Abstract
It has been discovered that dilute nitric acid in reversed micelle systems can oxidize the Br- ion to Br2 and we have proposed that the nitryl (or nitronium) ion NO2+ should be the active species in the oxidation process. Nitration of phenol in reversed micelle systems with dilute nitric acid, CHCl3/CTAC/H2O (2.0 mol dm-3 HNO3 in the 1.0% (v/v) H2O phase), has been performed at 35 ºC to obtain 2- and 4-nitrophenols, where CTAC represents cetyltrimethylammonium chloride. In aqueous 2.0 mol dm-3 HNO3 solution accompanied by 4.0 mol dm-3 LiCl (and a small amount of LiBr as the bromide resource), trans-1,4-dibromo-2-butene was successfully brominated to 1,2,3,4-tetrabromobutane. This result is good evidence that the Br- ion can be oxidized to Br2 in dilute nitric acid (2.0 mol dm-3) providing it contains concentrated salts. For chloride salts, the cation effects increased as Et4N+ << Na+ < Li+ < Ca2+ < Mg2+. Even the evolution of Cl2 has been demonstrated from < 2.0 mol dm-3 HNO3 solution containing concentrated LiCl, MgCl2, and CaCl2 as well as AlCl3. The dissolution of precious metals (Au, Pt, and Pd), especially, of gold has been demonstrated in 0.1 - 2 mol dm-3 HNO3 accompanied by alkali metal, alkaline earth metal, and aluminum chlorides. The complete dissolution time of pure gold plate (20±2 mg, 0.1 mm thickness) in 2.0 mol dm-3 HNO3 accompanied by 1.0 mol dm-3 AlCl3 has been shortened remarkably with temperature increase from 15 to 80 ºC. The dissolution rate constants, log (k /s-1), of a piece of gold wire (19.7±0.5 mg) in 20 mL of 2.0 mol dm-3 HNO3 accompanied by the metal chlorides, in general, increase with increasing salt concentrations at 40 and 60 ºC. The gold can be dissolved in the solution of -3 HNO3 and -3 HCl, i.e. a “dilute aqua regia." We have achieved a total dissolution of five pieces of the gold wire (totally 0.10 g) in 100 mL of the 1:1 mixture between seawater and 2.0 mol dm-3 HNO3 at ca. 100 ºC.