By Tadeusz Urbanski
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Extra info for Chemistry and Technology of Explosives: 3-Volume Set
Since in nitration FIG. 16. Variation of the rate of the nitration constant against the concentrations of sulphuric acid in the nitrating mixture: I - Nitration of nitrobenzene at 25°C (Westheimer and Kharasch ). II - Nitration of nitrobenzene at 25°C (Martinsen ); III - Nitration of dinitromesitylene at 25°C (Westheimer and Kharasch ); IV - Nitration of nitrobenzene at 0°C (Martinsen ); V - Nitration of anthraquinone at 25°C (Latter and Oda ); VI - Nitration of dinitrotoluene at 90°C (Bennett [S]).
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 ). Activity as a function was introduced by Lewis in 1908, and a full description was given by Lewis and Randall  in 1923. 76] as a value corresponding to the mole fraction of the substance “i” in the given phase.
Bunton and Halevi have examined the following reactions (O* denotes heavy oxygen) : + HNO 3 + HNO 3 <-> H 2NO 3 + NO 3 nitration : oxygen exchange: (a) H 2NO 3+ <-> NO2+ + H 2O (b) NO 2+ + RH <-> RNO2 + H + (c) NO 2+ + H 2O* <-> H 2NO 3* + H 2NO 3* + <-> H + + HNO 3* (d) (e) NITRATION AND NITRATING AGENTS 39 and have inferred that both nitration and oxygen exchange involve formation (b) and destruction (c, d) of the nitronium ion. Reactions (c) and (d) are competitive with preference for reaction (d).
Chemistry and Technology of Explosives: 3-Volume Set by Tadeusz Urbanski