BANSALCLASSES

TARGET IIT JEE 2007

CHEMISTRY
STERLING

NITROGEN FAMILY
 NITROGEN FAMILY
Nitrogen(N2)
Occurence: Nitrogen is widely distributed in nature both in free as well as in the combined state. Air is
the most abundant source of free nitrogen. It forms 75% by mass and 78% by volume of the air. In combined
state, it is found as nitrates such as Chile saltpetre (NaNO3), Indian saltpetre (KNO3) and ammonium
comopunds.

Preparation: Nitrogen can be obtained from the following two sources:

(i) Nitrogen Compounds (ii) Air

(i) Nitrogen from nitrogen compounds: (a) Nitrogen in the laboratory can be obtained by heating
ammonium nitrite or ammonium dichromate.
NH4Cl + NaNO2  NH4NO2 + NaCl
Ammonium nitrite
NH4NO2  N2 + 2H2O
(NH4)2Cr2O7  N2 + Cr2O3 + 4H2O
Nitrogen is collected by downward dispalcement of water.
(b) Pure nitrogen can be obtained by passing the ammonia vapours over heated CuO.
2NH3 + 3CuO  N2 + 3Cu + 3H2O
NH3 can also be oxidised to nitrogen by Cl2, Br2, a hypochlorite, a hypobromite or bleaching powder.
(c) It can be obtained by the action of nitrous acid (or NaNO2 and dil. H2SO4) on urea.
NH2CONH2 + 2HNO2  2N2 + CO2 + 3H2O
Urea

(d) Pure nitrogen is obtained in small amounts by heating sodium or barium azides in vacuum.
Ba(N3)2  3N2 + Ba
Barium azide

(ii) From air: (a) Commercially nitrogen is obtained by liquefaction of air. The resultant liquid isfractionally
distilled in Claude’s apparatus.
(b) By removing oxygen of the air with the use of chemical substances.
Purified air  Hot Cu  Nitrogen
2Cu + O2  2CuO
Purified air  Hot Cake  CO2, CO, N2
CO2 and CO are removed by usual methods.
Purified air  Phosphorus  P2O5 + N2

Properties:
(i) It is a colourless, tasteless and odourless gas. It is slightly lighter than air as its vapour density is 14.0. It
is sparingly soluble in water.
(ii) It can be liquefied to a colourless liquid (b. pt. –195.80C).
(iii) It does not help in combustion. Nitrogen itself is non-combustible.
(iv) It is chemically inert under ordinary conditions. However, it shows chemical activity under high
temperatures.
(a) Nitrogen combines with oxygen under the influence of very high temperature like electric spark.
N2 + O2 2NO (Nitric oxide)

Bansal Classes Nitrogen Family [2]

(b) Nitrogen combines with hydrogen in the presence of a catalyst (finely divided iron) at 200 atmospheres
and 400-5000C temperature.
N2+ 3H2 2NH3 (Ammonia)
(c) Nitrogen combines with metals at red heat to form nitrides.
6Li + N2 450

0
C
 2Li3N (Lithium nitride)
3Mg + N2 450

0
C
 Mg3N2 (Magnesium nitride)
2Al + N2 800 
0
C
 2AIN (Aluminium nitride)
Non-metals like boron, silicon at bright red heat also combine with nitrogen.
2B + N2  2BN (Boron nitride)
3Si + 2N2  Si3N4 (Silicon nitride)
(d) Nitrogen combines with calcium carbide to form calcium cyanamide at 1000 0C.
CaC2 + N2  CaCN2 + C
The mixture of calcium cyanamide and carbon is technically known as nitrolinm.

Uses: It is used in the manufacture of NH3, HNO3, CaCN2 and other nitrogen compounds.

Active nitrogen: When an electric discharge is allowed to pass through nitrogen under very low pressure
(about 2 mm), a brialliant luminiscence is observed which persists for sometime after the stoppage of the
discharge. It is observed that nitrogen after the discharge is more active. This nitrogen is termed active
nitrogen.
The exact nature of active nitrogen is not yet known.

Important compounds of Nitrogen

1. Ammonia
Nitrogen forms three well known hydrides with hydrogen:
(i) Ammonia, NH3, (ii) Hydrazine, NH2·NH2 (N2H4); (iii) Hydrazoic acid, N3H. Ammonia is the most
important of these hydrides.

Occurence: NH3 is found in traces in atmopshere. Ammonium salts such as ammonium chloride and
ammonium sulphate are found in small amounts in the soil.

Discovery: It was first isolated by Priestly by the action of ammonium chloride and lime. It was named
alkaline air.

Preparation: (i) Ammonium is obtained on a small scale from ammonium salts which evolve it when
heated with caustic soda or lime.
NH4Cl + NaOH  NH3 + NaCl + H2O
(Laboratory Preparation) 2NH4Cl + Ca(OH)2  2NH3 + CaCl2 + 2H2O
(slaked lime)
(ii) Ammonia is formed when ammonium chloride is heated with litharge.
2NH4Cl + PbO  2NH3 + PbCl2 + H2O
(iii) By reacting nitrides with water, ammonia is obtained.
AIN + 3H2O  Al(OH)3 + NH3
Mg3N2 + 6H2O  3Mg(OH)2 + 2NH3
(iv) Ammonium can also be formed by doing reduction of nitrates and nitrites with zinc and caustic soda.
Zinc and caustic soda produce nascent hydrogen which reacts with nitrates and nitrites to form ammonia.
NaNO3 + 8H Zn/   NaOH + NH3 + 2H2O
NaOH

NaNO2 + 6H Zn/
  NaOH + NH3 + H2O
NaOH

Bansal Classes Nitrogen Family [3]

(v) Calcium cyanamide is also obtained by heating ammonium compounds.
(NH4)2SO4 Heat NH3 + NH4HSO4
Ammonium Ammnoium hydrogen
sulphate sulphate
NH4H2·PO4 Heat
 NH3 + HPO3 + H2O
Ammonium Metaphosphoric
dihydrogen phosphate acid
(vi) Urea on treatment with caustic soda forms ammonia.
NH2CONH2 + 2NaOH  Na2CO3 + 2NH3
urea

Drying of Ammonia gas:

The common dehydrating agents like sulphuric acid or CaCl2 or P2O5 cannot be used as these react with
ammonia.
2NH3 + H2SO4  (NH4)2SO4
Ammonium sulphate
CaCl2 + 8NH3  CaCl2·8NH3
Addition product
P2O5 + 6NH3 + 3H2O  2(NH4)3PO4
Ammonium phosphate
Fro drying, quick lime is used as it does not react with ammonia but reacts readily with moisture.
CaO + H2O  Ca(OH)2
quick lime
Manufacture of Ammonia:
(i) Haber’s process: The method involves the direct combination of nitrogen and hydrogen according to
the following reaction:
N2 + 3H2 2NH3 + 24.0 kcal
Raw materials: Nitrogen and hydrogen are the chief raw materials. Nitrogen is obtained from air by
liquefaction followed by fractional evaporation of liquid air. Hydrogen is obtained by electrolysis of water.

(ii) Bosch Process: From Powder gas & water gas

(iii) Cyanamide process: CaCN2 + 3H2O 180


0
C
 CaCO3 + 2NH3
(steam) 3-4 atm

(iv) From ammoniacal liquor obtained during coal distillation: Large quantities of ammonia are obtained
as a by-product in the manufacture of coal gas.

Physical properties: (i) Ammonia is a colourless gas with a characterstic pungent odour. it brings tears
into the eyes.
(ii) It is highly soluble in water. This high solubility is due to the hydrogen bonding. The solubility of
ammonia increases with increase of pressure and decreases with increase of temperature.

Bansal Classes Nitrogen Family [4]

(iii) It can be easily liquefied at room temperature by the application of pressure.
(iv) Ammonia molecules link together to form associated molecules through hydrogen bonding.

Higher melting point and boiling point in comparison to other hydrides of V group are due to hydrogen
bonding.

Chemical Properties:(i) Stability : It is highly stable. It decomposes into nitrogen and hydrogen at red
heat or when electric sparks are passed through it.
2NH3 N2 + 3H2
(ii) Combustion: Ordinary, ammonia is neither combustible nor a supporter of combustion. However, it
burns in the presence of oxygen to form nitrogen and water.
4NH3 + 3O2  2N2 + 6H2O
(iii) Basic nature: Ammonia is a Lewis base, accepting proton to form ammonium ion as it has tendency
to donate an electron pair.

