The thermal decomposition kinetics of the high explosive 1,3,3-trinitroazetidine (TNAZ) have been measured by nonisothermal differential scanning calorimetry (DSC). Samples of TNAZ in open pans and pierced pans undergo mainly melting (DeltaH(fus) = 27 +/- 3 kJ mol(-1)) and vaporization (DeltaH(vap) = 74 +/-10 kJ mol(-1)) during heating. However, when confined in sealed high-pressure crucibles, exothermic thermal decomposition is observed. The activation energy for thermal decomposition has been determined as a function of the extent of reaction by isoconversional analysis. The initial value of 184 U mol-I at the start of the reaction decreases to 38 U mol(-1) near the end of the reaction. The rates clearly exhibit acceleratory behavior that is ascribed to autocatalysis. The measured heat release of thermal decomposition (Q = 640 150 kJ mol-1) is independent of the heating rate and the sample mass. These results are consistent with proposed mechanisms of TNAZ decomposition in which the initial step is preferential loss of the nitramine NO2 group over loss of a gemdinitroalkyl NO2 group.