Decomposition Pathways of Ammonium Dinitramide (ADN) and its HNO3‐Clusters Elucidated by DFT‐Calculations. Issue 2 (14th September 2020)

• Record Type: Journal Article
• Authors: Lang, Johannes; Bohn, Manfred A.
• Is Part Of: Propellants, explosives, pyrotechnics. Volume 46:Issue 2(2021)
• Page Start: 233
• Page End: 244
• Publication Date: 2020-09-14
• Subjects: Ammonium dinitramide (ADN) -- Density functional theory (DFT) -- Computational chemistry -- Decomposition pathways -- Transition state structures; Propellants -- Periodicals; Explosives -- Periodicals; 662.2
• DOI: 10.1002/prep.202000165
• Languages: English
• ISSNs: 0721-3115

Abstract

Abstract: Ammonium dinitramide (ADN) may serve as a 'green' oxidizer for rocket propellants since it provides chlorine free and minimum signature exhaust gases. However, stability issues and an erratic decomposition behaviour limit its non‐questionable general usability. Nitric acid (HNO3 ) is a decomposition product of ADN and is known to accelerate the decomposition autocatalytically. In this study, we investigate the effect of HNO3 on the initial decomposition steps of ADN via quantum chemical calculations based on density functional theory (DFT) in vacuo as well as in an aqueous solution. We establish and compare the reaction profiles of ADN, its anion DN − and its acid HDN as well as their HNO3 ‐clusters [NO3 H_ADN], [NO3 H_DN] − and [NO3 H_HDN] towards the products NO2, HNO3 and N2 O. All species exhibit various isomers with distinct decomposition pathways. We complement our study by investigating the protonated, cationic species [H_ADN] +, which may form in a low pH regime. The HNO3 clusters reveal modulated energy barriers and in part altered decomposition pathways in comparison to the free DN −, HDN, and ADN species. The altered pathways include the formation of reactive intermediates (such as H2 NO3 + ) as well as the formation of two HNO3 molecules starting from one HNO3 molecule, hinting at accelerated decomposition of ADN due to interaction with HNO3 . Abstract :