Chemistry and Technology of Explosives: 3-Volume Set by Tadeusz Urbanski
By Tadeusz Urbanski
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Extra resources for Chemistry and Technology of Explosives: 3-Volume Set
According to Titov in his early work of 1941, nitration with nitric acid of moderate concentration (60-80% HNO3) occurs through the action of NO2 (or N2O4) and nitric acid plays only the role of a source of NO2. However, Bunton and Halevi  have expressed the view that the nitronium ion mechanism is still responsible for C-nitration even in highly aqueous conditions. Bunton, Halevi and Llewellyn  in their work described above (p. 38) examined the mechanism of oxygen exchange between nitric acid and water in an aqueous nitric acid medium by using isotopically labelled water.
Konovalov  observed an important fact as long ago as 1895. He reported that aromatic hydrocarbons with side chains were nitrated with this mixture chiefly in the side chain. Shorygin and Sokolova  confirmed this observation in 1930. The kinetics of nitration of aromatic hydrocarbons with nitric acid in the presence of acetic anhydride was first studied by Tronov, Kamay and Kovalenko . Their studies will be discussed later. Menke  inferred from the results of his studies on nitration of aromatic hydrocarbons with mixtures of nitric acid and acetic anhydride that the latter acted not only as a dehydrating substance but also as a catalyst.
E. in the most common nitrating mixtures) are given in Figs. 11 and 12 respectively. NITRATION AND NITRATING AGENTS 29 The triangular diagram of Sapozhnikov was modified by Vandoni, on the basis of his own experimental data, to the diagram of HNO3 activities (Fig. 13). Thus instead of isobars of HNO3 vapour pressures he constructed curves of equal activities. The advantage of such a diagram is, among other things, that unlike vapour pressure, activity is independent of temperature. FIG. 12. Vapour pressure and activity H/H0 of HNO3 in the solution HNO3-H2SO4-H2O containing 50% HNO3 (Vandoni ).