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Thermal Decomposition of Energetic Materials 41. Fast thermolysis of cyclic and acyclic ethanediammonium dinitrate salts and their oxonium nitrate double salts, and the crystal structure of piperazinium dinitrate
Author(s) -
Russell T. P.,
Brill T. B.,
Rheingold A. L.,
Haggerty B. S.
Publication year - 1990
Publication title -
propellants, explosives, pyrotechnics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.56
H-Index - 65
eISSN - 1521-4087
pISSN - 0721-3115
DOI - 10.1002/prep.19900150303
Subject(s) - oxonium ion , thermal decomposition , chemistry , decomposition , molecule , crystal structure , ammonium nitrate , inorganic chemistry , ammonium , organic chemistry , ion
Fast thermolysis/FTIR spectroscopy of [H 3 NCH 2 CH 2 NH 3 ]‐(NO 3 ) 2 (EDD), [H 2 N(CH 2 CH 2 ) 2 NH 2 ](NO 3 ) 2 (PIPDN), and [HN(CH 2 CH 2 ) 3 NH](NO 3 ) 2 (DABCOD) and new oxonium nitrate (H 3 O + NO −3 ) double salts of PIPDN and DABCOD is described. EDD initially yields HNO 3 and then small molecule decomposition products from redox reactions when heated at ≥ 100°C (dcc.). PIPDN initially yields HNO 3 , but then generates a significant amount of N,N′‐dinitrosopiperazine along with small molecule fragments. DABCOD produces no HNO 3 (g), but instead gives CH 2 O, N,N′‐dinitrosopiperazine and small molecule products. These patterns are entirely consistent with the behavior observed for primary, secondary and teritary ammonium mononitrate salts in our previous work. The presence of nitrosamines strongly increases the health hazard of the matcrials upon heating. No nitramines were detected as thermolysis products. Thermolysis of the oxonium nitrate double salts liberates HNO 3 and H 2 O at a relatively low temperature (≥ 60 °C). Above this temperature, the thenmolysis proceeds in the same way as that of pure PIPDN and DABCOD. The crystal structure of PIPDN is described.