Nitric Acid - Reactions - Reactions With Metals

Reactions With Metals

Nitric acid reacts with most metals but the details depend on the concentration of the acid and the nature of the metal. Dilute nitric acid behaves as a typical acid in its reaction with most metals. Magnesium, manganese and zinc liberate H₂. Others give the nitrogen oxides.

Nitric acid can oxidize non-active metals such as copper and silver. With these non-active or less electropositive metals the products depend on temperature and the acid concentration. For example, copper reacts with dilute nitric acid at ambient temperatures with a 3:8 stoichiometry.

3 Cu + 8 HNO₃ → 3 Cu2+ + 2 NO + 4 H₂O + 6 NO₃-

The nitric oxide produced may react with atmospheric oxygen to give nitrogen dioxide. With more concentrated nitric acid, nitrogen dioxide is produced directly in a reaction with 1:4 stoichiometry.

Cu + 4 H+ + 2 NO₃− → Cu2+ + 2 NO₂ + 2 H₂O

Upon reaction with nitric acid, most metals give the corresponding nitrates. Some metalloids and metals give the oxides, for instance, Sn, As, Sb, Ti are oxidized into SnO₂, As₂O₅, Sb₂O₅ and TiO₂ respectively.

Some precious metals, such as pure gold and platinum group metals do not react with nitric acid, though pure gold does react with aqua regia, a mixture of concentrated nitric acid and hydrochloric acid. However, some less noble metals (Ag, Cu, ...) present in some gold alloys relatively poor in gold such as colored gold can be easily oxidized and dissolved by nitric acid, leading to colour changes of the gold-alloy surface. Nitric acid is used as a cheap means in jewelry shops to quickly spot low-gold alloys (< 14 carats) and to rapidly assess the gold purity.

Being a powerful oxidizing agent, nitric acid reacts violently with many non-metallic compounds and the reactions may be explosive. Depending on the acid concentration, temperature and the reducing agent involved, the end products can be variable. Reaction takes place with all metals except the noble metals series and certain alloys. As a general rule, oxidizing reactions occur primarily with the concentrated acid, favoring the formation of nitrogen dioxide (NO₂). However, the powerful oxidizing properties of nitric acid is thermodynamic in nature, but sometimes its oxidation reactions are rather kinetically non-favored. The presence of small amounts of nitrous acid (HNO₂) greatly enhance the rate of reaction.

Although chromium (Cr), iron (Fe) and aluminium (Al) readily dissolve in dilute nitric acid, the concentrated acid forms a metal oxide layer that protects the bulk of the metal from further oxidation. The formation of this protective layer is called passivation. Typical passivation concentrations range from 20–50% by volume (See ASTM A967-05). Metals which are passivated by concentrated nitric acid are Iron, Cobalt, Chromium, Nickel, and Aluminium.