Microscopic kinetics of scission and reformation in the pyrolysis of nitrocellulose

Abstract Nitrocellulose (NC) is essential in high‐energy propellants, with nitrogen content affecting its pyrolysis rate and thermal stability. This study creates all‐atom models of NC with varying nitrogen levels to explore pyrolysis mechanisms and validate them against experimental thermal response data. Results show that RO − NO 2 bond cleavage initiates NC decomposition. Lower nitration levels convert nitrogen oxides into carbon‐nitrogen compounds, primarily HCN. Additionally, HCHO production is linked to CH 2 ONO 2 group transformation, with low‐nitration, high‐hydrogen NC reducing HCHO yield. Kinetic parameters for cellulose thermal decomposition indicate that pyrolysis activation energies decrease with nitration levels, demonstrating that nitration significantly lowers the energy barrier for ring‐opening. Molecular dynamics simulations reveal pathways for HCHO, NO 2 , and NO generation during combustion, enhancing understanding of NC combustion mechanisms and safety in explosive applications.