AbstractThe simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) technique has been applied to measure the vapor pressures and evaluate the thermal decomposition chemistry of two energetic liquids, bis(2‐fluoro‐2,2‐dinitroethyl)formal (FEFO) and bis(2‐fluoro‐2,2‐dinitroethyl)difluoroformal (DFF). The resulting heat of vaporization (ΔHvap) and vapor pressure at 25°C are 20.3 ± 0.2 kcal/mol and 0.4 ± 0.1 millitorr for FEFO, and 17.3 ± 0.2 kcal/mol and 5.1 ± 1.1 millitorr for DFF. The thermal decomposition of FEFO indicates there are six major pyrolysis pathways. The results suggest that FEFO initially decomposes at 150°C by rearrangement of the nitro group (NO2) to the nitrite group (ONO), followed by loss of NO. Some NO2is also formed at 170°C. Between 200°C–300°C, further pyrolysis occurs. In one pathway, the FEFO backbone remains intact and a high molecular‐weight product is formed. The other three pathways involve scission of the FEFO backbone; one yielding CO2(possibly N2O), one yielding CH2O and CO, and one yielding C3H2NOF. Differences in the thermal decomposition behaviors in the liquid and gas phases are observed. In the thermal decomposition of DFF, the formal fluorine atoms stabilize the backbone structure. Numerous minor thermal decomposi