Nitric esters

Liquid and volatile nitric esters, being safer to handle and more stable chemically than nitroglycerine or diethylene glycol dinitrate (DGDN), can be employed as monopropellant jet fuels. Among these compounds methyl nitrate should be mention- 

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G. S. Biasutti, Safe Manufacture and Handling of Eiquid Nitric Esters, ACS Symposium Series No. 22, ACS, Washiagton, D.C., 1975. 

In 1833 Braconnot obtained nitric esters of cellulose and starch by acting with nitric acid on plant fibres and starch, at low temperature. 

Nitrolysis may also proceed without giving rise to alcohol in accordance with Eq (2), Nevertheless, a nitric ester is formed by the possible action of the N03— ion on a free alkyl cation ... 

Nitrogen tetroxide is formed as an undesirable product in several instances, eg, during the storage of some energetic materials, particularly NC, NG and mixts contg them, such as propints and Dynamite. In these Ihe nitric esters decomp at elevated temps. In some cases, even such stable nitrocompds as TNT can begin to evolve N02 when stored at higher than ambient temps. 

Schneider and Ziervogel (Ref 2) obtained nitric esters of pectin as intermediate products which were then esterified by means of acet anhydr to the corresponding acetates. In 1949, Rogovin, Treyvas and Shorygina (Ref 5) prepd pectin nitric esters by nitrating pectic acid for 4 hrs at 20° in a mixt composed of 48% HN03,... 

Data For Nitric Esters, Nitramines, Nitroalkyl-benzenes, and Derivatives of Phenol, Aniline, Urea, Carbamic Acid, Diphenylamine, and Tri-phenylamine , AnalChem 23,1740-7 (1951) CA 46, 5434 (1952) 71) T.L. Cottrel S. 

Expls may be classified both from the chemical point of view and according to their uses. From the chemical viewpoint we distinguish between chemical individual substances and mixts. The former are divided into (1) nitro compds, (2) nitric esters, (3) nitramines, (4) derivatives of chloric and perchloric acids, (5) azides, and (6) various compds capable of pro-during an expln, for example fulminates, acetyl-ides, nitrogen rich compds such as tetrazene, peroxides and ozonides, etc... 

The proplnts developed by Aerojet (Ref 3) use v small amts of ferric acetylacetonate as the catalyst or polymerization agent. Proplnts developed by JPL (Ref 2) use hexamethylene diisocyanate as the copolymer of PGN, together with a nitric ester plasticizer and ferric acetylacetonate as the curing catalyst. 

What has been said about sulfonic esters applies also to sulfuric, phosphoric and nitric esters and of course the hydrolysis of halides must necessarily always yield a carbonium cation. 

Photolysis of the nitric esters 80-82 causes nitrogen-oxygen bond-... 

Nitric Acid.—In the presence of concentrated sulphuric acid ethylene yields the nitric ester of nitroethyl alcohol. 

The photochemical removal of nitric esters may be conducted in yields of 92-100%, although byproducts resulting from ring fission may be expected. 

Hewkin, D. J., Hicks, J. A., fowling, J., and Watts, H., The Combustion of Nitric Ester-Based Propellants Ballistic Modification by Lead Compounds, Combustion Science and Technology, Vol. 2,1971,... 

C. P. Spaeth, 29, 5660 (1935) Ignition composition for the top charge in blasting caps, comprised of NC impregnated with a liquid explosive nitric ester, such as NG and KC103 USP 2007223 (1935)... 

It was shown by the above authors that nitrogen content of nitric esters such as NG or NC cannot be determined by the nitrometer method, if stabilizers such as centralite are present, because centralite absorbs some nitrogen oxides thus giving a low result for N. The difference between the nitrometer N content of NG in absence of a stabilizer and N content of NG in presence of a stabilizer may be taken as an index of stabilizing action of the stabilizer the bigger the difference, the better the stabilizer. This difference is called indice nitrometrique... 

Nitric esters also behave similarly to sulfonic esters in leading to epoxides,27 but the reactions are preparatively less satisfactory, and have not been exploited. 

Circular dichroism of the nitrato (ONO) chromophore of the mono- and di-nitric esters of l,4 3,6-dianhydrohexitols was found to consist of two dichroic bands, one weak and positive, at about 265 nm, and a stronger band at —228 nm, which was positive for the endo-(R)-nitrato chromophore and negative for the exo-(S)-nitrato group.68 However, for l,4 3,6-dianhydro-D-glucitol dinitrate, which has both an endo and an exo nitrato group, both bands were positive, but [ ]ma r (+ 7,260) for the band at 225 nm was about half of the algebraic sum of this band for the di-endo (+ 18,400) and di-exo (—4,460) compounds. 

Note Robpulvermasse, Raw Propellant Mass or Rawpaste was a mixture of water-wet NC witb an expl oil, such as MtrT NG, DEGDN, TEGDN, etc. Such wet mixt was safely transported when a smokeless propint plant was not located adjacent to the plants manufg NC and organic nitric esters. Prepn of Roh-... 

Explosive Compositions, Brisont (of High Density). The following expl compns con eg solid TNT and liquid nitric esters are described. Nitroglycerin 15—20, soluble Nitrocellulose 0—7.5, Kieselguhr 0—5, stabilizer 0-2.5, TNT 85-70%. The TNT is in the form of crushed flakes Ref J. Taylor and S.H. Davidson, BritP 578371 (1946) CA 41, 1842 (1947)... 

Explosiveness and Constitution, According to Majrich, the explosiveness depends not only on the nature of the carbon chain, but alsd on other groups. For instance the aldehyde, Keto and carboxylic groups lower the brisance, sensitiveness and stability, especially in nitric esters and the stability seems to increase with increasing mol wt Ref A. Majrich, Chem Obzor 7, 104-8,... 

Explosive Nitric Esters, Liquid. Spout wash water formed in the mfg of liquid expl nitric esters is created with a non expl aromatic nitro hydrocarbon e. g. 0-Nitro toluene (1), to extract the expl esters and render the wash water safe for disposal. Wash water from a Nitro glycerine (II) plant contg 0-35% II was treated at a rate of 25000 lbs/8 hrs with 1000 pounds of (I) which was continuous ly recycled so as to give a 2 1 wash water I vol ratio Ref W.G.Allan et al, Brit P7345 2 3 (1955)... 

J.T. Power K..R. Btown, USP 2102187 (1937) CA 32, 1455 (1938) (Gelatinization of NC with an organic nitric ester is improved by incorporating a small amt of an accelerator such as ethoxyethyl nitrate or acetate)... 

CDj) T. Urbanski, Vol 2(1965), pp 22-31 gives methods for determining the Stability of Nitric Esters, which include Abel Heat Test, Litmus Test (Vieille Test), Heat Test at 134.5°C, Silvered Vessel Test, Loss of Weight Test, Will Test, Bergmann Junk Test and Manometric Test... 

Nitramines differ from nitro compounds in possessing a somewhat better oxygen balance, due to the fact that the group N—N02 gives twice the volume of nitrogen as the group C—N02. On the other hand nitramines have a worse oxygen balance than nitric esters. 

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