Thermal Decomposition of Erythritol Tetranitrate: A Joint Experimental and Computational Study

• Published in: Journal of physical chemistry. C 2017-08, Vol.121 (30), p.16145-16157
• Main Authors: Oxley, Jimmie C, Furman, David, Brown, Austin C, Dubnikova, Faina, Smith, James L, Kosloff, Ronnie, Zeiri, Yehuda
• Format: Article
• Language: English
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.7b04668

Pentaerythritol tetranitrate (PETN) finds many uses in the energetic materials community. Due to the recent availability of erythritol, erythritol tetranitrate (ETN) can now be readily synthesized. Accordingly, its complete characterization, especially its stability, is of great interest. This work examines the thermal decomposition of ETN, both through experimental and computational methods. In addition to kinetic parameters, decomposition products were examined to elucidate its decomposition pathway. It is found that ETN begins its decomposition sequence by a unimolecular homolytic cleavage of the internal and external O–NO2 bonds, while the competing HONO elimination reaction is largely suppressed. The global activation energy for decomposition is found to be 104.3 kJ/mol with a pre-exponential factor of 3.72 × 109 s–1. Despite the ability to exist in a molten state, ETN has a lower thermal stability than its counterpart PETN.