It forms salts with acids.

NH3 + HCl  NH4Cl (Ammonium chloride)
Thick white fumes
2NH3 + H2SO4 (NH4)2SO4 (Ammonium sulphate)
It’s solution is a weak base. the solution is described as aqueous ammonia. It’s ionisation in water is
represented as:
NH3 + H2O  NH4OH NH4+ + OH–
The solution turns red litmus to blue and phenolphthalein pink.

(iv) Oxidation: It is oxidised to nitrogen when passed over heated CuO or PbO
3CuO + 2NH3  3Cu + N2 + 3H2O
3PbO + 2NH3  3Pb + N2 + 3H2O
Both chlorine and bromine oxidise ammonia.
2NH3 + 3Cl2  N2 + 6HCl
6NH3 + 6HCl  6NH4Cl
––––––––––––––––––––––––––––
8NH3 + 3Cl2  N2 + 6NH4Cl
(excess)
When chlorine is in excess an explosive substance nitrogen trichloride is formed.
NH3 + 3Cl2  NCl3 + 3HCl
Iodine flakes when rubbed with liquor ammonia form a dark brown precipitate of ammoniated nitrogen
iodide which explodes readily on drying.
2NH3 + 3I2  NH3·NI3 + 3HI

Bansal Classes Nitrogen Family [5]

Hypochlorites and hypobromites oxidise ammonia to nitrogen.
2NH3 + 3NaClO  N2 + 3NaCl + 32O
The oxidation of ammonia with bleaching powder occurs on warming.
3CaOCl2 + 2NH3  3CaCl2 + N2 + 3H2O
Thus, ammonia acts as a reducing agent.
The restricted oxidation of NH3 can be done with air, when the mixture is passed over heated platinum
gauze at 700-8000C.
4NH3 + 5O2  4NO + 6H2O
This is the Ostwald’s process and used for the manufacture of HNO3.
(v) Formation of amides: When dry ammonia is passed over heated sodium or potassium, amides are
formed with evolution of hydrogen.
2Na + 2NH3  2NaNH2 + H2
Sodamide

(vi) Reactions of aqueous ammonia: Many metal hydroxides are formed which may be precipitated or
remain dissolved in the form of complex compound in excess of NH4OH.
FeCl3 + 3NH4OH  Fe(OH)3 + 3NH4Cl
ppt.

AlCl3 + 3NH4OH  Al(OH)3 + 3NH4Cl

ppt.
CrCl3 + 3NH4OH  Cr(OH)3 + 3NH4Cl
ppt.
CuSO4 + 2NH4OH  Cu(OH)2 + (NH4)2SO4
Blue ppt.
Cu(OH)2 + (NH4)2CO4 + 2NH4OH  [Cu(NH3)4]SO4 + 4H2O
Tetramine copper
sulphate
(colourless solution)
CdSO4 + 4NH4OH  [Cd(NH3)4]SO4 + 4H2O
Cadmium tetramine
sulphate
(Colourless solution)
AgNO3 + NH4OH  AgOH + NH4NO3
White ppt.
AgOH + 2NH4OH  [Ag(NH3)2](OH) + 2H2O
soluble
AgCl also dissolve in NH4OH solution
AgCl + 2NH4OH  [Ag(NH3)2]Cl + 2H2O
Diamine silver chloride
ZnSO4 + 2NH4OH  Zn(OH)2 + (NH4)2SO4
ppt.
Zn(OH)2 + (NH4)2SO4 + 2NH4OH  [Zn(NH3)4]SO4 + 4H2O
Tetramine zinc sulphate
(soluble) colourless
Nickel salt first gives a green precipitate which dissolves in excess of NH4OH.
NiCl2 + 2NH4OH  Ni(OH)2 + 2NH4Cl
Ni(OH)2 + 2NH4Cl + 4NH4OH  [Ni(NH3)6]Cl2 + 6H2O
It forms a white precipitate with mercuric chloride.
HgCl2 + 2NH4OH  HgNH2Cl + NH4Cl + H2O
Amido mercuric
chloride

Bansal Classes Nitrogen Family [6]

It forms a grey precipitate with mercurous chloride.
Hg2Cl2 + 2NH4OH  Hg  HgNH 2 Cl + NH4Cl + H2O
 
Grey

(vii) Reaction with Nessler’s reagent: A reddish brown ppt. is formed.

2KI + HgCl2  HgI2 + 2KCl
2KI + HgI2  K2HgI4
Alkaline solution of K2HgI44 is called Nessler’s reagent.
This gives brown ppt. with NH3 called iodide of Million’s base.
2K2HgI4 + NH3 + 3KOH  H2NHgOHgI + 7KI + 2H2O
Brown ppt.

Uses: (i) Liquid hydrogen is not safe to transport in cylinders. Ammonia can be easily liquefied and
transported safely in cylinders. Ammonia can be decomposed into hydrogen and nitrogen by passing over
heated metallic catalyst. Thus, ammonia is the source for the production of hydrogen at any destination.
(ii) Ammonia is also used in the manufacture of urea which is an excellent fertilizer of nitrogen.

Hydrazine or Diamide NH2NH2 or N2H4

This is another hydride of nitrogen. It is prepared by following methods:

(i) Raschig’s method: A strogn aqueous solution of ammonia is boiled with sodium hypochlorite in presence
of a little glue.
NH3 + NaOCl  NH2Cl + NaOH
NH2Cl + NH3  NH2·NH2 + HCl
Chloramine Hydrazine
–––––––––––––––––––––––––––––––––––––––––––––––––––
2NH3 + NaOCl  NH2NH2 + NaCl + H2O

It burns in air liberating huge amount of energy. The alkyl derivatives of hydrazine are used these days as
potential rocket fuels. It reacts with nitrous acid to give hydrazoic acid, N3H.
N2H4 + HNO2  N3H + 2H2O

Hydrazine and its salts act as powerful reducing agents.

PtCl4 + N2H4  Pt + N2 + 4HCl
4AgNO3 + N2H4  4Ag + N2 + 4HNO3
4AuCl3 + 3N2H4  4Au + 3N2 + 12 HCl

It reduces Fehling’s solution to red cuprous oxide, iodates to iodides and decolourises acidified KMnO 4
solution. It is used as a fuel for rockets, reducing agent and a reagent in organic chemistry.

Structure

Hydrazoic Acid, N3H

It is the third hydride of nitrogen. It is an acid while other hydrides, NH3 and N2H4 are bases. It is prepared
by the action of nitrous acid on hydrazine.
NH2·NH2 + HNO2  N3H + 2H2O

Bansal Classes Nitrogen Family [7]

It is also formed in the form of sodium salt by passing nitrous oxide on sodamide.
Dry
 
NH 3
N

2O


It reduces acidified KMnO4, nitrous acid, etc.

2N3H + O  3N2 + H2O
N3H + HNO2  N2 + N2O + H2O
It oxidises HCl into Cl2
N3H + 2HCl  N2 + NH3 + Cl2
Oxides of Nitrogen
N2O3 and N2O5 monomeric other are dimeric

Nitrogen forms a number of oxides. The well known oxides of nitrogen are:
(i) Nitrogen oxide, N2O
(ii) Nitric oxide, NO
(iii) Nitrogen trioxide, N2O3
(iv) Nitrogen dioxide or Di-nitrogen tetroxide, NO2 or N2O
(v) Nitrogen pentoxide, N2O5

(I) Nitrogen Oxide, N2O or Laughing Gas (Neutral)

Preparation:

It can be prepared by heating ammonium nitrate or a mixture of sodium nitrate and ammonium sulphate.
NH4NO3  N2O + 2H2O
2NaNO3 + (NH4)2SO4  2NH4NO3 + Na2SO4

2N2O + 4H2O

FeSO4 + NO  FeSO4.NO
Addition product
H2SO4 + 2NH3  (NH4)2SO4
Ammonium Sulphate

The following reactions can also be used to prepare nitrous oxide.

NaNH2 + N2O  NaN3 + NaOH + NH3

(a) By the action of cold and dilute nitric acid on zinc metal.
Fe/4Zn + 10HNO3  4Zn (NO3)2 + N2O + 5H2O

(b) By reducing nitric acid with stannous chloride and hydrochloric acid.
4SnCl2 + 8HCl + 2HNO3  4SnCl4 + N2O + 5H2O

(c) By reducing nitric oxide with sulphur dioxide.

