This paper presents calorimeter measurement for the thermal decomposition of n-propyl nitrate (NPN), isopropyl nitrate (IPN) and 2-ethylhexyl nitrate (EHN). Similar experimental results of triethylene
glycol dinitrate (tri-EGDN) and tetraethylene glycol dinitrate (tetra-EGDN) are included for comparison. The potential energy
surfaces (PESs) along O-NO2 bond stretch are investigated using the DFT (B3P86, B3PW91 and B3LYP), ab initio Hartree-Fock and PM3 methods. The good coincidence
of experimental with theoretical results indicates that initial stage in the thermal decomposition of five nitrates is only
unimolecular homolytical dissociation of the O-NO2 bonds and the activation energies of thermolysis by DSC correspond to the energies of O-NO2 bond scission of nitrates.