The thermal decomposition of two energetic ionic liquids, formed by pairing the 4-amino-1,2,4-triazolium cation with chloride (4ATCl), and nitrate (4ATN) anions, was studied by confined rapid thermolysis. Rapidscan FTIR spectroscopy and time-of-flight mass spectrometry were utilized in conjunction to identify the products of decomposition. Decomposition was achieved under heating rates of 2000 K/s and temperatures up to 340 degrees C for 4ATCl and 4ATN in an ambient inert gas at 1 atm. Whereas a proton transfer from the N-1 position primarily initiated decomposition in 4ATCl, the amino group was found to primarily participate in the initiation reaction in case of 4ATN. The parent molecule, 1-H- 1,2,4-triazole, was detected during subsequent reactions. Ring fracture was also evident from the presence of HCN. The highly energetic nitrate salt formed copious amounts of H2O and N2O through multiple secondary reaction channels. (C) 2007 Elsevier B.V. All rights reserved.