3/22/2015

Nitric Acid
(Hydric Nitrate)
(HNO3)
Dr. Muhammad Aslam
Assistant Professor-Chemistry
Division of Science and Technology
University of Education, Township Campus, Lahore.

Books Recommended
Advanced Inorganic Chemistry (Volume 1)
S. Parakash
Inorganic Chemistry
Haq Nawaz Bhatti
Handbook of Industrial Chemistry (Volume 1)
KH Davis, FS Berner

Structure of HNO3

HNO3 is a monobasic acid and is supposed to exist in

the following two resonating forms:

Basic and Heavy Chemical Industries

Raw materials and chemicals
Flow sheet diagrams and commercial production of
Sulphuric acid
Nitric acid
Hydrochloric acid
Oxalic acid
Formic acid
Caustic soda
Washing soda
Applications of these chemicals in chemical
industries

Nitric Acid, HNO3

The most important and useful oxoacid of
nitrogen is nitric acid.
Its molecular formula is HNO3 and molar mass
63 01 g mol-1.
63.01
Nitric acid is a chemical of great commercial
importance because of its use in the manufacture
of explosives like nitroglycerine, trinitrotoluene,
gun cotton, picric acid etc., in the manufacture of
nitrates which are used as fertilizers and in the
manufacture of dyes, drugs and artificial silk.

Properties
Pure 100% nitric acid is a colourless, highly corrosive
liquid with powerful oxidizing properties.
The commercial acid varies from colourless to a
yellowish red colour, owing to the presence of
dissolved nitrogen oxides.

As indicated by
y electron diffraction studies,, the
molecule of nitric acid, in vapour state, possesses a
planar structure as shown below:
Soluble in all proportions in water and forms a
constant-boiling mixture at 760 mm. pressure of 68%
acid and 32% water with a boiling point of 110C.
Solutions containing more than 86% HNO3 are known
as fuming nitric acids.

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Manufacture of Nitric Acid

The following methods are used to manufacture nitric
acid:
(i) From Nitrates
Nitric acid is prepared on large scale by heating Chile
saltpetre (NaNO3) with concentrated sulphuric acid.
The mixture is placed in a cast iron retort and subjected
to distillation at a temperature of about 200C.
Potassium nitrate has also been employed.
The yellow colour of HNO3 is due to the presence of
NO2 in it which can be removed by distillation in
vacuum.

(ii) From Air by Birkland Eyde Process

Nitrogen and oxygen of the atmosphere can be made to
combine by passing an electric discharge through air or
the air may be passed through an electric arc (temp.
3500C).
This process at first gives nitric oxide, which is then
quickly cooled to 500C, when it further combines with
oxygen
yg to give
g about 2% nitrogen
g peroxide.
p

The vapours are then washed down by water trickling in

absorption towers filled with quartz stones when nitric
acid is produced:

The exothermic reaction proceeds without supply of heat

except the initial heating.
About 90% NH3 is converted to NO under these
conditions.
Oxidation of NO to NO2 and Formation of nitric acid
NO is converted to NO2 in the presence of air or oxygen
and passed through the absorption tower as mentioned
p
above in arc process.
The acid so obtained is dilute which can be concentrated
to 68% by distillation, when constant boiling mixture is
formed.
This constant boiling mixture of HNO3 has a specific
gravity of 1.42 and is the commercial concentrated
HNO3.

Before the gases escape in air, they are led through

towers containing lime or caustic alkali which recover all
the oxides of nitrogen.
(iii) From Ammonia (Ostwald's Process)
(Industrial Preparation)
On a commercial scale, nitric acid is manufactured through the
O t ld' process - the
Ostwald's
th process off catalytic
t l ti oxidation
id ti off ammonia.
i
The conversion of ammonia into nitric acid in this process is done
through the following steps:
Oxidation of ammonia to nitric oxide
In this method a mixture of ammonia gas with air in the ratio 1:8
is passed through a catalyst chamber packed with platinum gauze
maintained at temperature of 800C.
The ammonia is oxidized to nitric oxide.

More concentrated acid needed for certain uses is

produced by distillation with conc. H2SO4 which holds
back the water.
The distillate is 98% HNO3 having density 1.5.
Parts of Plant
The manufacturing plant for the production of nitric acid
by the Ostwald's process, has the following components
and processes.
Converter
The converter is made of aluminium and fitted with
platinum - rhodium gauze cylinder (23 cm x 34 cm).
The cylinder is closed at the bottom with a silica lid.
The gauze is initially heated to 800C electrically.
Thereafter no external heating is required as oxidation
of ammonia is an exothermic reaction.

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A mixture of ammonia and clear air (volume ratio =

(1:8) is then passed through the gauze from the top, and
the products leave from the bottom.
Every 1000 cm2 area of the gauze produces about 500
kg of nitric oxide, every 24 hours.

Converter for the

Ostwald's process

Ostwald's process for the manufacture of nitric acid.

Ostwald's process for manufacture of HNO3.

Oxidation tower
When nitric oxide, containing nitrogen and some water
vapors, come out of the converter, they are cooled to
about 100C by passing them through coolers.
In the oxidation tower, nitric oxide is mixed with more
air and it gets converted to NO2.
Absorption tower
NO2 is allowed to enter the absorption tower from the
lower end.
The tower is packed with quartz pieces and water is
sprinkled from the top.
Here, NO2 is absorbed into water in the presence of air to
yield nitric acid.

