In free state : it is found in rain water.
In combined state: it is found in in the form of metallic nitrates ex:
sodium nitrate.
Nitric Acid is also known as “Aqua Fortis” meaning 'Strong Water'
as it reacts with nearly all metals and convert them to soluble
nitrates.
FORMATION OF NITRIC ACID IN NATURE
1) Nitrogen combines with O2 in atmosphere during lightning
discharge to form Nitric Oxide.
N2 + O2 → 2NO (Nitric Oxide)
2) Nitric Oxide to further oxidised to
Nitrogen dioxide.
2NO + O2 → 2NO2
3) Nitrogen dioxide dissolve in rain water
with O2 and form Nitric Acid.
4NO2 + 2H2O + O2 → 4HNO3
The conversion of free atmospheric N2 into
useful Nitrogenous compound is called 'fixation of atmospheric
Nitrogen'.
LAB PREPARATION OF NITRIC ACID
Procedure : Equal weight of both Nitre/Chile Saltpetre + Conc.
H2SO4
is heated gently to 180 C – 200 C in glass retort.
Reactions:
Nitre/Chile Saltpetre + Conc. H2SO4 → Pot./Sod. Bisulphate +
HNO3
KNO3 + H2SO4 → KHSO4 + HNO3
NaNO3 + H2SO4 → NaHSO4 + HNO3
Collection : The vapours of Nitric acid are condensed by chilling
with ice cold water. HNO3 is light yellow because of presence of
NO2 (Reddish Brown Gas).
Pure Acid is colourless. To remove yellow colour of Lab HNO3:
i) Dry Air or CO2 is passed, it oxides NO2 to Nitric Acid.
ii) Adding excess of H2O which dissolves NO2.
Precautions:
(1)All glass apparatus should be used as Nitric acid vapour
attacks rubber and cork.
(2)Conc. HCl is not used in place of Conc. H2SO4, as it is volatile.
(3)Temp. should not exceed 200°C as it may damage the
apparatus & HNO3 may decompose. Even product forms hard
crust which sticks to the walls of the glass.
Manufacture of Nitric Acid
Step I:- Catalytic Oxidation of Ammonia
Dry Air and Dry Ammonia in 10:1 by volume is compressed
passed in Catalytic chamber containing platinum as catalyst at
800 C.
4NH3 + 5O2 → 4NO + 6H2O + Heat
Step II:- Oxidation of Nitric Oxide in oxidation of chamber- Nitric
oxide combines with O2 at 50 C to form Nitrogen oxide.
2NO(g) + O2(g) →2NO2(g)
Step III:- Absorption of nitrogen dioxide in water- The nitric acid is
collected at the bottom at 50% concentration which is distilled to
form 68% concentration.
4NO2(g) + 2H2O(l) + O2(g) → 4HNO3 (aq.)
Concentration of Nitric Acid
Nitric acid up to 98% (fuming nitric acid) is obtained by distilling
68% HNO3 over conc. sulphuric acid. It may concentrate upto
100% by strongly cooling at - 42 C.
Physical Properties:
1) Colour - pure HNO3 is colourless but commercial HNO3 is
yellowish brown.
2) Odour – Suffocating smell
3) Taste - Acidic.
4) Nature - Hygroscopic and fumes in air. So bottle is always
stoppered.
5) Physiological Nature – Non poisonous. It form blisters on
reacting with skin and gives yellow stains due to formation of
Xanthoproteic Acid.
6) Solubility : Soluble in water in all proportion.
7) Boiling and Melting point : Aqueous solution of Nitric acid
forms constant boiling mixture at 121 C. Nitric acid boils at 86 C.
Chemical Properties:
1) Stability - It is unstable to heat/sunlight. It decomposes into
NO2 and H2O and O2. That's why it is stored in coloured bottles.
