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Explosive properties

Hydrazinium azide hydrazinate is not sensitive to shock (> 5kg/ 50 cm),

friction, sparks (>20 kV). The explosion of hydrazinium azide hydrazinateyields nitrogen, ammonia and hydrogen.

Conclusion

Hydrazinium azide hydrazinate is less hygroscopic and less volatile than

hydrazinium azide, though its melting point is lower. The explosion of thehydrazine adduct gives more ammonia than the explosion of hydraziniumazide.

Ludwig

MaximiliansUniversittMnchen

Anton Hammerl, Gerhard Holl, Manfred Kaiser

Thomas M. Klaptke*, Holger Piotrowski

Hydrazinium Azide Hydrazinateepartment of Chemistry, University of Munich, Butenandtstr. 5-13 (D), 81377 Munich, e-mail: Thomas.M.Klapoetke@cup.uni-muenchen.de

cm114 12 10 8 6 4 2 0 -2 ppm

[ H2NNH3 ]+

[ N3 ]

2.63 N2 + 1.91 H2 + 1.73 NH3

30 barH2NNH2

[ H2NNH3 ]+ [ N3 ]

+ H2NNH2 [ H2NNH3 ]+ [ N3 ]

H2NNH2

Introduction

Most high energetic materials, such as TNT, RDX, HMX and CL-20 derivetheir energy from the oxidation of the carbon backbone. Modern compoundssuch as CL-20 [1] or the recently reported hepta- and octanitrocubanes [2]

possess very high densities and utilize the cage strain of the molecules. Highnitrogen materials were investigated in recent years where the energy is derivedfrom the high positive heat of formation of the compound. These compounds are

often insensitive to electrostatic discharge, friction and impact like the recent 3,3'-azobis(6-amino-1,2,4,5-tetrazine). [3]

It was shown that the detonation velocity of hydrazinium azide at similardensities is greater than the detonation velocity of RDX, due to the formation of

hydrogen during the explosion. [4] Unfortunately, hydrazinium azide ishygroscopic and volatile and, therefore, not in commercial use. Thecharacteristics of hydrazinium azide were not improved by introducing organic

substituents. [5] Here the coordination of a hydrazine molecule to hydraziniumazide was investigated.

Synthesis

The first indication for a hydrazine adduct of hydrazinium azide was found byRieger, who isolated a colorless solid from a solution of hydrazinium azide in a

mixture of ethanol and hydrazine that had a different melting point thanhydrazinium azide. [6] While hydrazinium azide hydrazinate was mentioned inthe literature [7] prior to this work, the compound had never been characterized or

examined thoroughly. Hydrazinium azide hydrazinate was synthesized in astraightforward, [8] quantitative synthesis from equimolar amounts ofhydrazinium azide and hydrazine in an evacuated schlenk vessel by heating the

vessel for two days to 50 C. [9]

References

[1] R. L. Simpson, P.A. Urtiew, D. L. Ornellas, G. L. Moody, K. J. Scribner, D. M. Hofman, Propellants, Explos.

Pyrotech.1997, 22, 249 and references therein.

[2] M-X. Zhang, P. E. Eaton, R. Gilardi, Angew. Chem.2000, 112, 422;Angew. Chem. Int. Ed. Engl.2000, 39, 409.

[3] D. E. Chavez, M. A. Hiskey, R. D. Gilardi, Angew. Chem.2000, 112, 1861;Angew. Chem. Int. Ed. Engl.2000, 39,1791.

[4] G. S. Yakovleva, R. Kh. Kurbangalina, L. N. Stesik, Fiz. Goreniya Vzryva 1974, 10(2), 270-274.

[5] a) T. Habereder, A. Hammerl, G. Holl, T. M. Klaptke, J. Knizek, H. Nth,Eur. J. Inorg. Chem.1999, 849-852. b) T.Habereder, A. Hammerl, G. Holl, T. M. Klaptke, P. Mayer, H. Nth, Int. Annu. Conf. ICT2000, 31st, 150-1. c) A.

Hammerl, G. Holl, K. Hbler, T. M. Klaptke, P. Mayer,Eur. J. Inorg. Chem.2000, 755-760.d) A. Hammerl, G. Holl, M. Kaiser, T. M. Klaptke, P. Mayer, H. Nth, M. Warchhold, Z. Anorg. Allg. Chem., in press.

[6] H. D. Rieger, Ph.D. Thesis: Hydronitric acid and hydrazine trinitrate, Cornell University, Ithaca, New York, 1910.

[7] a) A. L. Dresser, A. W. Browne,J. Am. Chem. Soc.1933, 58, 261. b) E. P. Kirpichev, A. P. Alekseev, Y. I. Rubtsov,G. B. Manelis,Russian Journal of Physical Chemistry1973, 47, 1654.

[8] m.p.: 65 C. 1H NMR ([D6]DMSO): = 5.07 (s, NH). 14N NMR ([D6]DMSO): = -133 (NNN), -278 (NNN), -321

(NH2NH3, NH2NH2).15N NMR ([D6]DMSO): = -133.4 (NNN), -278.2 (NNN), -332.5 (NH3NH2), NH2NH2). IR (KBr):

/cm-1 = 3451 w, sh, 3356 m, 3285 m, 3168 m, 3063 m, 2958 m, 2603 m, sh, 2029 s, 1603 m, 1530 w, sh, 1342 w,

1260 w, 1096 m, 1016 w, sh, 949 w, 798 w, 649 w, 621 w, 552 w. - Raman (100 mW): /cm-1 = 3272 w, 3187 m,1643 w, 1337 s, 1250 w, 1143 w, 961 w, 942 w, 439 w, 325 w, 233 m, 195 m, 154 m, 129 m. DSC: 16 C, 65 C (m.p.),

151.5C. - N7H9: (107.12): Calc.: H 8.5 %, N 9 1.5 %; found: H 8.9 %, N 9 0.2 %.

Characterization

1H NMR

15N NMR

14N NMR

Raman

IR

N5N4

N6N7

2.24(2) 2.21(2)

2.30(2)

2.07(2)

1.92(2)

1.73(2)

2.21(2)

2.22(2) 2.26(2)

N5N4

N3N2N1N6

N7

2.07(2)

2.30(2)

2.21(2)

2.21

2.26 (2)

2.22(2)

DSC