AbstractThe hydrolysis reactions ofN‐(2,4,6‐trinitrophenyl)piperidine (2) andN‐(2,4,6‐trinitrophenyl)‐morpholine (3) were studied. Two kinetic processes well separated in time are observed in both reactions. The fastest process, which is reversible, leads to the formation of a species of λmax260 and 410 nm and is attributed to the formation of a σ complex of stoichiometry 1 : 2 due to the addition of a second HO−to the σ complex of 1 : 1 stoichiometry. The slowest process leads quantitatively to picrate ion. The equilibrium constants for the formation of the σ complexes of 1:1 and 1:2 stoichiometries and the rate of formation and decomposition of the latter complex were determined. The kinetic data for the slow process lead to the conclusion that the picrate ion is formed from the attack of HO−on the two σ complexes, confirming previous findings. There are some differences in the calculated rates for2and3which may be an indication that the elimination of the amine is partiall