Oxyacids of Nitrogen

An oxyacid is an acid that contains an oxygen atom bonded to

hydrogen atom and at least one other element. An oxyacid
dissociates in water to form H+ cation and anion of acid.
Nitrogen forms a number of oxyacids . The common oxyacids of
nitrogen are listed below
i. Hyponitrous acid (H2N2O2)
ii. Nitroxylic acid (H4N2O4)
iii. Nitrous acid (HNO2 )
iv. Nitric acid (HNO3)
v. Peroxonitric acid (HNO4)
Manufacture of nitric acid (Ostwald's process) :

Principle :

a) Catalytic oxidation of NH3 to NO :

Ammonia is oxidized to nitric oxide in presence of air (oxygen) at 800
o
C to 850 oC over the catalyst platinum gauze( or rhodium-platinum
alloy) . Pt gauze/ 800 oC

4NH3 + 5O2 4NO + 6H2O + heat

b) Oxidation of NO to NO2 :
Nitric oxide is cooled at a temperature below 100o C and air oxidized
to NO2..

2NO + O2 2NO2
c) Oxidation of NO2 to nitric acid in presence of air and water :

NO2 formed is dissolved in water in presence of air (O2 ) and

then nitric acid is obtained.

4NO2 + O2 + 2H2O 4HNO3

(Nitric acid)
Fig: manufacture of nitric acid by Ostwald’s process
 Working of the plant:
i) Converter:
NH3 gas is obtained from Haber’s process is mixed with pure and
dry air in the ratio of 1:8 by volume. The mixture is passed
through a converter containing platinum gauze ( 10% rhodium
and 90% platinum) catalyst . The converter is heated electrically
to about 800o C . Here, ammonia is catalytically oxidized to nitric
oxide.
Pt gauze/800o C
4NH3 + 5O2 4NO + 6H2O + heat

The above reaction is exothermic, therefore, the heat evolved in

the reaction maintains the required temperature and further
heating is not required.
 ii) Cooler :
The nitric oxide along with unreacted gases and air coming out
of the converter are cooled a temperature below 100o C with
the help of cooler.

iii) Oxidation chamber :

Thus, cooled nitric oxide with air is passed into oxidation
chamber where it mixes with air (O2 ) and oxidizes to nitrogen
dioxide .
2NO + O2 2NO2

iv) Absorption tower :

The NO2 gas from oxidation chamber are then passed through
absorption tower which is packed with acid-proof stone or
quartz. Water and air are sprayed from the top of absorption
tower. Water dissolves NO2 gas and produces nitric acid in the
presence of O2.
 4NO2 + 2H2 O + O2 4HNO3

v) Concentration of nitric acid :

Thus, obtained nitric acid is about 60% concentrated. On
distillation , the concentration of nitric acid can be increased up to
68% . This is the commercial nitric acid. Further concentration of
this 68% HNO3 by distillation under reduced pressure in the
presence of conc. H2 SO4 or P2 O5 (i.e. dehydrating agent) gives
98% HNO3 .
 Chemical properties

A. HNO3 as an acid
Nitric acid is a strong acid and ionizes completely in dilute
aqueous solutions .

HNO3 + H2 O H3O + + NO3-

It exhibits the general properties of an acid . Thus it reacts with
basic oxides hydroxides , carbonates , sulphites etc. to form the
corresponding salts.
HNO3 + Mg O Mg (NO3)2 + 2 H2O
HNO3 + NaOH NaNO3 + H2O
HNO3 + CaCO3 Ca(NO3) 2 + CO2 + H2O
B. HNO3 as an oxidizing agent
Nitric acid is strong oxidizing agent. Most of the oxidation
reactions of nitric acid are due to the reduction of NO3- in acid
medium.
I. Action on metals
The oxidizing power of nitric acid enable it to dissolves almost all
common metals except some noble metals like Au and Pt.
Nitric acid oxidized metal to their respective oxides while itself
reduced to form variety of reduction products.
During the reactions , the reduction products (i.e. the extent to
which the NO3 – ion of HNO3 is reduced) depend upon the
concentration of acid , activity of metal and temperature
1. Reaction with more active metals
Metal which are above the hydrogen in the electrochemical
series (Na, K, Ca, Mg, Al, Zn , Fe, Co, Sn etc.) are called more
active metals .
Metal + HNO3 Metal Nitrate + [H]
[H]+ HNO3 Reduction product + H2O

The nitric acid reduced to variety of reduction products such as

NO2, NO, NH3,NH4NO3, and N2O as shown below.
i. Very dilute nitric acid
Magnesium and manganese are only metals which produces
hydrogen with very dilute (1-2%) nitric acid

Mg + HNO3 Mg (NO3)2 + H2

Mn + HNO3 Mn (NO3)2 + H2

More active metals like zinc, iron react with very dilute HNO3 to
form NH4NO3

Zn + 2HNO3 Zn(NO3)2 + 2[H] ] *4

HNO3 + 8[H] NH3 +3H2O
NH3 + HNO3 NH4NO3

4Zn + 10 HNO3 4 Zn (NO3)2 + NH4NO3 + 3 H2O

Similarly,
4 Fe + 10 HNO3 4 Fe (NO3)2 +NH4NO3 + 3 H2O

ii. With dilute nitric acid

With dilute nitric acid , N2O is formed
Zn + 2 HNO3 Zn(NO3)2 + 2[H] ] *4
2HNO3 + 8[H] N2O +5H2O

4Zn + 10 HNO3 4 Zn (NO3)2 + N2O + 5 H2O

Similarly,

4 Mg + 10 HNO3 4 Mg (NO3)2 + N2O + 5 H2O

iii) With moderately conc. nitric acid (1:1)
Zn gives Nitric oxide (NO)

