Mechanism of enhanced oxidation ability of dilute nitric acid and dissolution of pure gold in seawater with nitric acid

doi:10.26565/2220-637X-2019-33-01

Masashi Hojo Kochi University https://orcid.org/0000-0001-7936-8104

DOI: https://doi.org/10.26565/2220-637X-2019-33-01

Keywords: nitryl or nitronium ion, CTAC, evolution of chlorine, oxidation of bromide, salt effect, bulk water structure, dilute aqua regia, tetrachloroaurate, concentrated salt, Raman spectrum

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 CaCl₂as 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 <1.0 mol dm^-3 HNO₃ and <1.0 mol dm^-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.

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