Chemical Technology

Subject Code: CH2001

Module II-Lecture 3
Nitric Acid

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 Nitric Acid
Synonyms: Molar mass 63.013 g/mol
• NITRIC ACID Appearance Colorless, yellow or red fuming liquid
• Azotic acid Odor acrid, suffocating
• Hydrogen nitrate Density 1.51 g cm
−3

Melting point −42 °C

• Nitric acid, red fuming appears as a pale yellow to Solubility in water Completely miscible
reddish brown liquid generating red-brown fumes
and having a suffocating odor. Boiling point 83 °C
• It is inorganic acid. Commercially available nitric acid is
• Very toxic by inhalation. Corrosive to metals or an azeotrope with water at a concentration of 68%
HNO3. This solution has a boiling temperature of
tissue. Prolonged exposure to low concentrations 120.5 °C at 1 atm. It is known as "concentrated
or short term exposure to high concentrations nitric acid". Pure concentrated nitric acid is a
may result in adverse health effects, Very colourless liquid at room temperature.
corrosive to skin/mucous membranes as well as Two solid hydrates are known: the monohydrate
(HNO3·H2O or [H3O]NO3) and the trihydrate
metals & other materials. (HNO3·3H2O).

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 Video lecture and notes links

• https://www.youtube.com/watch?v=FIxz7biiIG0
• https://www.youtube.com/watch?v=QTRXdaWBP2s
• www.technology.matthey.com › pmr-v11-i1-002-009
• https://www.essentialchemicalindustry.org/chemicals/nitric-
acid.html

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 History of Nitric Acid Production
• Nitric acid occurs in nature in the form of nitrate salts. Initially, large scale production
of nitric acid began with sodium nitrate as a feed stock.
• Near the beginning of the 20th century, world reserves of sodium nitrate were low
and processes were being developed to replace nitrate with nitrogen.
• Nitric acid is made by reaction of nitrogen dioxide (NO2) with water.
4 NO2 + 2 H2O → 2 HNO3 + NO + NO2 + H2O
• Or, shortened:
3 NO2 + H2O → 2 HNO3 + NO
• Normally, the nitric oxide produced by the reaction is reoxidized by the oxygen in air to
produce additional nitrogen dioxide.
• Bubbling nitrogen dioxide through hydrogen peroxide can help to improve acid yield.
2 NO2 + H2O2 → 2 HNO3

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 Ostwald process
Commercial grade nitric acid solutions are usually between 52% and 68% nitric acid.
Production of nitric acid is via the Ostwald process, named after German
chemist Wilhelm Ostwald. The Ostwald process was discovered just in time for the
First World War, nitric acid that was essential for the production of the explosives
used in artillery shells, such as TNT and nitroglycerin.

In this process, anhydrous ammonia is oxidized to nitric oxide, in the presence

of platinum or rhodium gauze catalyst at a high temperature of about 500 K and a
pressure of 9 atm.
4 NH3 (g) + 5 O2 (g) → 4 NO (g) + 6 H2O (g) (ΔH = −905.2 kJ/mol)

Nitric oxide is then reacted with oxygen in air to form nitrogen dioxide.
2 NO (g) + O2 (g) → 2 NO2 (g) (ΔH = −114 kJ/mol)

This is subsequently absorbed in water to form nitric acid and nitric oxide.
3 NO2 (g) + H2O (l) → 2 HNO3 (aq) + NO (g) (ΔH = −117 kJ/mol)

The nitric oxide is cycled back for reoxidation. Alternatively, if the last step is carried
out in air:
4 NO2 (g) + O2 (g) + 2 H2O (l) → 4 HNO3 (aq)
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• The aqueous HNO3 obtained can be concentrated by distillation up to about 68% by mass.
• Further concentration to 98% can be achieved by dehydration with concentrated H2SO4.
• By using ammonia derived from the Haber process, the final product can be produced from
nitrogen, hydrogen, and oxygen which are derived from air and natural gas as the sole
feedstocks.
• 100% pure, anhydrous nitric acid is a colourless anhydrous solid.
• Concentrated nitric acid' is actually a solution of 68% by weight HNO3 in water.
• By dissolving even more NO2 into the pure material produces red 'fuming' nitric acid, which is an
extremely powerful acid and oxidising agent using in the semiconductor industry for cleaning
silicon wafers.
• Aqua Regia (approx 3 vols HCl to 1 vol HNO3) contains free Cl2 and nitrosyl chloride (NOCl).
This powerful acid attacks even the inert metals gold and platinum owing to the ability of Cl- to
stabilise the complexes AuCl4- and PtCl62-.

