Property and Preparation of Ethyl Nitrate

Ethyl nitrate, with other names of ethanol nitrate ester and nitric acid ethyl ester, is a transparent oily liquid with a slight sweetish odor. It can be dissolved into water and be miscible with alcohols and most other organic reagents. It also can dissolve cellulose nitrate. 

The nitration heat of ethanol is 25.94 kJ/mol, Thomson calculated the combustion heat -A77 and detonation heat (water) of ethyl nitrate to obtain the values of 1355.78 kJ/mol and 3568.95 J/g, respectively. The explosion property of ethyl nitrate has been well known. However, in a long period, few attentions have been paid to the compound. It only has been used as a component in the liquid fuel of rockets and in explosive mixture with other oxidizers for blasting. 

The expanding value of lead block with water of ethyl nitrate is 345 cm. The detonation velocity of ethyl nitrate in wide tubes is 6,000-7,000 m/s. A steady detonation can be obtained to fill ethyl nitrate into a thick-wall metal tube. The detonation velocities in a steel tube with a diameter of 27 and 60 mm are 5,800 and 6,020 m/s, respectively. In a steel tube with a diameter of 10 mm, the detonation cannot happen. The lead-block value of ethyl nitrate is larger than chrysolepic acid approximately by 20 %. Its shock sensitivity is low. 50 % of ethyl nitrate would be exploded at the height of 500 mm for 2,000 g faUing weight. 

In the preparation method of ethyl nitrate, cold ethanol will be dissolved into concentrated nitric acid with the density of 1.41 g/cm without nitrogen oxides. The 

The writer [53] invented the approach of continuous nitration of nitric acid vapor to prepare ethyl nitrate. The solution of alcohol and nitric acid was added dropwise into a reactor, in which a protective agent of carbonyl groups was contained. The products were continuously distilled out of the reaction system during the process of nitration reaction. Thus, the removal of ethyl nitrate makes the concentration of products low, favoring the forward reaction and increasing the yield of nitration. Meanwhile, because the retention time of nitrate esters in the thermal reactor is shortened, the amount of nitrous acid, as well as intermediates, is reduced, improving the safety of the production process. The reaction process can be described by the following equation. 

---