2NO + SO2 + H2O  H2SO4 + N2O

(d) By heating the mixture of hydroxylamine hydrochloride and sodium nitrite (1 : 1)

NH2OH.HCl + NaNO2  N2O + NaCl + 2H2O

Bansal Classes Nitrogen Family [8]

Properties:
(a) It is a colourless gas with pleasant odour and sweet taste.
(b) When inhaled in moderate quantity, it produces hysterical laughter, hence named as laughing gas. However,
when inhaled for long, it produces insensibility and may prove fatal too.
(c) It is heavier than air.
(d) It is fairly soluble in cold water but not in hot water.
(e) It is neutral to litmus.
(f) It does not burn but support combustion. The burning material decompose nitrous oxide into nitrogen
and oxygen. The oxygen then helps in the buring.
2N2O 520
  2N2 + O2
900 o C

It supports combustion of sulphur, phosphorus, magnesium, sodium, candle and a splineter.

S + 2N2O  SO2 + 2N2
4P + 10N2O  2P2O5 + 10N2
Mg + N2O  MgO + N2

(g) It is decomposed by red hot copper.

Cu + N2O  CuO + N2

(h) A mixture of hydrogen and nitrous oxide (equal volumes) explodes with violence.
N 2O + H 2  N 2 + H 2O

(i) N2O + NaNH2  NaH3 + NH3 + NaOH

Uses:
(i) It is used as the propellant gas for whipped ice-cream.
(ii)A mixture of nitrous oxide and oxygen is used as an ananesthetic in dental and other minor surgical
operations.

Structure:
N2O is linear and unsymmetrical molecule. It is considered as a resonance hybrid of the following two
structures:

        
:N 
N 
O : : N 2 
N

It has a very small value of dipole moment (0.116D)

Tests:
(i) It has sweet smell.
(ii) It supports the combustion of glowing splinter.
(iii) It does not form brown fumes with nitric oxide.
(iv) N2O does not form H2N2O2 with H2O nor hyponitrites with alkali.

(II) Nitric oxide, NO Neutral

Preparation:
(a) By the action of dilute nitric acid on copper (Lab. Method). the nitric oxide liberated is collected over
water.
Ag/Hg/Pb/3Cu + 8HNO3  3Cu(NO3)2 + 2NO + 4H2O

Bansal Classes Nitrogen Family [9]

The liberated gas may contain NO2 and N2O. These are separated by passing the mixture through ferrous
sulphate solution. NO forms a dark nitroso-ferrous sulphate. When this solution is heated, pure nitric oxide
is liberated.
FeSO4 + NO  FeSO4.NO heate  FeSO4 + NO
(impure gas) (Dark Brown) (Pure gas)

(b) A pure sample of nitric oxide is obtained when a mixture of KNO3, FeSO4 and dilute H2SO4 is heated.
This is also a laboratory method.

2KNO3 + H2SO4  K2SO4 + 2HNO3

2HNO3  H2O + 2NO + 3O
[2FeSO4 + H2SO4 + O  Fe2(SO4)3 + H2O] x 3
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
2KNO3 + 6FeSO4 + 4H2SO4  K2SO4 + 3Fe2(SO4)3 + 2NO + 4H2O
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
(c) Nitric oxide is the first product obtained from the following two processes during the manufacture of
nitric acid.

(i) Electric arc process:

By passing air through an electric arc, nitrogen and oxygen of the air combine together to form nitric oxide.
N2 + O2 2NO
(ii) Ostwald’s process:
By restricted oxidation of ammonia with air in presence of platinum gauze catalyst at 750 0C, nitric oxide is
formed.
4NH3 + 5O2    4NO + 6H2O
Pt . gauze
0
750 C , 6 atm

Properties:
(a) It is a colourless gas, slightly heavier than air.
(b) It is sparingly soluble in water.
(c) It is paramagnetic indicating the presence of unpaired electron in the molecule.
(d) It is neutral to litmus.
(e) It at once reacts with oxygen to give brown fumes of nitrogen dioxide.
2NO + O2  2NO2
(f) It is stable oxide. It decomposes into nitrogen and oxygen when heated at 8000C.
2NO 800 
0
C
 N2 + O2
(g) It is combustible and supports combustion of boiling sulphur and burning phosphorus.
S + 2NO  SO2 + N2
(h) It dissolves in cold ferrous sulphate solution by forming a hydrated nitrosyl complex.
[Fe(H2O)6]SO4 + NO [Fe(H2O)5NO]SO4 + H2O
Ferrous sulphate Hydrated nitrosyl
complex (Brown colour)
 Heat
FeSO4 + NO + 5H2O
(i) It is oxidised to nitric acid by oxidising agents like acidified KMnO 4 or hypochlorous acid. Thus, it acts
as a reducing agent.
6KMnO4 + 9H2SO4 + 10NO  3K2SO4 + 6MnSO4 + 10HNO3 + 4H2O
[HClO  HCl + O] x 3
[NO + O  NO2] x 3
3HClO + 2NO + H2O  2NO3 + 3HCl

Bansal Classes Nitrogen Family [10]

HNO3 oxidises nitric oxide into NO2.
2HNO3 + NO  H2O + 3NO2

(j) It acts as an oxidising agent. It oxidises SO2 to H2SO4 ande H2S to S.

SO2 + 2NO + H2O  H2SO4 + N2O
H2S + 2NO  H2O + S + N2O

When exploded with hydrogen it liberates nitrogen.

2H2 + 2NO  2H2O + N2

However, when a mixture of hydrogen and nitric oxide is passed over platinum black, ammonia is formed.
2NO + 5H2  2NH3 + 2H2O
Stannous chloride reduces nitric oxide to hydroxylamine.
[SnCl2 + 2HCl  SnCl4 + 2H] x 3
2NO + 6H  2NH2OH
–––––––––––––––––––––––––––––––––––––––––
3SnCl2 + 6HCl + 2NO  3SnCl4 2NH2OH

(k) Nitric oxide directly combines with halogen (fluorine, chlorine, bromine) to form corresponding nitrosyl
halides.
2NO + X2  2NOX
(F2, Cl2 or Br 2) Nitrosyl halide

Uses:
(i) In the manufacture of nitric acid.
(ii) As a catalyst in lead chamber process for the manufacture of sulphuric acid.
(iii) In the detection of oxygen to ditinguish it from nitrous oxide.

Structure:
The molecule NO has eleven valnecy electrons and it is impossible for all of them to be paired.Hence, the
molecule contains an odd electron which makes the gaseous nitric oxide as paramagnetic.

The structure is represented as a resonance hybrid.

In the liquid and solid states NO is known to form a loose dimer, N2O2

(III) Dinitrogen Trioxide, N2O3

This oxide is also called nitrogen sesquioxide or nitrous anhydride.

Preparation: It is obtained by the reduction of nitric acid with arsenious oxide.

2HNO3  H2O + N2O3 + 2O
As2O3 + 2O  As2O5
As2O5 + 3H2O  2H3AsO4
––––––––––––––––––––––––––––––––––––––––
As2O3 + 2HNO3 + 2H2O  2H3AsO4 + N2O3

Bansal Classes Nitrogen Family [11]

It is known in pure state in solid form at very very low temperature. In the vapour state, it is present as an
equimolar mixture of NO and NO2. The mixture of NO and NO2 may be obntained by the action of 6N
nitric acid on copper.
2Cu + 6HNO3 2Cu(NO3)2 + NH  NO
2 + 3H2O
N 2O3

(a) It condenses to a bluw coloured liquid at –30 C. The liquid when warmed at room temperature,
0

decomposes to a mixture of NO and NO2 (Brown coloured)

N 2O3 Room
 
Temperature NO  O 2
 
Blue coloured Brown coloured gas
liquid

(b) It is an acidic oxide. If forms nitrous acid and water and hence the name nitrous anhydride.
N2O3 + H2O  2HNO2
The oxide combines with caustic alkali forming corresponding nitrite.
2NaOH + N2O3  2NaNO2 + H2O