Zn + 2HNO3 Zn(NO3)2 + 2[H] ] *3

HNO3 + 3[H] NO +2H2O ] *2

3Zn + 8 HNO3 3 Zn (NO3)2 + 2 NO + 4 H2O

Fe gives ‘ic’ salt and NO2 gas

Fe + 3HNO3 Fe(NO3)3 + 3[H] ]

HNO3 + [H] NO2 + H2O ] *3

Fe + 6 HNO3 Fe (NO3)3 + 3NO2 + 3 H2O

(iv)With conc. nitric acid
Zn and Mg give nitrogen dioxide NO2

Zn + 2HNO3 Zn(NO3)2 + 2[H] ]

HNO3 + [H] NO2 + H2O ] *2

Zn + 4 HNO3 Zn (NO3)2 + 2NO2 + 2H2O

Similarly
Mg + 4HNO3 Mg (NO3)2 + 2NO2 + 2H2O
Passivity
When dipped in conc. HNO3, metals like iron , chromium, nickel
and aluminium loses their normal activity and become passive.
The passivity of these metals is due to formation of a thin
protective layer of metal oxide on surface of metal which
prevents further reaction.
Fe form ferroso ferric oxide ( Fe3O4) on the outer surface. As a
result inner surface of iron is protected by Fe3O4 .
conc.2HNO3 2 NO2 + H2O + [O] } *4
3Fe +4 [O] Fe3O4
3Fe + conc.8HNO3 Fe3O4 + 8NO2 +4 H2O
2. Reaction with less active metals
Metals which are below the hydrogen in the electrochemical
series (Cu, Ag, Hg) are called less active metals.
In this case hydrogen is not liberated . Instead nitric acid oxidizes
these metal to their respective metal oxides while itself is
reduced to form brown fumes of NO2 or colorless vapours of
NO or N2 gases

HNO3 Reduction product + H2O + [O]

Metal + [O] Metal Oxide
Metal Oxide + HNO3 metal Nitrate +H2O
 With Copper
 Cold and conc. HNO3 gives NO2 gas

2HNO3 2NO2 + H2 O + [ O ]
Cu + [ O ] CuO
CuO + 2HNO3 Cu( NO 3 )2 + H2 O

Cu + 4HNO3 Cu(NO3 ) 2 + 2NO2 + 2H2O

 hot and conc. HNO3 gives N2 gas
2HNO3 N2 + H2 O + 5[ O ]
Cu + [ O ] CuO ] *5
CuO + 2HNO3 Cu( NO 3 )2 + H2 O ] *5

5Cu + 12HNO3 5Cu(NO3 ) 2 + N2 + 6H2O

 moderately conc. HNO3 gives NO gas

2HNO3 2NO + H2 O + 3[ O ]
Cu + [ O ] CuO ] *3
CuO + 2HNO3 Cu( NO 3 )2 + H2 O ] *3

Cu + 8HNO3 3 Cu(NO3 ) 2 + 2NO + 4H2O

 ii. Oxidation of Non metals

Dilute nitric acid has no action on non metals . However, conc.

Nitric acid oxidizes many non metals such as carbon , Sulphur
into their corresponding oxy acids . While nitric acid itself
reduced to nitrogen dioxide .
i. Carbon is oxidized to carbonic acid (H2CO3)

2HNO3 H2O + NO2 + [O] ] *2

C +2 [O] + H2O H2CO3

C + 4HNO3 H2CO3 + H2O + 4NO2

ii. Sulphur is oxidized to suphuric acid ( H2SO4)

2HNO3 H2O +2 NO2 + [O] ] *3

S + 3[O] + H2O H2SO4

S + 6HNO3 H2SO4 + 2 H2O + 6NO2

 iii. Oxidation of reducing compounds

concentrated nitric acid oxidizes number of reducing compounds

.
i. Hydrogen sulphide (H2S) is oxidized to Sulphur

Conc. 2HNO3 H2O + NO2 + [O]

H2 S + [O] S + H2 O

H2S + 2HNO3 S + 2 H2O + 2NO2

ii. SO2 is oxidized to H2SO4

Conc. 2HNO3 H2O + 2NO2 + [O]

SO2 + [O] + H2O H2SO4

SO2 + 2HNO3 H2SO4 + 2NO2

 Ring test for nitrate ion (NO3-)

Presence of nitrate ion in nitrate salt or nitric acid is detected by

ring test
 In this test , aqueous solution containing nitrate ion is taken
in clean test tube and double volume of conc. H2 SO4 is added
to it. Then solution is cooled under tap water .
 A freshly prepared Ferrous sulphate (FeSO4) solution is added
dropwise from the wall of slightly inclined test tube .
 A brown ring is formed at the junction of two liquids layer
indicates the presence of NO3- ion.
 The brown ring is due to formation of addition compound
Nitrosyl ferrous sulphate which decompose on shaking
 Reaction involved

NO3- + conc. H2 SO4 HSO4 - + HNO3 ] * 2

2 HNO3 H2 O + 2 NO + 3 [ O }
2FeSO4 + H2 SO4 + [O] Fe2 ( SO4 )3 + H2 O ] * 3

2NO3- + 5H2 SO4 + 6FeSO4 3 Fe2 ( SO4 )3 + 2NO + 2 HSO4 - + 4H2 O

and
FeSO4 + NO FeSO 4 . NO
( Nitrosyl ferrous sulphate)
Brown ring
Q. Why is conc. HNO3 stored in dark brown bottle?
Ans : conc. HNO3 undergoes decomposition to produce NO2 , H2 O
and O2 gas in presence of light.
sun light(hv)
4HNO3 4NO2 + 2H2 O + O2
In order to cut off light , conc. HNO3 is stored in dark brown bottle.