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Freshly prepared aqua regia is colorless, but it turns orange within seconds. Here, fresh aqua regia has been added to these NMR tubes to remove all traces of organic material.
Freshly prepared aqua regia to remove metal salt deposits.

Aqua regia or aqua regis (Latin for royal water or king's water) is a highly corrosive, fuming yellow or red solution, also called nitro-hydrochloric acid. The mixture is formed by freshly mixing concentrated nitric acid and concentrated hydrochloric acid, usually in a volumetric ratio of 1:3 respectively. It was so named because it can dissolve the so-called "royal metals," or noble metals, gold and platinum. However, tantalum, iridium, osmium, titanium and a few other metals are capable of withstanding chemical attack from it.

Contents

Applications

Aqua regia is primarily used to produce chloroauric acid, the electrolyte in the Wohlwill process. This process is used for refining highest quality (99.999%) gold. (See dissolving gold)

Aqua regia is also used in etching and in specific analytic procedures. It is also used in some laboratories to clean glassware of organic compounds and metal particles. This method is preferred over the "traditional" chromic acid bath for cleaning NMR tubes, because no traces of paramagnetic chromium can remain to later spoil acquired spectra.[1] Furthermore, chromic acid baths are discouraged because of the high toxicity of chromium and the potential for explosions. Aqua regia is itself very corrosive and has been implicated in several explosions due to mishandling.[2]

Due to the reaction between its components resulting in its decomposition, aqua regia quickly loses its effectiveness. As such, its components should only be mixed immediately before use. While local regulations may vary, aqua regia may be disposed of by carefully neutralizing with an appropriate agent—such as sodium bicarbonate—before pouring down the sink. If there is a large amount of metal in solution with the acid, it may be preferable to carefully neutralize it, and absorb the solution with a solid material such as vermiculite before discarding it with solid waste.

Chemistry

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Dissolving gold

Aqua regia dissolves gold, though neither constituent acid will do so alone, because, in combination, each acid performs a different task. Nitric acid is a powerful oxidizer, which will actually dissolve a virtually undetectable amount of gold, forming gold ions (Au3+). The hydrochloric acid provides a ready supply of chloride ions (Cl-), which react with the gold ions to produce chloroaurate anions, also in solution. The reaction with hydrochloric acid is an equilibrium reaction which favors formation of chloroaurate anions (AuCl4-). This results in a removal of gold ions from solution and allows further oxidation of gold to take place. The gold dissolves to become chloroauric acid. In addition, gold may be dissolved by the free chlorine present in aqua regia. Appropriate equations are

Au (s) + 3 NO3- (aq) + 6 H+ (aq) → Au3+ (aq) + 3 NO2 (g) + 3 H2O (l) and
Au3+ (aq) + 4 Cl- (aq) → AuCl4- (aq).

The oxidation reaction can also be written with nitric oxide as the product rather than nitrogen dioxide:

Au (s) + NO3- (aq) + 4 H+ (aq) → Au3+ (aq) + NO (g) + 2 H2O (l).

Dissolving platinum

Similar equations can be written for platinum. As with gold, the oxidation reaction can be written with either nitric oxide or nitrogen dioxide as the nitrogen oxide product.

Pt (s) + 4 NO3 (aq) + 8 H+ (aq) → Pt4+ (aq) + 4 NO2 (g) + 4 H2O (l)
3Pt (s) + 4 NO3 (aq) + 16 H+ (aq) → 3Pt4+ (aq) + 4 NO (g) + 8 H2O (l)

The oxidized platinum ion then reacts with chloride ions resulting in the chloroplatinate ion.

Pt4+ (aq) + 6 Cl (aq) → PtCl62− (aq)

Experimental evidence reveals that the reaction of platinum with aqua regia is considerably more complex. The initial reactions produce a mixture of chloroplatinous acid (H2PtCl4) and nitrosoplatinic chloride ((NO)2PtCl4). The nitrosoplatinic chloride is a solid product. If full dissolution of the platinum is desired, repeated extractions of the residual solids with concentrated hydrochloric acid must be performed.

