Dinitrogen trioxide (also known as nitrous anhydride) is the chemical compound with the formula . It is one of the simple nitrogen oxides. It forms upon mixing equal parts of nitric oxide and nitrogen dioxide and cooling the mixture below −21 °C (−6 °F):
Dinitrogen trioxide is only isolable at low temperatures, i.e. in the liquid and solid phases. In liquid and solid states, it has a deep blue color. At higher temperatures the equilibrium favors the constituent gases, with KD = 193 kPa (25 °C).
This compound is sometimes called "nitrogen trioxide", but this name properly refers to another compound, the (uncharged) nitrate radical .
Structure and bonding
Dinitrogen trioxide molecule contains an N–N bond. One of the numerous resonant structures of the molecule of dinitrogen trioxide is , which can be described as a nitroso group attached to a nitro group by a single bond between the two nitrogen atoms. All atoms and bonds of dinitrogen trioxide molecule contribute to the resonancy. The oxidation state of the nitrogen atom of the nitroso group is +3, while the oxidation state of the nitrogen atom of the nitro group is +5. This isomer is considered as the "anhydride" of the unstable nitrous acid (), and produces it when mixed with water, although an alternative structure might be anticipated for the true anhydride of nitrous acid, i.e. , but this isomer is not observed.
Typically, N–N bonds are similar in length to that in hydrazine (145 pm). Dinitrogen trioxide, however, has an unusually long N–N bond at 186 pm. Some other nitrogen oxides also possess long N–N bonds, including dinitrogen tetroxide (175 pm). The molecule is planar and exhibits Cs symmetry. The dimensions displayed on the picture below come from microwave spectroscopy of low-temperature, gaseous :
If the nitrous acid is not then used up quickly, it decomposes into nitric oxide and nitric acid. Nitrite salts are sometimes produced by adding to water solutions of bases: