Decomposition temperatures have been compiled for a set of 24 compounds including nitroalkanes, nitramines and nitric esters. In an attempt to rationalize their values, correlations involving either the dissociation energy for the weakest bond in the molecule or the proportion of trigger linkages are investigated. The latter quantity correlates fairly well with thermal stabilities. A simple model based on kinetic parameters associated with the breaking of trigger linkages allows the estimation of decomposition temperatures with an average absolute deviation from experiment < 11degreesC and no error >30degreesC, except two outliers with errors similar or equal to70-80degreesC. The latter are associated with nitramines bearing esters or furazan moieties, which prove less stable than expected on the basis of their number of trigger linkages. (C) 2004 Elsevier B.V. All rights reserved.