Structure:
Since the oxide is unstable in liquid and gaseous states and decomposes into NO and NO2, it may be
assumed that it has the following electronic structure:
or O=N–O–N=O
The structure is supported by its diamagnetic behaviour strucutre of N2O3 is of two forms:

(IV) Nitrogen Dioxide, NO2 or DInitrogen Tetroxide, N2O4

This oxide exists as NO2 in gaseous state while at low temperature, it exists as a dimer N2O4 (Solid state)
2NO2 N 2O 4
Brown gas Colourless solid

Preparation: It is prespared in the laboratory either by heating nitrates of heavy metal or by the action of
concentrated nitric acid on metals like copper, silver, lead etc.
2Pb(NO3)2  2PbO + 4NO2 + O2

The mixture of nitrogen dioxide and oxygen is passed through a U-tube cooled by freezing mixture. Nitrogen
dioxide condenses to a pale yellow liquid while oxygen escapes.
Zn(NO3)2  ZnO + NO2 + O2
AgNO3  Ag + NO2 + O2
Cu + 4HNO3  Cu(NO3)2 + 2NO2 + 2H2O
It is also obtained by air oxidation of nitric oxide.
2NO + O2  2NO2

Properties:
(a) It is brown colored gas wit pungent odour. Above 140 0C, it is 100%NO2. The liquid as well as solid is
entirely N2O4 (dimer) at low temperature. The liquid boils at 220C and solid melts at –110C.
(b) It decomposes completely into nitric oxide and oxygen at 6200C.
NO2 + HCl  NOCl + Cl2 + H2O

Bansal Classes Nitrogen Family [12]

 2NO2 2 NO  O 2
 
Gaseous mixture
colourless
(c) When reacted with cold water, it forms a mixture of nitrous acid and nitric acid.
2NO2 + H2O  HNO2 + HNO3
On account of this, it is known as mixed anhydride of these two acids. However, with an excess of warm
water it forms nitric acid and nitric oxide.
3NO2 + H2O  2HNO3 + NO

(d) When absorbed by alkalies, nitrites and nitrates are formed.

2NO2 + 2NaOH  NaNO2+ NaNO3 + H2O

(e) It acts as an oxidising agent. It oxidises metals like sodium, potassium, mercury, tin copper, etc.
NO2 + 2Na  Na2O + NO
NO2 + 2Cu  Cu2O + NO

None metals like carbon, sulphur, phosphorus when burnt in its stmosphere, are converted into corresponding
oxides.
5NO2 + 2P  P2O5 + 5NO
2NO2 + S  SO2 + 2NO
2NO2 + C  CO2 + 2NO
It liberates iodine from KI and turns starch-iodide paper blue.
2KI + 2NO2  2KNO2 + I2

In aqueous solution, it oxidises SO2 to sulphuric acid

SO2 + H2O + NO2  H2SO4 + NO
This reaction is used for the manufacture of H2SO4 by lead chamber process.
H2S is oxidised to S and CO to CO2.
H2S + NO2  H2O + S + NO
CO + NO2  CO2 + NO
(f) It behaves also as a reducing agent. It redduces ozone to oxygen.
2NO2 + O3  N2O5 + O2

It decolourises acidified KMnO4 solution.

2KMnO4 + 3H2SO4  K2SO4 + 2MnSO4 + 3O2 + 5O
10NO2 + 5H2O + 5O  10HNO3
-----------------------------------------------------------------------
2KMnO4 + 3H2SO4 + 10NO2 + 2H2O  K2SO4 + 2MnSO4 + 10 HNO3

Uses
(i) It is used for the manufacture of nitric acid.
(ii) It is employed as a catalyst in the lead chamber process for the manufacture of sulphuric acid.

Structure
NO2 molecule has V-shaped structure with O-N-O bond angle 132o and N-O bond length of about
1.19Å which is intermediate between a single and a double bond. Hence, NO2 is regarded as a resonance
hybrid of the following two streuctures.



Bansal Classes Nitrogen Family [13]

The molecule is an odd electron molecule. The paramagnetic behaviour of NO 2 confirms this view. Due to
prossession of odd eledtron, it is colored and has a tendency to polymerize to form a colour less dimer,
N2O4. the dimer is planar in structure with N-N bond length 1.75Å.

(v) Nitrogen Pentoxide, N2O5

This oxide is also known as nitric anhydride.

Preparation
It is prepared by distilling concentrated nitric acid with phosphorus pentoxide in a glass apparatus.
2NHO3  H2O + N2O5
P2O5 + H2O  2HPO3
----------------------------------------
P2O5 + 2HNO3  2HPO3 + N2O5
----------------------------------------

It is also prepared by the action of dry chlorine on solid silver nitrate at 95oC.
4AgNO3 + 2Cl2  4AgCl + 2N2O5 + O2

Properties
(a) It is a white crystalline solid. The crystals melt at 30oC giving a yellow liquid which decomposes at 40oC
to give brown NO2. The decompostion occurs with explosion.
2N2O5  4NO2 + O2

(b) It is an acidic oxide. It reacts with water with hissing sound forming nitric acid.
N2O5 + H2O  2HNO3
On account of this, it is known as nitric anhydride. With alkalies if forms nitrates.
2NaOH + N2O5  2NaNO3 + H2O

(c) It acts as a strong oxidising agent. It affect organic substances such as cork, rubber, etc. It oxidises
iodine readily into iodine pentoxide.
I2 + 5N2O5  I2O5 + 10NO2

(d) With aqueous NaCl, the ionic reaction takes place.

N2O5 + NaCl naNO3 + NO2Cl
The reaction proves that N2O5 exists as ionic nitronium nitrate (NO2, NO3)

(e) N2O5 is decomposed by alkali metals.

N2O5 + Na  naNO3 + NO2

Structure
In the gaseous state, it exists as a symmetrical molecule having the structure O2N - O - NO2, N - O - N
bond is almost linear. It may be represented as:

Bansal Classes Nitrogen Family [14]

X- ray studies suggest that solid N2O5 is ionic in nature, i.e. nitronium nitrate, NO2, NO3-.

5. Oxyacids of Nitrogen
Nitrogen forms a number of oxyacids. The most common and important oxyacids are:

(i) Hyponitrous acid, H2N2O2

Preparation

Properties
It is colourless, hygroscopic. It is very weak dibasic acid but a strong reducing agent.
H2N2O2  H2O + N2O
It has zero dipole moment which is based on its trans structure.

(ii) Nitrous Acid, HNO2

The free acid is unknown. It is known only in solution.

Preparation
A solution of nitrous acid can be prepared by acidifying solutions of nitrites with mineral acids.
2NaNO2 + H2SO4  Na2SO4 + 2HNO2
KNO2 + HCl  KCl + HNO2
Nitrates on heating with lead decompose to give nitrite.
NaNO3 + Pb  
 NaNO2 + 2HNO2
An aqueous solution of the acid, free from any salt, can be prepared by treating barium nitrite with calculated
amount of dilute sulphuric acid. Singce the acid is very unstable, the reaction is carried out at low temperature
(freezing mixture temperature). The insoluble barium sulphate is filtered off.

Ba(NO2)2 + H2SO4  BaSO 4 + 2HNO2

inso lub le

A solution of nitrous acid may also the prepared by dissolving N2O3 in water.
HNO2 + NaOH  NaNO2 + H2O
NH3 + H2O2  HNO2 + H2O

Properties
(a) Aqueous solution of nitrous acid is pale blue. This is due to the presence of nitrogen trioxide, N 2O3 the
colour fades on standing for sometime.

(b) It is weak acid and reacts with alkalies to form salts known as nitrites.
HNO2 + NaOH  NaNO2 + H2O

Bansal Classes Nitrogen Family [15]

(c) Auto-oxidation
The acid is unstable and even in cold solution, it undergoes auto-oxidation.
2H NO 2  2NO + H2O + O
HNO2 + O  HNO3
----------------------------------
2HNO2  2NO + HNO3 + H2O
-----------------------------------

On heating, it decomposes into nitric oxide and nitrogen dioxide.

2HNO2  H2O +

(d) Oxidising nature

It acts as an oxidising agent due to ease with which it decomposes to give nascent oxygen. the potential
equation when it acts as an oxidising agent is:
2HNO2  H2O + 2NO + O

(i) Iodine is liberated from potassium iodide.

2KI + H2SO4 + 2HNO2  K2SO4 + 2NO + I2 + 2H2O

(ii) Stannous chloride is oxidised to stannic chloride.

