Nitric acid (HNO3), also known as aqua fortis and spirit of nitre, is a highly corrosive and toxic strong acid that can cause severe burns. The synthesis of nitric acid was first recorded circa 800 AD by the alchemist Jabir ibn Hayyan (Geber).
Colorless when pure, older samples tend to acquire a yellow cast due to the accumulation of oxides of nitrogen. If the solution contains more than 86% nitric acid, it is referred to as fuming nitric acid. Fuming nitric acid is characterized as white fuming nitric acid and red fuming nitric acid, depending on the amount of nitrogen dioxide present.
which means that anhydrous nitric acid should be stored below 0 °C to avoid decomposition. The nitrogen dioxide (NO2) remains dissolved in the nitric acid coloring it yellow, or red at higher temperatures. While the pure acid tends to give off white fumes when exposed to air, acid with dissolved nitrogen dioxide gives off reddish-brown vapours, leading to the common name "red fuming acid" or "fuming nitric acid". Fuming nitric acid is also referred to as 16-molar nitric acid –– as the most concentrated form of nitric acid at Standard Temperature & Pressure (STP).
Nitric acid is miscible with water in all proportions and distillation gives an azeotrope with a concentration of 68% HNO3 and a boiling temperature of 120.5 °C at 1 atm. Two solid hydrates are known; the monohydrate (HNO3·H2O) and the trihydrate (HNO3·3H2O).
Nitrogen oxides (NOx) are soluble in nitric acid and this property influences more or less, all the physical characteristics depending on the concentration of the oxides. These mainly include the vapor pressure above the liquid and the boiling temperature, as well as the color mentioned above.
Nitric acid is subject to thermal or light decomposition with increasing concentration and this may give rise to some non-negligible variations in the vapour pressure above the liquid because the nitrogen oxides produced dissolve partly or completely in the acid.
Nitric acid has an acid dissociation constant (pKa) of −1.4: in aqueous solution, it almost completely (93% at 0.1 mol/L) ionizes into the nitrate ion NO3− and a hydrated proton, known as a hydronium ion, H3O+.
Being a powerful oxidizing agent, nitric acid reacts violently with many organic materials and the reactions may be explosive. Depending on the acid concentration, temperature and the reducing agent involved, the end products can be variable. Reaction then takes place with all metals except the precious metal series and certain alloys. This characteristic has made it a common agent to be used in acid tests. As a general rule, oxidizing reactions occur primarily with the concentrated acid, favouring the formation of nitrogen dioxide (NO2).
The acidic properties tend to dominate with dilute acid, coupled with the preferential formation of nitrogen oxide (NO).
Red fuming nitric acid, or RFNA, contains substantial quantities of dissolved nitrogen dioxide (NO2) leaving the solution with a reddish-brown color. One formulation of RFNA specifies a minimum of 17% NO2, another specifies 13% NO2.
An inhibited fuming nitric acid (either IWFNA, or IRFNA) can be made by the addition of 0.6 to 0.7% hydrogen fluoride, HF. This fluoride is added for corrosion resistance in metal tanks (the fluoride creates a metal fluoride layer that protects the metal).
Dilute nitric acid may be concentrated by distillation up to 68% acid, which is an azeotropic mixture with 32% water. Further concentration involves distillation with sulphuric acid which acts as a dehydrating agent. In the laboratory, such distillations must be done with all-glass apparatus at reduced pressure, to prevent decomposition of the acid.
The acid can also be synthesized by oxidizing ammonia, but the product is diluted by the water also formed as part of the reaction. However, this method is important in producing ammonium nitrate from ammonia derived from the Haber process, because the final product can be produced from nitrogen, hydrogen, and oxygen as the sole feedstocks.
The dissolved NOx are readily removed using reduced pressure at room temperature (10-30 min at 200 mmHg or 27 kPa) to give white fuming nitric acid. This procedure can also be performed under reduced pressure and temperature in one step in order to produce less nitrogen dioxide gas.
A solution of nitric acid and alcohol, Nital, is used for etching of metals to reveal the microstructure.
Commercially available aqueous blends of 5-30% nitric acid and 15-40% phosphoric acid are commonly used for cleaning food and dairy equipment primarily to remove precipitated calcium and magnesium compounds (either deposited from the process stream or resulting from the use of hard water during production and cleaning).
Alone, it is useful in metallurgy and refining as it reacts with most metals, and in organic syntheses. When mixed with hydrochloric acid, nitric acid forms Aqua Regia, one of the few reagents capable of dissolving gold and platinum.
Aqua Regia is technically a reagent –– not an acid. Aqua Regia is made by (carefully) mixing three parts of hydrochloric acid with one part nitric acid. That mixture produces nitrosyl chloride and free chlorine gas (in the aqueous solution). These two agents are individually exceptionally powerful oxidizing agents. Combined, each acid performs a different function. This is what gives Aqua Regia the ability to dissolve gold and platinum –– where neither acid by itself was able to dissolve the metals by themselves.
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