Pt (s) + 2 HNO3 (aq) + 4 HCl (aq) → (NO)2PtCl4 (s) + 3 H2O (l) + 1/2 O2 (g)
(NO)2PtCl4 (s) + 2 HCl (aq) → H2PtCl4 (aq) + 2 NOCl (g)

The chloroplatinous acid can be oxidized to chloroplatinic acid by saturating the solution with chlorine while heating.

H2PtCl4 (aq) + Cl2 (g) → H2PtCl6 (aq)

Dissolving platinum solids in aqua regia was the mode of discovery for the most dense metals. Iridium and osmium, both of which are found in platinum ore and will not be dissolved by the acid, instead collecting on the base of the vessel.

Decomposition of aqua regia

Upon mixing of concentrated hydrochloric acid and concentrated nitric acid, chemical reactions occur. These reactions result in the volatile products nitrosyl chloride and chlorine as evidenced by the fuming nature and characteristic yellow color of aqua regia. As the volatile products escape from solution, the aqua regia loses its potency.

HNO3 (aq) + 3 HCl (aq) → NOCl (g) + Cl2 (g) + 2 H2O (l)

Nitrosyl chloride can further decompose into nitric oxide and chlorine. This dissociation is equilibrium-limited. Therefore, in addition to nitrosyl chloride and chlorine, the fumes over aqua regia contain nitric oxide.

2 NOCl (g) → 2 NO (g) + Cl2 (g)

History

Jabir ibn Hayyan, medieval manuscript drawing, anonymous

Hydrochloric acid was first discovered around the year 800 by the alchemist Abu Musa Jabir ibn Hayyan (Geber) by mixing common salt with vitriol (sulfuric acid). Jabir's invention of gold-dissolving aqua regia, consisting of hydrochloric acid and nitric acid, contributed to the effort of alchemists to find the philosopher's stone.[3]

When Germany invaded Denmark in World War II, the Hungarian chemist George de Hevesy dissolved the gold Nobel Prizes of Max von Laue and James Franck into aqua regia to prevent the Nazis from stealing them. He placed the resulting solution on a shelf in his laboratory at the Niels Bohr Institute. It was subsequently ignored by the Nazis who thought the jar—one of perhaps hundreds on the shelving—contained common chemicals. After the war, de Hevesy returned to find the solution undisturbed and precipitated the gold out of the acid. The gold was returned to the Royal Swedish Academy of Sciences and the Nobel Foundation who recast the medals and again presented them to Laue and Franck.[4]

In art and entertainment

Literature

  • Cryptonomicon, by Neal Stephenson - The fuel for the "Galvanick Lucipher" (a sort of specialized lantern) used by the butler Ghnxh on Qwghlm.
  • The Crying of Lot 49, by Thomas Pynchon - During The Courier's Tragedy, the faithful servant Ercole pours aqua regia into a steel box around the traitor Domenico's head.
  • Octopussy, a James Bond film; Bond is provided by Q with a fountain pen containing a mixture of hydrochloric and nitric acids, which Bond utilizes to cut his way through metal prison bars.
  • In the children's novel Pigeon Post, by Arthur Ransome, Dick Callum dissolves the ore they have discovered in Aqua Regia, and thinks it is gold, not an ore of copper. But copper is what Captain Flint and Timothy wanted to find.
  • In "The Devil In The Dark," an episode of Star Trek's first season in the Original Series, as James Blish wrote in his script novelizations, the silicon-based horta exudes aqua regia naturally as it tunnels through rock.

See also

References

External links


s to remove all traces of organic material.]]

Aqua regia (Latin:royal water) or aqua regis is a highly corrosive, fuming yellow or red solution, also called nitro-hydrochloric acid. The mixture is formed by freshly mixing concentrated nitric acid and concentrated hydrochloric acid, usually in a molar ratio of 1:3 respectively. It was named so because it can dissolve the so-called royal metals, or noble metals, gold and platinum. However, ruthenium, tantalum, iridium, osmium, titanium, rhodium and a few other metals are capable of withstanding chemical attack from it.