SnCL2 + 2HCL + 2HNO2  SnCl4 + 2NO + 2H2O

(iii) Sulphur chloride is oxidised to sulphuric acid.

SO2 + 2HNO2  H2SO4 + 2NO

(iv) Sulphur is formed by oxidation of hydrogen sulphide.

H2S + 2HNO2  S + 2H2O + 2NO

(v) Acidified ferrous sulphate is oxidised to ferric sulphate.

2FeSO4 + H2SO4 + 2HNO2  Fe2(SO4)3 + 2NO + 2H2O

(vi) Sodium arsentie is oxidised to sodium arsenate.

Na3AsO3 + 2HNO2  Na3AsO4 + 2NO + H2O

(e) Reducing nature

Nitrous acid acts as a reducing agent as it can be oxidised into nitric acid.
HNO2 + O  HNO3

(i) It reduces bromine to hydrobromic acid.

Br2 + H2O + HNO2  2HBr + HNO3
(ii) Acidified potassium permanganate is decolourised.
2KMnO4 + 3H2SO4 + 5HNO2  K2SO4 + 2MnSO4 + 5HNO3 + 3H2O
(iii) Acidified potassium dichromate is reduced to chromic sulphate (green)
K2Cr2O7 + 4H2SO4 + 3HNO2  K2SO4 + Cr2(SO4)3 + 3HNO3 + 4H2O
(iv) Hydrogen peroxide is reduced to water
H2O2 + HNO2  HNO3 + H2O

Bansal Classes Nitrogen Family [16]

(f) Reaction with ammonia
It reacts with ammonia to form nitrogen and water.
NH3 + HNO2  [ NH 4 NO 2 ]  N2 + 2H2O
Intermediate

(g) Reaction with urea

It decomposes urea and aliphatic primary amines to nitrogen
NH 2 CONH 2 + 2HNO  2N + CO + 3H O
Urea 2 2 2 2

C 2 H 5 NH 2 + HO . NO  C 2 H 5OH + N2 + H2O
Ethyla min e Ethyl alcohol

Structure
Since nitrous acid forms two types of organic derivatives, the nitrites (R-ONO) and nitro compounds (R-
NO2), it is considered to be a automeric mixture ot two forms.

HON=O and

or and

(iii) Nitric acid, HNO3

It was named aqua fortis (means strong water) by alchemists.

Preparation
(i) Laboratory Method
KNO3 + conc. H2SO4  KHSO4 + HNO3(vap)
vapours of nitric acid evolved are condensed in a glass receiver.

(ii) Industrial Preparation

(A) Birkeland Eyde Process or arc process
0

N2 + O2   2NO - heat

3000 C
step 1 Electric Arc

step 2 NO + O2  NO2
step 3 NO2 + H2O  HNO2 + HNO3
step 4 HNO2  HNO3 + NO + H2O

(B) Ostwald’s Process

NH3 + O2 700  NO + H O + heat
Pt . gauze
step 1 8000 C 2

step 2 NO + O2  NO2
step 3 NO2 + H2O  HNO2 + HNO3
step 4 HNO2  HNO3 + NO + H2O

Bansal Classes Nitrogen Family [17]

Properties
Physical
Nitric acid usually acquires yellow colour due to its decomposition by sunlight into NO 2.
4HNO3 Sunlight
 4NO2 + 2H2O + O2
The yellow colour of the acid can be removed by warming it to 60-80oC and bubbling dry air through it.
It has extremely corrosive action on the skin and causes painful sores.

Chemical
(a) It is very strong acid. It exhibits usual properties of acids. It reacts with basic oxides, carbonates,
bicarbonates and hydroxides forming corresponding salts.
CaO + 2HNO3  Ca(NO3)2 + H2O
Na2CO3 + 2HNO3  2NaNO3 + H2O + CO2
NaOH + HNO3  NaNO3 + H2O

(b)Oxidising nature : Nitric acid acts as a strong oxidising agent as it decomposes to give nascent oxygen
easily.
2HNO3  H2O + 2NO2 + O
or 2HNO3  H2O + 2NO + 3O

(i) Oxidation of non-metals: The nascent oxygen oxidises various non-metals to their corresponding
highest oxyacids.

(1) Sulphur is oxides to sulphuric acid

S  6 HNO 3  H SO + 6NO + 2H O
conc. and hot 2 4 2 2

(2) Carbon is oxidised to carbonic acid

C + 4HNO 3  H 2 CO 3 + 4NO 2 + 2H 2 O
(3) Phosphorus is oxidised to orthophosphoric acid.
2P + 10HNO 3  2H 3 PO 4 + 10NO 2 + 2H 2 O
conc. and hot
(4) Iodine is oxidised to iodic acid
I2 + 10HNO 3  2HIO 3 + 10NO 2 + 4H 2 O
conc. and hot
(ii) Oxidation of metalloids
Metalloids like non-metals also form highest oxyacids
(1) Arsenic is oxidised to arsenic acid
2As + 10HNO 3  2H 3 AsO 4 + 10NO 2 + 2H 2 O
or As + 5HNO 3  H 3 AsO 4 + 5NO 2 + H 2 O
conc. and hot
(2) Antimony is oxidised to antimonic acid
Sb + 5HNO 3  H 3 SbO 4 + 5NO 2 + H 2 O
conc. and hot
(3) Tin is oxidised to meta-stannic acid.
Sn + 2HNO 3  H 2 SnO3 + 4NO 2 + H 2 O

Bansal Classes Nitrogen Family [18]

(iii) Oxidation of Compounds:
(1) Sulphur dioxide is oxidised to sulphuric acid
SO 2 + 2HNO 3  H 2 SO 4 + 2NO 2
(2) Hydrogen sulphiode is oxidised to sulphur
H 2 S + 2HNO 3  2NO 2 + 2H 2 O + S
(3) Ferrous sulphate is oxidised to ferric sulphate in presence of H 2SO 4
6FeSO 4 + 3H 2 SO 4 + 2HNO 3  3Fe 2 (SO 4 ) 3 + 2NO + 4H 2 O
(4) Iodine is liberated from KI.
6KI + 8HNO 3  6KNO 3 + 2NO + 3I2 + 4H 2 O
(5) HBr, HI are oxidised to Br 2 and I2 , respectively.
2HBr + 2HNO 3  Br 2 + 2NO 2 + 2H 2 O
Similarly, 2HI + 2HNO 3  I2 + 2NO 2 + 2H 2 O
(6) Ferrous sulphide is oxidised to ferrous sulphate
FeS + HNO 3  FeSO 4 + 8NO 2 + 4H 2 O
(7) Stannous chloride is oxidised to stannic chloride is presence of HCl.
2HNO 3 + 14H  NH 2 OH + NH 3 + 5H 2 O
Hydroxylamine
NH 3 + HNO 3  NH 4 NO 3
------------------------------------------------------------------------------
7SnCl 2 + 14HCl + 3HNO 3  7SnCl 4 + Nh 2 OH + NH 4 NO 3 + 5H 2 O
(8) Cane sugar is oxidised to oxalic acid.
C 12H 22O 11 + 36HNO 3  6(COOH) 2 + 36NO 2 + 23H 2 O

(c) Action on Metals: Most of the metals will the exveption of noble metals like gold and platinum are
attacked by Nitric acid plays a double role in the action of metals, i,e, it acts as an acid as well as an
oxidising agent. ARmstrong postulated that primary action of nitric acid is to produce hydrogen in the
nascent form. Before this hydrogen is allowed to escape, it reduces the nitric acid into number of products
like NO2, NO, N2O, N2 or NH3 according to the following reactions:
Metal + HNO3  Nitrate + H
2HNO3 + 2H  2NO + 2H2O
2HNO3 + 6H 2NO + 4H2O
2HNO3 + 10H  N2 + 6H2O
2HNO3 + 16 H  2NH3 + 6H2O
The progress of the reaction is controlled by a number of factors:
(a) the nature of the metal,
(b) the concentration of the acid,
(c) the temperature of the reaction,
(d) the presence of other impurities.