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 Nitric acid production process
Raw materials
• NH3 from synthesis ammonia process
• Filtered air
• Platinum-rhodium make-up catalyst

Quantitative requirements
Basis 1 ton HNO3
• Anhydrous NH3: 0.287-0.29 ton
• Air: 3000 Nm3
• platinum (2-10% Rh prompted): 0.1 gm
• Process water: 120 tons
• Steam credit: 1 ton @ 200Psig
• Power: 10-30 kWh

Plant capacity: 50-250 tons/day

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 Process description
• Compressed air is mixed with anhydrous NH3, fed to a shell and tube convertor designed so
that the preheater and steam heat recovery boiler-superheater are within the same reactor
shell.
• The convertor section consist of 10-30 sheets of Pt-Rh alloy in the form of 60-80 mesh wire
gage packed in layers inside the tubes.
• Gas passes downward with velocity designed to give a contact time of about 2.5 x 10-4 sec in
the catalyst zone at 800C.
• Product gases from the reactor containing 10-12 % NO, are send through heat recovery units, a
quench unit for rapid cooling to recover a large fraction of the product heat and into the
oxidizer-absorber system.
• Air is added to convert NO to NO2 at the more favourable low temp (40-50C) environment of
the absorption system.
• The equipment in the absorption train may be a series of packed or sieve tray vertical towers
or series of horizontal cascade absorbers.
• The product from this water absorption system is 57-60% HNO3 solution which can be sold as
conc. HNO3.

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 Concentration of nitric acid

• Concentration by H2SO4 : Rectification by 93% H2SO4 in silicon iron

or stone ware towers produces concentrated nitric acid and 70%
H2SO4 can be re-evaporated to 93%.
• Concentration by Mg(NO3 )2 : Magnesium nitrate solution
containing 70-75% Mg(NO3) is fed to dehydrating tray tower along
with dilute HNO3 from absorption system. The salt solution acts as
an extractive distillation agent, removing water at 100 C. or higher
thus allowing rectification without azeotropic formation. Dilute
Mg(NO3 )2 solution is reconcentrated by evaporation.

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 Major engineering problems:
Thermodynamic and kinetic considerations

All of the important oxidation reactions are exothermic.

Reaction has extremely favorable equilibrium constant so that a one step high temperature
converter design may be used.

There is slight equilibrium advantage to operation at low pressure (1 atm.).

The reaction to form NO is favored by increasing temperature until an optimum is reached which
increases with higher gas velocities. This results from the prevention of back diffusion of NO into
the higher NH3 concentration region.

Alloying platinum with rhodium improves yield at given set of conditions.

Rate of NO formation very nearly corresponds to diffusional transport of ammonia molecules to

catalyst surface.
 Grades
• The concentrated nitric acid of commerce consists of the maximum boiling azeotrope of nitric acid and water.
• Technical grades are normally 68% HNO3 , (approx 15 molar), while reagent grades are specified at 70%
HNO3. The density of concentrated nitric acid is 1.42 g/mL.
• White fuming nitric acid, also called 100% nitric acid or WFNA, is very close to anhydrous nitric acid.
• One specification for white fuming nitric acid is that it has a maximum of 2% water and a maximum of 0.5%
dissolved NO2 .
• Anhydrous nitric acid has a density of 1.513 g/mL and has the approximate concentration of 24 molar.
• A commercial grade of fuming nitric acid, referred to in the trade as "strong nitric acid" contains 90% HNO3
and has a density of 1.50 g/mL. This grade is much used in the explosives industry.
• Red fuming nitric acid, or RFNA, contains substantial quantities of dissolved nitrogen dioxide (NO2 ) leaving
the solution with a reddish-brown color.
• 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.

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 Uses

• The main use of nitric acid is for the production of fertilizers; other
important uses include the production of explosives, etching and
dissolution of metals, especially as a component of aqua regia for the
purification and extraction of gold, and in chemical synthesis.
• It is used in manufacturing several types of polymers like polyamides
and polyurethane. Nitric acid is also commonly used as rocket
propellants in the aerospace industry. It is also used for manufacturing
nitrogen-based compounds like nylon as well as most of the explosives
like trinitrotoluene (T.N.T.), nitroglycerin, amongst others.
• Other uses include, production of nitrate salts, making dyes, coal tar
products and drugs.

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