By Tadeusz Urbanski
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Extra resources for Chemistry and Technology of Explosives: 3-Volume Set
Also Brennecke and Kobe  drew attention to the experiments of McKinley and White  who found that the acids for mononitration lie outside the nitronium ion envelope. All this created doubt as to whether the nitronium ion mechanism can be applied to all cases. As will be pointed out later, it seems that the mechanism of the nitration reaction is more complicated and may proceed under the influence of nitrating agents other than the NO2+ ion. 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.
Fredenhagen  developed a method sometimes referred to as “Fredenhagen nitration” . g. potassium nitrate in anhydrous or highly concentrated hydrogen fluoride. Metal nitrates in the presence of Friedel-Crafts catalysts Apart from the investigations on nitration with the nitrates of some metals in the presence of sulphuric or nitric acid Topchiyev  has carried out extensive studies on nitration with metal nitrates in the presence of AlCl3, FeCl3, SiCl4, and BF3. He showed that all the nitrates had nitrating properties, and he ordered the nitrates he studied according to their increasing nitration activity in the presence of AlCl3: NITRATION AND NITRATING AGENTS 47 Ba Ingold, Hughes and Reed  studied the kinetics of nitration of aromatic compounds with nitric acid only and found that it was a first order reaction. Its rate, VN, may be expressed by an approximate equation: V N = k 1 [ArH] at [HNO3] = const. g. nitration of dinitro- to trinitro compounds, or nitro derivatives of naphthalene, which are sparingly soluble in a nitrating mixture, nitration takes place in a two-phase system: acid-organic compound, the acid phase being a saturated solution of the organic compound.
Ingold, Hughes and Reed  studied the kinetics of nitration of aromatic compounds with nitric acid only and found that it was a first order reaction. Its rate, VN, may be expressed by an approximate equation: V N = k 1 [ArH] at [HNO3] = const. g. nitration of dinitro- to trinitro compounds, or nitro derivatives of naphthalene, which are sparingly soluble in a nitrating mixture, nitration takes place in a two-phase system: acid-organic compound, the acid phase being a saturated solution of the organic compound.