Bansal Classes Nitrogen Family [19]

--------------------------------------------------------------------------------------------------------
Concentration of Metal Main Products
nitric acid
--------------------------------------------------------------------------------------------------------
Mg, Mn H2 + Metal nitrate
Very dilute HNO3 (6%) ----------------------------------------------------------
Fe, Zn, Sn NH4NO3 + metal nitrate + H2O
--------------------------------------------------------------------------------------------------------
Pb, Cu, Ag, Hg NO + metal nitrate + H2O
----------------------------------------------------------
Dilute HNO3 (20%) Fe, Zn N2O + metal nitrate + H2O
----------------------------------------------------------
Sn NH4NO3 + Sn(NO3)2
--------------------------------------------------------------------------------------------------------
Zn, Fe, Pb, Cu, Ag NO2 + metal nitrate + H2O
Conc. HNO3(70%) ----------------------------------------------------------
Sn NO2 + H2SnO3
Metastannic acid
--------------------------------------------------------------------------------------------------------
Action on Proteins
(i) Nitric acid attacks proteins forming a yellow nitro compound called xanthoprotein. It, therefore, stains
skin and renders wool yellow. This property is utilized for the test of proteins.

(ii) Oxidation A number of organic compounds are oxidised.

Sawdust catches fire when nitric acid is poured on it. Turpentine oil bursts into flames when treated with
fuming nitric acid. Cane sugar is oxidised to oxalic acid. Toluene is oxidised to benzoic acid with dil.
HNO 3.

Structure
Nitric acid is a monobasic acid, i.e., the molecule consist of one hydroxyl group as it is formed by the hydrolysis
of nitryl chloride, NO2Cl. It may be structurally represented as below:

or
Gaseous nitric aicd is a planar molecule. The bond lengths and bond angles as present in the molecule are
represented in the figure:

It is supposed to exist in two resonting forms.

Bansal Classes Nitrogen Family [20]

PHOSPHORUS
It glows in the dark and was, therefore, called phosphorus (Greek work, phos=light, and phero=1 carry)

Occurrence
Since phosphorus is an active element, it is not found free in nature. It is widely distributed in nature in the
combined state. It occurs as phosphates in the rocks and in the soil and as phosphoproteins in all living beings. It
is an essential constituents of bones, teeth, blood and nervous tissure. It is necessary for the growth of plants.
Bone ash contains about 80% calcium phosphate. it is present in milk, eggs and guano (excreta of seabirds). The
principal minerals of phosphorous are
(i) Phosphorite Ca3(FO4)2
(ii) Fluorapatite 3Ca3(PO4)2.CaF2
(iii) Chlorapatite 3Ca3(PO4)2.CaCl2

Extraction
Phosphorus is extracted either from phosphorite or bone ash by the application of following two processes.

(i) Retort process or old process.

(ii) Electrothermal process or modern process.

(i) Retort process or old process

The phosphorite mineral or bone ash is digested with concentrated sulphuric acid (about 60%). Insoluble calcium
sulphate and orthophosphoric acid are formed.
Ca(PO4)2 + 3H2SO4  3CaSO4 + 3H3PO4
The syrupy liquid is separated from insoluble residue by filtration. The liquid is evaporated when it changes into
metaphosphoric acid with evolution of water.
H3PO4  HPO 3 + H 2O
Metaphosph oric
acid

The metaphosphoric acid is mixed with powdered coke and distilled in fireclay retorts at a bright red het. The
acid is reduced to phosphorus by carbon which comes in vaporized form. The vapours are condensed below
water.
4HPO3 + 10C  P4 + 10CO + 2H2O

(ii) Electrothermal process or modern process.

The mixture of phosphorite, carbon and silica is dried and then introduced into the electric furnace. The furnace
is an iron tank lined inside with refractory bricks. Carbon electrodes are fitted on either side of the furnace. The
furnace has two exits, one for removal of vapours in the upper part of the furnace and the other for removal of
slag in the lower part of furnace. The charge is introduced through the closed hopper arrangement.

The mixture is heated at 1400-1500oC by the discharge of an alternating current between carbon electrodes.
Silica combines with calcium phosphate and forms phosphorus pentaxide which is reduced by carbon into
phosphorus.
[Ca3(PO4)2 + 2SiO2  3CaSiO3 + P2O5] x 2
2P2O5 + 10C  P4 + 10CO
----------------------------------------------------------------
2Ca3(PO4)2 + 6SiO2 + 10C  6CaSiO3 + P4 + 10COs

Vapours of phosphorus and carbon monoxide leave the furnace through the upper exit and are condensed under
water. The liquid slag is tapped out periodically through an exit in the base.s

Bansal Classes Nitrogen Family [21]

Purification
Phosphorus obtained is further purified by melting under acidified potassium dichromate solution when the impurities
are oxidised. It is redistilled.

Allotropic modifications of phosphorus

Phosphorus exists in a number of allotropic forms. These forms are:
(i) Yellow or white phosphorus
(ii) Red phosphorus
(iii) Scarlet phosphorus
(iv)  -black phosphorus
(v)  -black phosphorus
(vi) violet phosphorus

The main allotropic forms, however, are white and red.

White or yellow phosphorus

This is the common variety and is obtained by the methods described above. This form is chemically very active.

Properties
(a) The pure form is white but attains yellow colour on long standing due to the formation of a thin film of the red
variety on the surface.
(b) It is a transparent waxy solid (sp. gr. 1.8) and can be easily cut with knife.
(c) It has characteristic garlic smell and is poisonous in nature. 0.15 g is the fatal dose. Vapours are also injurious.
Persons working with phosphorus develop a disease in which the jaw bones decay. This disease is known as
phossy jaw.
(d) It is insoluble in water but readily soluble in carbon disulphide.
(e) It melts at 44oC into a yellow liquid. It boils at 280oC.
(f) In contact with air, it undergoes slow combustion and glows dark. ths property is called phosphorescence.
(g)Its ignition temperature is low (about 30oC). It readily catches fire giving dense fumes of phosphorus pentoxide.
it si, therefore, kept in water.
P4 + 5O2  P4O10 or 2O2O5
(h) It dissolves in caustic alkalies on boiling in an inert atmosphere and forms phosphite.
3NaOH 3NaH 2 PO 2
P4 + Caustic + 3H2O  sodium + PH3 
soda hypophosphite

(i) It directly combines with halogens forming first trihalides and then pentahalides.
P4 + 6Cl2  4PCl3; P4 + 10Cl2  4PCl5
(j) It combines with a number of metals forming phosphides.
6Mg + P4  2Mg3P2(Magnesium phosphide)
6Ca + P4  2Ca3P2 (Calcium phosphide)
(k) It combines with sulphur with explosive violence forming a number of sulphides such as P2S3, P2S5, P4S3 and
P 4S 7.
(l) It acts as a strong reducing agent. It reduces nitric acid and sulphuric acid.
P4 + 20HNO3  4H3PO4 + 20NO2 + 4H2O
P4 + 10H2SO4  4H3PO4 + 10SO2 + 4H2O
It reduces solutions of copper, silver and gold salts to corresponding metals,
P4 + 10CuSO4 + 16H2O  10Cu + 4H3PO4 + 10H2SO4
When the solution is heated, cuprous phosphide is formed.
3P4 + 12 CuSO4 + 24 H2O heat  4Cu3P + 8H3PO3 + 12H2SO4
P4 + 20AgNO3 + 16H2O  20Ag + 4H3PO4 + 20HNO3

Bansal Classes Nitrogen Family [22]

(m) when heated in inert atmosphere at 240oC, it changes into red variety.
o

Yellow P 240  Red P
250 C
Inert atm.

(n) Structure
The vapour density of white phosphorus between 500-700oC, is 62 which corresponds to the molecular formula
P4. The four phosphorus atoms lie at the corners of a regular tetrahedron. Each phosphorus atom is linked to
each of the other three atoms by covalent bonds. The P-P bond length is equal to 2.21Å. The bond angle is equal
to 60o which suggests that he molecule is under strain and hence active in nature.

Red Phosphorus
Preparation
Red phosphorus is formed by heating yellow phosphorus, between 240-250oC, in presence of an inert gas. The
heating is done in an egg shaped iron vessel provided with a upright tube closed by safety value. the thermometers
placed in iron tubes help to regulate the temperature.

Structure of red phosphorus

The exact structure of red phosphorus is not yet known. It is regarded as a polymer consisting of chains of P4
tetrahedral linked together possible in the manner as shown in the figure.

