample. Only a small fraction of the deposited oxygen was reactive for CO oxidation. Pump-probe experiments at different time delays (0-2 s) between the pulses of nitrous oxide and the reducing agent indicated the markedly different mechanisms of the N₂O-¹³CO and N₂O-C₃H₈ reactions in the temperature range of 623-673 K. Fe-silicalite is active for propane oxidation in the presence of short-lived oxygen species, that are produced when N₂O and C₃H₈ are pulsed simultaneously. Time delays between the N₂O and C₃H₈ pulses greater than 0.1 s are sufficient to transform these active oxygen species for hydrocarbon conversion into inactive ones. In contrast, the oxidation of CO by N₂O does not depend on the lifetime of the oxygen species in the range of time delays investigated. The mechanisms of the N₂O-mediated ¹³CO and C₃H₈ oxidations differ as a consequence of the different interactions of the two reducing agents with iron species in the zeolite. Pulse experiments support the occurrence of the scavenging mechanism with both propane and carbon monoxide. In this mechanism, short-lived oxygen deposited by N₂O is efficiently eliminated by the reductant. Distinctive to propane, the strikingly high affinity of carbon monoxide for isolated Fe3+ ions in the zeolite gives rise to an additional pathway for N₂O reduction in the presence of chemisorbed CO species. These particular Fe³⁺-CO species were identified by in situ UV/vis and EPR spectroscopies.