The thermal decomposition of the highly energetic 1,5-diamino-4-methyl-1H-tetrazolium nitrate (2b), 1,5-diamino-4-methyl-1H-tetrazolium dinitramide (2c) and 1,5-diamino-4-methyl-1H-tetrazolium azide (2d) were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Mass spectrometry and IR spectroscopy were used to identify the gaseous products. Decomposition appears in the cases of 2c and 2d to be initiated by a proton transfer to form the corresponding acid HN3 and HN3O4 whereas in the case of 2b a methyl group transfer to MeONO2 is observed as initial process. The gaseous products after the exothermic decomposition are comparable and are in agreement of the possible decomposition pathways discussed for the corresponding compounds. For all processes, possible decomposition schemes are presented. The decomposition temperatures of 2b and 2c are significantly higher than that of 2d and were supported by evaluation the values of the activation energy according the method of Ozawa and Kissinger. (C) 2005 Elsevier B.V. All rights reserved.