Contents

Applications

Aqua regia is primarily used to produce chloroauric acid, the electrolyte in the Wohlwill process. This process is used for refining highest quality (99.999%) gold. (See dissolving gold)

Aqua regia is also used in etching and in specific analytic procedures. It is also used in some laboratories to clean glassware of organic compounds and metal particles. This method is preferred over the "traditional" chromic acid bath for cleaning NMR tubes, because no traces of paramagnetic chromium can remain to later spoil acquired spectra.[1] Furthermore, chromic acid baths are discouraged because of the high toxicity of chromium and the potential for explosions. Aqua regia is itself very corrosive and has been implicated in several explosions due to mishandling.[2]

Due to the reaction between its components resulting in its decomposition, aqua regia quickly loses its effectiveness. As such, its components should only be mixed immediately before use. While local regulations may vary, aqua regia may be disposed of by carefully neutralizing with an appropriate agent—such as sodium bicarbonate—before pouring down the sink. If there is a large amount of metal in solution with the acid, it may be preferable to carefully neutralize it, and absorb the solution with a solid material such as vermiculite before discarding it with solid waste.

Chemistry

Dissolving gold

[[File:|thumb|right|Pure gold precipitate produced by the aqua regia chemical refining process]] Aqua regia dissolves gold, though neither constituent acid will do so alone, because, in combination, each acid performs a different task. Nitric acid is a powerful oxidizer, which will actually dissolve a virtually undetectable amount of gold, forming gold ions (Au3+). The hydrochloric acid provides a ready supply of chloride ions (Cl-), which react with the gold ions to produce chloroaurate anions, also in solution. The reaction with hydrochloric acid is an equilibrium reaction which favors formation of chloroaurate anions (AuCl4-). This results in a removal of gold ions from solution and allows further oxidation of gold to take place. The gold dissolves to become chloroauric acid. In addition, gold may be dissolved by the free chlorine present in aqua regia. Appropriate equations are

Au (s) + 3 NO3- (aq) + 6 H+ (aq) → Au3+ (aq) + 3 NO2 (g) + 3 H2O (l) and
Au3+ (aq) + 4 Cl- (aq) → AuCl4- (aq).

The oxidation reaction can also be written with nitric oxide as the product rather than nitrogen dioxide:

Au (s) + NO3- (aq) + 4 H+ (aq) → Au3+ (aq) + NO (g) + 2 H2O (l).

Dissolving platinum

File:Platin loest sich in heissem
Platinum being dissolved in aqua regis

Similar equations can be written for platinum. As with gold, the oxidation reaction can be written with either nitric oxide or nitrogen dioxide as the nitrogen oxide product.

Pt (s) + 4 NO3 (aq) + 8 H+ (aq) → Pt4+ (aq) + 4 NO2 (g) + 4 H2O (l)
3Pt (s) + 4 NO3 (aq) + 16 H+ (aq) → 3Pt4+ (aq) + 4 NO (g) + 8 H2O (l)

The oxidized platinum ion then reacts with chloride ions resulting in the chloroplatinate ion.

Pt4+ (aq) + 6 Cl (aq) → PtCl62− (aq)

Experimental evidence reveals that the reaction of platinum with aqua regia is considerably more complex. The initial reactions produce a mixture of chloroplatinous acid (H2PtCl4) and nitrosoplatinic chloride ((NO)2PtCl4). The nitrosoplatinic chloride is a solid product. If full dissolution of the platinum is desired, repeated extractions of the residual solids with concentrated hydrochloric acid must be performed.

Pt (s) + 2 HNO3 (aq) + 4 HCl (aq) → (NO)2PtCl4 (s) + 3 H2O (l) + 1/2 O2 (g)
(NO)2PtCl4 (s) + 2 HCl (aq) → H2PtCl4 (aq) + 2 NOCl (g)

The chloroplatinous acid can be oxidized to chloroplatinic acid by saturating the solution with chlorine while heating.

H2PtCl4 (aq) + Cl2 (g) → H2PtCl6 (aq)

Dissolving platinum solids in aqua regia was the mode of discovery for the most dense metals. Iridium and osmium, both of which are found in platinum ore and will not be dissolved by the acid, instead collecting on the base of the vessel.

Reactions with other metals

Aqua regia reacts with tin to form tin(IV) chloride, containing tin in its highest oxidation state:

4 HCl + 2 HNO3 + Sn → SnCl4 + NO2 + NO + 3 H2O

Decomposition of aqua regia

Upon mixing of concentrated hydrochloric acid and concentrated nitric acid, chemical reactions occur. These reactions result in the volatile products nitrosyl chloride and chlorine as evidenced by the fuming nature and characteristic yellow color of aqua regia. As the volatile products escape from solution, the aqua regia loses its potency.

