Nitrogen: Inorganic ChemistryBased in part on the article Nitrogen: Inorganic Chemistry by Harry H. Sisler which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Abstract

The chemistry of nitrogen and its compounds with hydrogen, oxygen, and halogens is discussed in this article. The high stability of the nitrogen–nitrogen triple bond in dinitrogen in comparison with nitrogen–nitrogen single or double bonds makes polynitrogen compounds promising, highly energetic materials. Recently, several new polynitrogen species have been detected experimentally and salts of the polynitrogen cation N 5 + have been isolated in bulk. Salts of the azide anion N 3 − are already used as highly energetic materials. Binary compounds of nitrogen and hydrogen include ammonia, hydrazine, and several metastable species with nitrogen–nitrogen bonds. Ammonia, which is the starting material for all industrially produced nitrogen compounds, is probably the most important industrial chemical. Most of the ammonia produced is used as fertilizer, whereas hydrazine is used as an energetic material. The monomeric nitrogen oxides are among the most simple odd‐electron molecules and play an important role in the chemistry of the atmosphere. In combustion engines, huge amounts of nitric oxide are formed, which influence the ozone cycle both in the troposphere and in the stratosphere. Nitric oxide is a chemical messenger in biological systems and it helps to regulate a diverse array of physiological processes, such as neurotransmission, blood pressure and blood clot prevention. Oxoacids of nitrogen include hydroxylamine, nitrous acid, and nitric acid. Nitric acid is a major industrial chemical, which is primarily used for nitrate fertilizer production. Hydroxylamine is a starting material for the production of polyamide synthetics. Chlorine, bromine, and iodine halogen nitrogen compounds include halogensubstituted derivatives of ammonia, hydrazine, and diimine. They are unstable species that decompose to molecules in excited states. Nitrogen fluorides are thermodynamically more stable than the other nitrogen halides. Ternary compounds of nitrogen, oxygen, and halogens include nitrosyl‐ and nitrylhalides as well as the halogen nitrates. The stability of these compounds decreases from fluorine to iodine.