2) Acidic property: It is monobasic acid. It ionises into H+ and
NO3- ions.
a) It turn BLR And MOP and PRC.
b) It reacts with Alkali to form salt and water only.
c) It reacts with carbonates/bicarbonates to give salt, water & CO2.
d) it reacts with metalic sulphites/bisulphites to give metal nitrate,
water and SO2.
3)Oxidising Property - HNO3 oxidises metal/nonmetal,
organic/inorganic substances. It has powerful oxidising property
due to Nascent Oxygen (O) produced on decomposition.
For Ex:
Action on Non-Metal:
C + 4HNO3 → CO2 + 2H2O + 4NO2 (Carbon oxidised to CO2)
S + 6HNO3 → H2SO4 + 2H2O + 6NO2 (Sulphur oxidised to H2SO4)
Action on Metals:
All metals react with Nitric acid except gold and platinum.
a) Cold and Dil Nitric Acid - oxides metals to nitrates and nitric
oxide
3Cu + Dil. 8HNO3 → 3Cu(NO3)2 + 4H2O + 2NO.
b) Hot and Conc Nitric acid – liberates Nitrogen oxide
Cu + Conc. 4HNO3 → Cu(NO3)2 + 2H2O + 2NO2
c) Metals like Iron, Al, Ni & Co become passive on reacting with
Conc. HNO3 - due to formation of thin layer of insoluble
Metallic Oxide which stops the reaction. Passivity can be
removed by rubbing with sand paper or reacting with strong
reducing agent.
d) Very dilute Nitric Acid reacts with Magnesium and Manganese
at room temp to give nitrates and Hydrogen gas.
Mg + 2HNO3 → Mg(NO3)2 + H2
This reaction proves that nitric acid contains Hydrogen.
Reaction as Aqua Regia : 1:3 Con.Nitric acid and
Con.Hydrochloric acid.
HNO3 + HCl → NOCl + 2H2O + 2Cl
This mixture can react with platinum and gold due to nascent
Chlorine.
USES OF NITRIC ACID
1. To etch designs on copper and brassware.
2. To purify gold.
3. Act as rocket fuel and used in preparation of nitric acid.
Tests For Nitric Acid:
1. Conc. Nitric Acid produces Nitrogen dioxide brown fumes on
heating.
2. Brown Ring Test. --Freshly prepared solution of Iron II
sulphate is added to nitric acid then add conc. Sulphuric acid
is carefully added to the sides. Cool the test tube.
A brown Ring is produced at the junction of 2 liquids. The
Brown ring is of Nitroso ferrous sulphate.
Precaution :
Freshly prepared solution of iron II sulphate is used as it get
oxidised.
EFFECTS OF HEAT ON NITRATES
(i) Sodium and potassium nitrates or alkali metal nitrates.
When heated, they melt into colourless liquids which decompose
on heating to give oxygen gas.
2NaNO3 → 2NaNO2 + O2
(ii) All other nitrates except those of silver and mercury
decompose into their oxides, nitrogen dioxide and oxygen.
1. Calcium Nitrate- white crystals on heating produce white ppt
with brown gas.
2Ca(NO3)2 → 2CaO + 4NO2(g) + O2
2. Zinc Nitrate – on heating produces yellow when hot and white
on cooling solid with brown gas
2Zn (NO3)2 → 2ZnO + 4NO2 + O2
3. Lead Nitrate- on heating produces yellow solid with brown gas
2Pb(NO3)2 → 2PbO+ 4NO2 + O2
4. Copper Nitrate on heating produces black compound with
brown gas
2Cu(NO3)2 → 2CuO + 4NO₂ + O2
(iii) Silver and mercury nitrates: On heating produce respective
metals, nitrogen dioxide and oxygen.
1. Silver nitrate (Lunar caustic)
2AgNO3 → 2Ag + 2NO2 + O2
2. Mercuric nitrate
Hg (NO3)2 → Hg + 2NO2 + O2
(iv) Ammonium nitrate: Ammonium nitrate decomposes
explosively leaving behind no residue.
NH4NO3 → N₂O[g] + 2H2O [vap.]