Commercial nitric acid has a brown color due to

dissolved NO2.
The procedure of bubbling dry air through warm
commercial nitric acid, is to drive away the dissolved
nitrogen dioxide so that the acid becomes colorless.
Concentrating nitric acid
Aqueous nitric acid obtained by this method can be
concentrated by distillation to 68.5%
68 5% by mass.
mass
Further concentration to 98% acid can be achieved by
dehydration with concentrated sulphuric acid.
Anhydrous nitric acid
Anhydrous nitric acid can be obtained by distillation of
concentrated aqueous nitric acid with phosphorus
pentoxide (P2O5 or P4O10).

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Fuming Nitric Acid

Fuming nitric acid is made by distilling conc. HNO3
with a little starch.
The starch reduces some acid to NO2 which dissolves in
the remainingg acid to form fumingg nitric acid.
It is yellow in colour due to NO2.
It is a much more powerful oxidizing agent and
nitrating agent than conc. HNO3.

Laboratory Preparation
Nitric acid is usually prepared by heating potassium
nitrate with concentrated sulphuric acid.
This heating is done in a glass retort and vapors of nitric
acid are condensed in a receiver, which is cooled by
water.
The reaction is:

Production Unit of Nitric Acid and Nitric

Fertilizers
The section of nitric products practically consists of two
separate units.
units
The first one produces Nitric Acid and the second one
produces Nitric Ammonia and Nitric Fertilizers.
The production procedure is briefly shown in the
following graph:
Laboratory preparation of nitric acid

The unit of nitric acid uses ammonia as raw material

which is oxidized in the presence of a catalyst initially
to nitrogen monoxide and then to nitrogen dioxide.
The produced nitrogen oxides after giving their energy
indirectly (steam turbine) or directly (gas turbine), they
are converted into nitric acid by absorbing water.
In the ammonium nitrate production unit, the nitric
acid
id reacts
t with
ith gaseous ammonia
i andd produces
d
a
solution of ammonium nitrate.
A part of the produced solution of ammonium nitrate is
led via a pipe to the production unit of compound
fertilizers.
The remaining quantity after first being condensed is
used for the production of nitric fertilizers.

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Grades
In addition to the various grades of nitric acid, a
nitrating or mixed acid (nitric acid, sulphuric acid and
water) is produced by nitric acid manufacturers in the
following standard promotions:

Economic Aspects
Nearly all nitric acid manufactured today comes from
the catalytic oxidation of ammonia.
Further most of it is converted to ammonium nitrate at
the same site.
Thus nitric acid manufacture is tied very closely to the
fertilizer industry, and only secondarily to the explosive
industry.
industry
The most promising new uses of nitric acid are as an
acidulant for superphosphate manufacture and as a
component of the oxidant for missiles and rockets.
Both uses are still only problematical.
Efforts to develop processes for making nitric acid
directly from the nitrogen of the air have not been
successful.

Containers
Technical grades of weak acids (50 to 70%) in glass
carboys and bottles.
Concentrated acid (95%) in aluminium or stainless
steel drums and tank cars.
Mixed acid (nitric and sulphuric) in iron drums or
tank cars.

Neither the Wisconsin "pebble bed" process nor nuclear

nitrogen fixation using uranium 235 have proved
economically competitive with ammonia oxidation.
A small amount of acid may still be made from sodium
nitrate, but the process is practically extinct.
Most current nitric acid plants are built in batteries of
55 tons per day.
Recently the size of individual units has been increasing
and one plant produces 250 tons per day in a single
absorber and a single cooler.
The single burner also has the same capacity.

Uses
It is used:
in the manufacture of nitrates which are important
chemicals of commerce.
Basic calcium nitrate is used as fertilizer.
Silver nitrate is used in photography and sodium
nitrate is used in the manufacture of gun powder.
in the manufacture of explosives
p
like nitroglycerine,
gy
,
dynamite, trinitrotoluene, picric acid etc.
in the manufacture of artificial silk, dyes, medicines,
and perfumes.
in the purification of gold and silver.
as a important reagent in the laboratory.
in the manufacture of H2SO4.
in the preparation of aqua regia.

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Safety
Nitric acid is a corrosive acid and a powerful oxidizing
agent.
The major hazard posed by it is chemical burns as it
carries out acid hydrolysis with proteins (amide) and
fats (ester) which consequently decomposes living tissue
(e.g. skin and flesh).
Concentrated nitric acid stains human skin yellow due to
its reaction with the keratin.
These yellow stains turn orange when neutralized.
Systemic effects are unlikely, however, and the
substance is not considered a carcinogen or mutagen.
The standard first aid treatment for acid spills on the
skin is, as for other corrosive agents, irrigation with
large quantities of water.

Washing is continued for at least ten to fifteen minutes

to cool the tissue surrounding the acid burn and to
prevent secondary damage.
Contaminated clothing is removed immediately and the
underlying skin washed thoroughly.
Being a strong oxidizing agent, reactions of nitric acid
with compounds such as cyanides, carbides, metallic
powders can be explosive and those with many organic
compounds, such as turpentine, are violent and
hypergolic (i.e. self-igniting).
Hence, it should be stored away from bases and
organics.