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Gas chromatography/mass spectrometry was used to analyze the pyrolytic byproducts from an Army-unique propellant compound (AA2) that is composed of predominantly nitrocellulose and nitroglycerin. Compounds produced by AA2 pyrolysis were compared to compounds detected in the gaseous effluent from AA2 incineration. The light permanent gases and most of the higher molecular weight byproducts produced by AA2 incineration are replicated by laboratory pyrolysis on AA2. The reverse case also holds whereby 18 out of 24 high molecular weight AA2 pyrolytic byproducts are found in the incinerator emissions. Poor matching, however, was obtained between the two processes for the volatile, water-soluble species. None of these low molecular weight compounds produced under pyrolytic conditions were detected in the AA2 incinerator samples, likely indicating inefficient capture of these compounds from the effluent stream. Separate pyrolytic degradation of the individual components of AA2 provides evidence that nearly all of the incomplete combustion products detected during incineration originate not from the prevalent energetic ingredients but rather from the minor and trace additives in AA2. In addition, pyrolysis successfully identified the AA2 components capable of surviving the incineration process intact. This work illustrates the potential of bench-scale pyrolysis for predicting incineration behavior.