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Dinitrogen tetroxide

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Dinitrogen tetroxide

Dinitrogen tetroxide, commonly referred to as nitrogen tetroxide (NTO), and occasionally (usually among ex-USSR/Russian rocket engineers) as amyl, is the chemical compound N2O4. It is a useful reagent in chemical synthesis. It forms an equilibrium mixture with nitrogen dioxide. Its molar mass is 92.011 g/mol.

Dinitrogen tetroxide is a powerful oxidizer that is hypergolic (spontaneously reacts) upon contact with various forms of hydrazine, which has made the pair a common bipropellant for rockets.

Dinitrogen tetroxide could be regarded as two nitro groups (-NO2) bonded together. It forms an equilibrium mixture with nitrogen dioxide. The molecule is planar with an N-N bond distance of 1.78 Å and N-O distances of 1.19 Å. The N-N distance corresponds to a weak bond, since it is significantly longer than the average N-N single bond length of 1.45 Å. This exceptionally weak σ bond (amounting to overlapping of the sp2 hybrid orbitals of the two NO2 units) results from the simultaneous delocalization of the bonding electron pair across the whole N2O4 molecule, and the considerable electrostatic repulsion of the doubly occupied molecular orbitals of each NO2 unit.

Unlike NO2, N2O4 is diamagnetic since it has no unpaired electrons. The liquid is also colorless but can appear as a brownish yellow liquid due to the presence of NO2 according to the following equilibrium:

Higher temperatures push the equilibrium towards nitrogen dioxide. Inevitably, some dinitrogen tetroxide is a component of smog containing nitrogen dioxide.

Solid N2O4 is white, and melts at −11.2 °C.

Nitrogen tetroxide is made by the catalytic oxidation of ammonia (the Ostwald process): steam is used as a diluent to reduce the combustion temperature. In the first step, the ammonia is oxidized into nitric oxide:

Most of the water is condensed out, and the gases are further cooled; the nitric oxide that was produced is oxidized to nitrogen dioxide, which is then dimerized into nitrogen tetroxide:

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