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Dinitraminic acid (HDN) isomerization and self-decomposition revisited
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Physical Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Physical Chemistry.ORCID iD: 0000-0003-2673-075X
2008 (English)In: Chemical Physics, ISSN 0301-0104, E-ISSN 1873-4421, Vol. 348, no 1-3, 53-60 p.Article in journal (Refereed) Published
Abstract [en]

Density functional theory (DFT) and the ab initio based CBS-QB3 method have been used to study possible decomposition pathways of dinitraminic acid HN(NO2)(2) (HDN) in gas-phase. The proton transfer isomer of HDN, O2NNN(O)OH, and its conformers can be formed and converted into each other through intra- and intermolecular proton transfer. The latter has been shown to proceed substantially faster via double proton transfer. The main mechanism for HDN decomposition is found to be initiated by a dissociation reaction, splitting of nitrogen dioxide from either HDN or the HDN isomer. This reaction has an activation enthalpy of 36.5 kcal/mol at the CBS-QB3 level, which is in good agreement with experimental estimates of the decomposition barrier.

Place, publisher, year, edition, pages
2008. Vol. 348, no 1-3, 53-60 p.
Keyword [en]
Ammonium dinitramide (ADN), Decomposition pathways, Double proton transfer, Solid rocket propellant, Quantum chemistry, DFT
National Category
Theoretical Chemistry
URN: urn:nbn:se:kth:diva-17603DOI: 10.1016/j.chemphys.2008.02.044ISI: 000256737200007ScopusID: 2-s2.0-43849097420OAI: diva2:335647
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2010-11-03Bibliographically approved
In thesis
1. Green Propellants
Open this publication in new window or tab >>Green Propellants
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

To enable future environmentally friendly access to space by means of solid rocket propulsion a viable replacement to the hazardous ammonium perchlorate oxidizer is needed. Ammonium dinitramide (ADN) is one of few such compounds currently known. Unfortunately compatibility issues with many polymer binder systems and unexplained solid-state behavior have thus far hampered the development of ADN-based propellants.

Chapters one, two and three offer a general introduction to the thesis, and into relevant aspects of quantum chemistry and polymer chemistry.

Chapter four of this thesis presents extensive quantum chemical and spectroscopic studies that explain much of ADN’s anomalous reactivity, solid-state behavior and thermal stability. Polarization of surface dinitramide anions has been identified as the main reason for the decreased stability of solid ADN, and theoretical models have been developed to explain and predict the solid-state stability of general dinitramide salts. Experimental decomposition characteristics for ADN, such as activation energy and decomposition products, have been explained for different physical conditions. The reactivity of ADN towards many chemical groups is explained by ammonium-mediated conjugate addition reactions. It is predicted that ADN can be stabilized by changing the surface chemistry with additives, for example by using hydrogen bond donors, and by trapping radical intermediates using suitable amine-functionalities.

Chapter five presents several conceptual green energetic materials (GEMs), including different pentazolate derivatives, which have been subjected to thorough theoretical studies. One of these, trinitramide (TNA), has been synthesized and characterized by vibrational and nuclear magnetic resonance spectroscopy.

Finally, chapter six covers the synthesis of several polymeric materials based on polyoxetanes, which have been tested for compatibility with ADN. Successful formation of polymer matrices based on the ADN-compatible polyglycidyl azide polymer (GAP) has been demonstrated using a novel type of macromolecular curing agent. In light of these results further work towards ADN-propellants is strongly encouraged.

Place, publisher, year, edition, pages
Stockholm: KTH, 2010. 77 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2010:43
Quantum chemistry, reaction kinetics, ammonium dinitramide, high energy density materials, rocket propellants, chemical spectroscopy, polymer synthesis
National Category
Theoretical Chemistry Physical Chemistry
urn:nbn:se:kth:diva-25835 (URN)978-91-7415-758-1 (ISBN)
Public defence
2010-11-23, F1, Lindstedtsvägen 22, KTH, Stockholm, 09:30 (English)
QC 20101103Available from: 2010-11-03 Created: 2010-11-02 Last updated: 2011-03-21Bibliographically approved

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