Mechanism study of ammonium nitrate decomposition with chloride impurity using experimental and molecular simulation approach

Highlights: • Advanced Reactive System Screening Tool used to investigate AN decomposition. • AN thermal decomposition releases more heat in presence of KCl. • Reaction mechanisms were proposed and supported by molecular simulation. • Cl radical catalyzes more exothermic AN side-decomposition reaction. -- Abstract: Fire/explosion due to ammonium nitrate (AN) decomposition poses significant safety hazards which are exacerbated in the presence of salts including potassium chloride (KCl). In this work, key thermal parameters of AN decomposition over a range of KCl mass fraction were experimentally measured using advanced reactive chemical screening tool (ARSST). Based on experimental findings and past literature review, AN/KCl decomposition mechanism was proposed consisting of four separate pathways, specifically, (i) direct AN main decomposition pathway, (ii) indirect AN main decomposition pathway via chlorine radical, (iii) direct pure AN side decomposition pathway and (iv) indirect AN side decomposition pathway via chlorine radical. Gaussian software was used to estimate activation energies for each reaction step involved in the proposed mechanism via density function theory (DFT). The computational chemistry model explained experimental data with good agreement. Both computational and experimental findings confirm that chlorine radical reduce reaction barrier of AN decomposition via indirect pathways (ii) and (iv). As these indirect decomposition pathways are more exothermic than the primary paths (i), (iii), KCl addition not only accelerates AN decomposition but also increases reaction heat release.