Nitrogen
Oxides

Nitrogen forms nine molecular oxides, some of which were the first gases to be identified: N O (nitrous oxide), NO (nitric oxide), N O (dinitrogen trioxide), NO (nitrogen dioxide), N O (dinitrogen tetroxide), N O (dinitrogen pentoxide), N O (nitrosylazide), and N(NO) (trinitramide). All are thermally unstable towards decomposition to their elements. One other possible oxide that has not yet been synthesised is oxatetrazole (N O), an aromatic ring.

Nitrous oxide (N O), better known as laughing gas, is made by thermal decomposition of molten ammonium nitrate at 250 °C. This is a redox reaction and thus nitric oxide and nitrogen are also produced as byproducts. It is mostly used as a propellant and aerating agent for sprayed canned whipped cream, and was formerly commonly used as an anaesthetic. Despite appearances, it cannot be considered to be the anhydride of hyponitrous acid (H N O) because that acid is not produced by the dissolution of nitrous oxide in water. It is rather unreactive (not reacting with the halogens, the alkali metals, or ozone at room temperature, although reactivity increases upon heating) and has the unsymmetrical structure N–N–O (N≡N O ↔ N=N =O): above 600 °C it dissociates by breaking the weaker N–O bond. Nitric oxide (NO) is the simplest stable molecule with an odd number of electrons. In mammals, including humans, it is an important cellular signaling molecule involved in many physiological and pathological processes. It is formed by catalytic oxidation of ammonia. It is a colourless paramagnetic gas that, being thermodynamically unstable, decomposes to nitrogen and oxygen gas at 1100–1200 °C. Its bonding is similar to that in nitrogen, but one extra electron is added to a π * antibonding orbital and thus the bond order has been reduced to approximately 2.5; hence dimerisation to O=N–N=O is unfavourable except below the boiling point (where the cis isomer is more stable) because it does not actually increase the total bond order and because the unpaired electron is delocalised across the NO molecule, granting it stability. There is also evidence for the asymmetric red dimer O=N–O=N when nitric oxide is condensed with polar molecules. It reacts with oxygen to give brown nitrogen dioxide and with halogens to give nitrosyl halides. It also reacts with transition metal compounds to give nitrosyl complexes, most of which are deeply coloured.

Blue dinitrogen trioxide (N O) is only available as a solid because it rapidly dissociates above its melting point to give nitric oxide, nitrogen dioxide (NO), and dinitrogen tetroxide (N O). The latter two compounds are somewhat difficult to study individually because of the equilibrium between them, although sometimes dinitrogen tetroxide can react by heterolytic fission to nitrosonium and nitrate in a medium with high dielectric constant. Nitrogen dioxide is an acrid, corrosive brown gas. Both compounds may be easily prepared by decomposing a dry metal nitrate. Both react with water to form nitric acid. Dinitrogen tetroxide is very useful for the preparation of anhydrous metal nitrates and nitrato complexes, and it became the storable oxidiser of choice for many rockets in both the United States and USSR by the late 1950s. This is because it is a hypergolic propellant in combination with a hydrazine -based rocket fuel and can be easily stored since it is liquid at room temperature.

The thermally unstable and very reactive dinitrogen pentoxide (N O) is the anhydride of nitric acid, and can be made from it by dehydration with phosphorus pentoxide. It is of interest for the preparation of explosives. It is a deliquescent, colourless crystalline solid that is sensitive to light. In the solid state it is ionic with structure; as a gas and in solution it is molecular O N–O–NO. Hydration to nitric acid comes readily, as does analogous reaction with hydrogen peroxide giving peroxonitric acid (HOONO). It is a violent oxidising agent. Gaseous dinitrogen pentoxide decomposes as follows:
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