Proposed molecular structure of red phophorus

Comparison between White and Red Phosphorus

S.No. Property White Phosphorus Red Phosphorus
1. Physical State Soft waxy solid Brittle powder
2. Colour White when pure. Attains yellow Red
colour on standing
3. Odour Garlic Odourless
4. Specific gravity 1.8 2.1
5. Melting point 440C Sublimes in absence of air at 2900C
6. Ignition temperature Low, 300C High, 2600C
7. Solubility in water Insoluble Insoluble
8. Solubility in CS2 Soluble Insoluble
9. Physiological action Poisonous Non-poisonous
10. Chemical activity Very active Less active
11. Stability Unstable Stable

Bansal Classes Nitrogen Family [23]

12. Phosphorescence Glows in dark Does not glow in dark
13. Burning in air Forms P4O10 Forms P4O10
14. Reaction with NaOH Evolves phosphine No action
15. Action of Cl2 Combines spontaneously to form Reacts on heating to form PCl3 & PCl5
PCl3 & PCl5
16. Reaction with hot Forms H3PO4 Forms H3PO4
HNO3
17. Molecular formula P4 Complex Polymer

Uses of phosphorus
(i) It is largely used in the match industry. Red phosphorus or scarlet phosphorus is preferred to yellow variety.
(ii) Yellow phosphorus is used as a rat poison.
(iii) Red phosphorus is used for the preparation of HBr and HI.
(iv) Radioactive phosphorus (P32) is used in th treatement of leukemia and other blood disorders.
(v) It is used for making incendiary bombs and smoke screens.
(vi) It is used in the manufacture of phosphor bronze, an alloy of phosphorus, copper and tin.
(vii)It is used in the manufacture of compounds like hypophosphites (medicine), phosphorus chlorides in industry,
calcium phosphide used in making Holme’s signals and orthophosphoric acid.

Compouns of Phosphorus
1. Phosphine, PH3
It is analogous to ammonia.

Laboratory preparation
It is prepared by blining yellow phosphorus with a concentrated solution of solution of sodium hydroxide in an
inert atmosphere.
P4 + 3NaOH + 3H2O  3NaH 2 PO 2 + PH3
sodium
hypophosphite

Besides PH3, small amounts of hydrogen and phosphorus dihydride (P2H4) are also formed.
P4 + 4NaOH + 4H2O  3NaH2PO2 + 2H2
3P4 + 8NaOH + 8H2O  8NaH2PO2 + 2P2H4
As soon as the bubbles of the gas come in contact with air, they catch fire spontaneously forming rings of smoke
known as vortex rings. This combustion is due to the presence of highly inflammable phosphorus dihydride
(P2H4).
2P2H4 + 7O2  4HPO 3 + 2H2O
Metaphosph oric
acid

P2H4 can be removed from phosphine by the following methods:

(i) By passing the evolved gas through a freezing mixture which condenses P2H4.
(ii) By passing the gas through HI. PH3 is absorbed forming phosphonium iodide. This on treatment with casutic
potash gives pure phosphine.
PH4I + KOH  KI + H2O + PH3

Physical properties
It is a colourless gas having unpleasant garlic like odour or rotten fish odour.

Bansal Classes Nitrogen Family [24]

(a) Decomposition
When heated out of contact of air to 440OC or when electric sparks are passed through, phosphine decomposes
into red phosphorus and hydrogen.
PH3  P4 + 6H2

(b) Combustibility
A pure sample of phosphine is not spontaneously inflammable. It burns in air or oxygen when heated at 150oC.
2PH3 + 4O2  P2O5 + 3H2O

The spontaneous in flammability of phosphine at the time of preparation is due to the presence of highly inflammable
phosphorus dihydride, P2H4. This property is used in making Holme’s signal. A mixture of calcium carbide and
calcium phosphide is placed in metallic containers. Two holes are made and the container is thrown into the sea.
Water enters and produces acetylene and phosphine respectively. The gaeous mixture catches fire spontaneously
due to the presence of P2H4. The acetylene produces a bright luminous flame which serves as a signal to the
approaching ship.

(c) Action of chlorine

Phosphine burns in the atmosphere of chlorine and forms phosphorus pentachloride.
PH3 + 4Cl2  PCl5 + 3HCl

(d) Basic nature

Phosphine is neutral to litmus. However, it si a weak base, even weaker than ammonia. It reacts with HCl, HBr
or HI to form phosphonium compounds.
PH3 + HCl  PH4Cl (Phosphonium chloride)
PH3 + HBr  PH4Br (Phosphonium bromide)
PH3 + HI  PH4I (Phosphonium iodide)

(e) Action of nitric acid

In contact with nitric acid phosphine begins to burn.
2PH3 + 16 HNO3  P2O5 + 16NO2 + 11H2O

(f) Addition compounds

In forms addition compounds with anhydrous AlCl3 and SnCl4
AlCl3 + 2PH3  AlCl3.2PH3
SnCl4 + 2PH3  SnCl4.2PH3

When PH3 is passed through cuprous chloride solution in HCl, it forms an addition compound.
Cu2Cl2 + 2PH3  2CuCl. PH3

(g) Formation of phosphides

(i) When phosphine is passed through copper sulphate solution, a black precipitate of cupric phosphide is
formed.
3CuSO4 + 2PH3  Cu3P2 + 3H2SO4

(ii) A black precipitate of silver phosphide is formed when phosphine is circulated through silver nitrate solution.
3AgNO3 + PH3  Ag3P + 3HNO3
(h) The mixture of PH3 and N2O or PH3 and NO explodes in presence of electric spark.
PH3 + 4N2O  H3PO4 + 4N2

Bansal Classes Nitrogen Family [25]

2. Oxides of Phosporus
Phosphorus forms three important oxides. These exist in dimeric forms.
(i) Phosphorus trioxide, P2O3 or P4O6
(ii) Phosphorus tetroxide, P2O4 or P4O8
(iii) Phosphorus pentoxide, P2O5 or P4O10

(i) Phosphorus trioxide P2O3 or P4O6

It is formed by burning phosphorus in limited supply of air.
P4 + 3O2  P4O6
The pentoxide, formed in small amount, is removed by passing through glass wool. The vapours of trioxide pass
through the glass wool and are condensed in a reveiver cooled by a freezing mixture.

Structure of Phosphine
Phosphine is a covalent molecule. It has pyramidal structure like ammonia.

The bond angle H-P-H is 93o.

Uses:
(i) For making Holme’s signals.
(ii) For making smoke screens.
(iii) For making metallic phosphides.
Vapours of phosphorus at low pressure react with N2O at 600oC to form P2O3.
P4 + 6N2O 600

o
C
 2P2O3 + 6N2

Properties
(a) It is a waxy solid having garlic odour.
(b) It is poisonous in nature.
(c) It is soluble in benzene or chloroform.
(d) When heated above 210oC, it forms red phosphorus and another oxide, P4O8.
4P4O6  3P4O8 + 4RePd
Phosphorus
tetroxide

When heated at about 440oC, it dissociates to phosphorus dioxide.

2P2O3  3PO2 + P
(e) In contact with air, it is oxidised to phosphorus pentoxide.
P4O6 +2O2  P4O10
(f) It burns in chlorine forming oxy-chlorides.
2POCl3 2PO Cl 2
P4O6 + 4Cl2  Phosphorus + Metaphosphorus
Oxy  chloride Oxy  chloride

(g) In cold water it dissolves slowly forming phosphorus acid.

P4O6 + 6H2O (cold)  4H3PO3
With hot water, a violent reaction occurs forming orthophosphoric acid and phosphine.
P4O6 + 6H2O (hot)  3H3PO4 + PH3
The above reaction is actually the conversion of phosphorus acid into orthophosphoric acid and phosphine.
4H3PO3  3H3PO4 + PH3
This oxide is known as acid anhydride of phosphorus acid.

