Nitration in concentrated and aqueous nitric acid

Molecular nitric acid is the main species present in this medium, but physical measurements demonstrate the existence of significant concentrations of other species. 

At the freezing point of nitric acid (— 42 °C), the concentrations of water, nitronium ion, and nitrate ion were found to be 0.41 mol 1 , but more recent work suggests the value 0-69 mol 1 . Measurements of the electrical conductivity of nitric acid at —10 °C give a value of 0-51 mol 1 , and at —20 °C of o-6i mol 1 for the concentrations of the three species.  

The Raman spectrum of nitric acid shows two weak bands at 1050 and 1400 cm. By comparison with the spectra of isolated nitronium salts ( 2.3.1), these bonds were attributed to the nitrate and nitronium ion respectively. Solutions of dinitrogen pentoxide in nitric acid show these bands , but not those characteristic of the covalent anhydride , indicating that the self-dehydration of nitric acid does not lead to molecular dinitrogen pentoxide. Later work on the Raman spectrum indicates that at —15 °C the concentrations of nitrate and nitronium ion are 0-37 mol 1 and 0 34 mol 1 , respectively. The infra-red spectrum of nitric acid shows absorption bands characteristic of the nitronium ion. The equivalence of the concentrations of nitronium and nitrate ions argues against the importance of the following equilibrium  

The state of aqueous solutions of nitric acid In strongly acidic solutions water is a weaker base than its behaviour in dilute solutions would predict, for it is almost unprotonated in concentrated nitric acid, and only partially protonated in concentrated sulphuric acid. The addition of water to nitric acid affects the equilibrium leading to the formation of the nitronium and nitrate ions ( 2.2.1). The intensity of the peak in the Raman spectrum associated with the nitronium ion decreases with the progressive addition of water, and the peak is absent from the spectrum of solutions containing more than about 5% of water a similar effect has been observed in the infra-red spectrum.  

Because water is not protonated in these solutions, its addition reduces the concentration of ions, and therefore the electrical conductivity. The conductivity reaches a minimum in solutions containing 97% of acid, but rises on further dilution as a result of the formation of nitrate and hydroxonium ions.  

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