Reaction Mechanisms of Inorganic Nitrogen Compounds

Stedman, G. Reaction Mechanisms of Inorganic Nitrogen Compounds, Adv. Inorg. Chem. Radiochem. 22 [1979] 113/70,121. 

One of the most active fields in the study of mechanisms of reactions of inorganic nitrogen compounds is electrophilic nitrosation reactions. A very comprehensive monograph has been published on this topic, with a chapter devoted to nitrosation by inorganic nitrosyl complexes. The rate law for the most active nitrosating species normally takes the form of equation (24), and there has been... 

Andrews and co-workers have used the matrix reaction between lithium atoms and some inorganic compounds to produce species of spectroscopic interest. Reaction of lithium with molecular oxygen [301] produces, in addition to the molecule Li02, the molecule LiO and a dimer Li2 02. Reaction with nitric oxide produced a nitroxide compound [302], but analysis of the infrared spectrum indicated that in this compound the lithium atom was bound to the oxygen atom (LiON), rather than to the nitrogen atom (LiNO), as would be expected by analogy with the known compounds HNO and RNO. The matrix deposition of lithium and nitrous oxide [303] leads to the formation of LiO and LijO. The other alkali metals have also been reacted in the same way with nitrous oxide [304]. Potassium, rubidium and caesium all led to the formation of the compounds MO and M2O. No sodium oxides were produced when sodium and nitrous oxide were co-deposited. This is to be compared with the mechanism advanced for the sodium-catalysed gas-phase reaction between N2O and CO, where sodium is assumed to react with N2O, (Section 4, ref. 

Current processes for the manufacture of trinitrotoluene (TNT) produce atmospheric and water pollution that is only partly relieved by mechanical clean-up methods. TNT is currently produced from toluene by successive mono-, di-, and trinitrations with mixed aqueous nitric and sulfuric acids in the first two steps and anhydrous mixed acid in the last. Each stage in the current process is conducted at elevated temperatures, and side reactions in the overall process directly produce thousands of pounds of oxides of nitrogen, sulfuric acid aerosols, and volatile nitro organic products (such as tetranitromethane and nitroaro-matics). These pollutants derive from the thermal decomposition of the aqueous nitric acid solutions, from oxidative side reactions that produce as many as 40 by-product compounds, and from formation of unsymmetrlcal "meta" Isomers. Since symmetrical TNT is inevitably accompanied by meta isomers as well as oxidation products, the crude material is treated with sodium sulfite solutions to remove the undesirable Isomers and nitroaromatics by derivatization. The spent sulfite solution, known as "red water, is then disposed of by combustion to an inorganic ash. Itself a disposal problem. 

---