Energetic compounds nitrate esters

Methyl nitrate and methyl nitramine have been chosen as models for two other important classes of energetic materials, nitrate esters and nitramines. The X-NO2 bond dissociation energy for the nitrate was calculated to be 38 kcal/mol and that of the nitramine 47 kcal/mol, consistent with the well known trends in stability and sensitivity for nitro, nitrate and nitramine compounds. Assuming that X-NO2 bond scission is rate determining, then neither nitrate nor nitramine decomposition is affected by the presence of ammonia. 

This change in editorial leadership has resulted, perhaps inevitably, in a change in editorial policy which is reflected in the contents of Volume 8. There has been a marked de-emphasis on the inclusion of organic parent compounds followed by an exhaustive and voluminous cataloging of azide, azido, azo, diazido, diazonium, diazo, nitro, dinitro, polynitro, hitr amine, nitrate (esters and salts), dinitrate, poly nitrate, nitroso, polynitroso, chlorate, perchlorate, peroxide, picrate, etc, derivatives — regardless of whether any of these derivatives exhibit documented explosive or energetic properties. Only those materials having such properties have been included in this volume... 

The energetic nature of the N-NO2 group means that At-nitro-based explosives are some of the most powerful explosives available and these have largely superseded aromatic C-nitro compounds for military applications. Many nitramines exhibit high brisance and high chemical stability in combination with a favourable low sensitivity to impact and friction compared to nitrate ester explosives of similar power. 

In literature, there are several attempts described to predict and calculate the impact sensitivity of energetic materials. Most of these papers deal only with nitro- and nitrate ester compounds, whereas the impact sensitivity of azides has not been the subject of detailed calculations so far, apart from recently published structure-sensitivity correlations on inorganic azides. ... 

In evaluating the energetics of oxidizers, it is apparent that the perchlorate salts are more desirable than nitrate salts. Therefore one would expect that attempts would be made to incorporate the perchlorate group into binder structures. The study of perchlorate esters was not pursued when it was found that simple model compounds obtained from alcohols and perchloric acid were excessively shock sensitive. However, when the C104 group existed in ionic or salt-like form, these materials were found to be far less sensitive. Bell Aerosystems Corp., in conjunction with the Food Machinery Corp. prepared the polyethylene hydrazine perchlorates. 

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