HNO3 (aq) + 3 HCl (aq) → NOCl (g) + Cl2 (g) + 2 H2O (l)

Nitrosyl chloride can further decompose into nitric oxide and chlorine. This dissociation is equilibrium-limited. Therefore, in addition to nitrosyl chloride and chlorine, the fumes over aqua regia contain nitric oxide.

2 NOCl (g) → 2 NO (g) + Cl2 (g)

History

Aqua regia first appeared in the work of the medieval European alchemist Pseudo-Geber (probably Paul of Taranto).[3]

Lavoisier called it nitro-muriatic acid in 1789.[4]

When Germany invaded Denmark in World War II, the Hungarian chemist George de Hevesy dissolved the gold Nobel Prizes of the German physicists Max von Laue and James Franck in aqua regia to prevent the Nazis from confiscating them. The German government had prohibited Germans from accepting or keeping any Nobel Prize after the jailed peace activist Carl von Ossietzky had received the Nobel Peace Prize in 1935. De Hevesy placed the resulting solution on a shelf in his laboratory at the Niels Bohr Institute. It was subsequently ignored by the Nazis who thought the jar—one of perhaps hundreds on the shelving—contained common chemicals. After the war, de Hevesy returned to find the solution undisturbed and precipitated the gold out of the acid. The gold was returned to the Royal Swedish Academy of Sciences and the Nobel Foundation who recast the medals and again presented them to Laue and Franck.[5]

In literature

  • Cryptonomicon, by Neal Stephenson - The fuel for the "Galvanick Lucipher" (a sort of specialized lantern) used by the butler Ghnxh on Qwghlm.
  • The Crying of Lot 49, by Thomas Pynchon - During The Courier's Tragedy, the faithful servant Ercole pours aqua regia into a steel box around the traitor Domenico's head.
  • Octopussy, a James Bond film; Bond is provided by Q with a fountain pen containing a mixture of hydrochloric and nitric acids, which Bond utilizes to cut his way through metal prison bars.
  • In the children's novel Pigeon Post, by Arthur Ransome, Dick Callum dissolves the ore they have discovered in Aqua Regia, and thinks it is gold, not an ore of copper. But copper is what Captain Flint and Timothy wanted to find.
  • In "The Devil In The Dark," an episode of Star Trek's first season in the Original Series, as James Blish wrote in his script novelizations, the silicon-based horta exudes aqua regia naturally as it tunnels through rock.

See also

References

External links


Simple English

File:Platin loest sich in heissem
Platinum being dissloved in hot aqua regia

Aqua regia (translates to Royal water in Latin) is a chemical substance. It is made by mixing one part nitric acid and three parts hydrochloric acid. It is one of the few substances that can dissolve gold and platinum, and other noble metals. Tantalum, iridium and a few other metals are not dissolved by it.

History

Aqua regia was discovered around 800 AD, by the Persian alchemist Geber, when he mixed common salt with vitriol (sulphuric acid). In the Middle Ages it was one of the ways that alchemists tried to find the philosopher's stone.

When Germany invaded Denmark in World War II, the Hungarian chemist George de Hevesy took the Nobel Prize medals of Max von Laue and James Franck to keep them safe. De Hevesy dissolved the medals, which were made of gold, into aqua regia. He did this so the Nazis would not steal them. He placed the jar that held the solution of aqua regia and gold on a shelf in his laboratory at the Niels Bohr Institute. The jar looked the same as hundreds of other jars in the laboratory. The Nazis thought that all the jars had normal chemicals in them. After the war, de Hevesy returned to the lab. He found the jar with the solution and removed the gold from it. He returned the gold to the Royal Swedish Academy of Sciences. The Nobel Foundation used the gold to make new medals for Laue and Franck.[1]

Uses

Aqua Regia is used in metal etching and scientific analysis. It is also used to clean certain lab machines from tiny metal particles. It is particularly used in the purification and extraction of gold and platinum.

References

  1. Birgitta Lemmel (2006). "The Nobel Prize Medals and the Medal for the Prize in Economics". The Nobel Foundation. http://nobelprize.org/nobel_prizes/medals/. 



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