Bansal Classes Nitrogen Family [26]

Structure of phosphorus trioxide

(ii) Phosphorus pentoxide, P4O10

It is prepared by heating phosphorus in a free supply of air or oxygen.
P4 + 5O2  P4O10
It is further purified by sublimation.
Phosphorus burns in CO2 at 100oC to form P2P5.
2P + 5CO2  P2O5 + 5CO
Properties
(a) It is a white crystalline compounds
(b) It is odourless when pure. The usual garlic odour is due to presence of small amount of P4O6 as impurity.
(c) It sublimes on heating.
(d) It has great affinity for water. The final product is orthophosphoric acid. It is therefore, termed phosphoric
anhydride.

i.e.P4O10 + 6H2O  4H3PO4

It is, thus used as a powerful dehydrating or drying agent. It removes water from inorganic and organic compounds
like H2SO4, HNO3, RCOOH, RCONH2, etc.
2H2PO4 + P4O10  2SO3 + 4HPO3
4HNO3 P4O10  2N2O5 + 4HPO3
4CH3-COOH + P4O10  2(CH3CO)2O + 4HPO3
2CH3CONH2 + P4O10  2CH3Cn + 4HPO3

It also chars wood, paper, sugar etc.

(e) when heated strongly with carbon, it forms red phosphorus.

P4O10 + 10C  10CO + 4P(red phosphorus)

(f) when fused with basic oxides, it forms phosphates.

6CaO + P4O10  2Ca3(PO4)2

(g) 30% H2O2 react on P2O5 in acetonitrile solution at low temperature to form peroxy monophosphoric acid.
P2O5 + 2H2O2 + H2O  2H3PO5

Bansal Classes Nitrogen Family [27]

(h) Mixture of P2O5 and O2 in vapour state combine in presence of electric discharge to form P 2O6 called
phosphorus peroxide.
P2O5 + 1/2O2  P2O6

Uses
It is most effective drying or dehydrating agent below 100oC

Structure of phosphorus pentoxide

3. Oxyacids of phosphorus
Phosphorus forms a number of oxyacids. Common oxyacids are given below.

Name of Oxyacid Formula Basicity Oxidation state of P

Hydrophosphorus acid H3PO2 1 +1
Phosphorus acid H3PO3 2 +3
Orthophosphoric acid H3PO4 3 +5
Metaphosphoric acid HPO3 1 +5
Hypophosphoric acid H2P 2O 6 4 +4
Pyrophosphoric acid H4P 2O 7 4 +5

(i) Phosphorus acid, H3PO3, Prepartion

(i) It is obtained by dissolving phosphorus trioxide in water.
P4O6 + 6H2O  H3PO3

(ii) It is also obtained by hydrolysis of phosphorus trichloride.

PCl3 + 3H2O  H3PO3 + 3HCl
Chlorine is passed over molten white phosphorus under water when phosphorus trichloride formed undergoes
hydrolysis.
2P + 3Cl2  2PCl3
The solution is heated until the temperature becomes 180oC. On cooling crystals of phosphorus acid are obtained.

Properties
(a) It is colourless crystalline compound. It melts at 73oC. It is highly soluble in water.

Bansal Classes Nitrogen Family [28]

(b) When heated, it forms orthophosphoric acid and phosphine.
4H3PO3 200 o
 C
 3H3PO4 + PH3
(c) It si strong acid. It is diabasic in nature.
H3PO3H– + H2PO3–  2H– + HPO3–
K1 = 10–1; K2 = 2 x 10–7
It thus forms two series of salts such as NaH2PO3 adn Na2HPO3 known as primary phosphites and secondary
phosphites respectively.
(d) It acts as a strong reducing agent. The potential equation is:
H3PO3 + H2O  H3PO4 + 2H
It reduces CuSO4 to Cu, AgNO3 to Ag, HgCl2 to Hg2Cl2, I2 to HI and acidfied KMnO4 solution.
CuSO4 + 2H  Cu + H2SO4
AgNO3 + H  Ag + HNO3
2HgCl2 + 2H  Hg2Cl2 + 2HCl
I2 + 2H  2HI
2KMnO4 + 3H2SO4  K2SO4 + 2MnSO4 + 3H2O + 5O
[H3PO3 + O  K3PO4] x 5
----------------------------------------------------------------------------
2KMnO4 + 3H2SO4 + 5H3PO3  K2SO4 + 2MnSO4 + 5H3PO4 + 3H2O

Structure of Phosphorus acid

It is diabasic acid, i.e. two hydrogen atoms are insoluble or two hydroxyl groups are present. Thus, the structure
is:

The phosphorus lies in sp3 hybrid state.

(ii) Orthophosphoric aicd, H3PO4

This acid is commonly called as phosphoric acid.

Preparation
(i) It is formed when phosphorus pentoxide is boiled with hot water.
(ii) ORthophosphoric acid is also formed when PCl5 (Phosphorus pentachloride) is boiled with water.
PCl5 + 4H2O  H3PO4+ 5HCl

(iii) Laboratory preparation

The best method for its preparation in the laboratory is to heat red phosphorus with concentrated nitric acid in a
flask with a reflux condenser.
P + 5HNO3  H3PO4 + H2O + 5NO2
The reaction is usually carried out is presence of a crystal of iodine. The iodine acts as a catalyst.
P + 3I  PI3
PI3 + 3H2O  H3PO3 + 3HI
3HI + 3HNO3  3H2O + 3NO2 + 3I
H3PO3 + 2HNO3  H3PO4 + H2O + 2NO2
------------------------------------------------------------
P + 5HNO3  H3PO4 + 5NO2 + H2O

Bansal Classes Nitrogen Family [29]

The solution is concentrated till it becomes syrupy about 170oC. It is cooled over conc. H2SO4 in vacuum
dessicator when crystals of orthophosphoric acid are formed.

Manufacture
It is prepared on large scale from bone ash or phosphoric mineral.
(a) By decomposing calcium phosphate present is bone ash or phosphoric meneral with conc. H2SO4.
Ca3(PO4)2 + 3H2SO4  3CaSO4 + 2H3PO4
On standing calcium sulphate settles down and the clear supernatant liquid separates out. The liquid is concentrated
when about 85% concentrated orthophosphoric acid is obtained.

(b) The bone ash is dissolved in minimum amount of nitric acid and lead acetate is added as to precipitate lead
phosphate. The lead salt is then decomposed by passing H2S.
Pb3(PO4)2 + 3H2S  3PbS + 2H 3 PO 4
inso lub le solution

(c) Bone ash or calcium phosphate is converted into phosphorous pentoxide when heated with silica in electric
furnace.
2Ca3(PO4)2 + 6SiO2  6CaSiO3 + P4O10
P4O10 is then dissolved in hot water.
P4O10 + 6H2O  4H3PO4

properties
(a) It is transparent deliquescent solid. It melts at 42.3oC. It absorbs water and forms colourless syrupy mass. It
is highly soluble in water.

(b) Heating effect

When heated at 250oC, it is converted into pyrophosphoric acid.
2H3PO4 250 
o
C
 H4P2O7 + H2O
On further heating, it is converted into metaphosphoric acid.
H3PO4 600
o  HPO + H O
heat
C 3 2

H4P2O7 heat  2HPO3 + H2O

When strongly heated at red heat, it forms P4O10.
(c) Acidic mature
It is tribasic acid, i.e. all the three hydrogen atoms are ionizable. It forms three series of salts.
H3PO4  H+ + H2PO4-  2H+ + HPO42-  3H+ + PO43-
NaH2 PO 4 Na 2 HPO 4 Na 3 PO 4
( primarysalt ) (sec ondary salt ) ( normalsalt )

Primary salt on heating forms a slat of metaphosphoric acid.

NaH PO 2 4  NaPO3 + H2O
heat
Sodium dihydrogen Sodium
phosphate metaphosphate

Secondary salt on heating forms a slat of pyrophosphoric acid.

 Na 4 P2O 7 + H2O
2 Na 2 HPO 3 heat
Disod .Hydrogen Sodium
phosphate pyrophosph ate

Normal salt is not affected by heating.

In case, ammonium ion is present in the slat it behaves as hydrogen.
2MgNH4PO4 heat  Mg2P2O7 + 2NH3 + H2O
NaNH4HPO4 heat
 naPO3 + NH3 + H2O

Bansal Classes Nitrogen Family [30]

(d) Reaction with AgNO3
A yellow precipitate of silver phosphate is formed.
3AgNO4 + H3PO4  Ag 3PO 4 + 3HNO3
yellow ppt .

(e) Reaction with BaCl2

A white ppt. of barium phosphate is formed in neutral or alkaline solution.
3BaCl2 + 2H3PO4  Ba 3 (PO 4 ) 2 + 6HCl
white ppt .

(f) Reaction with bromides and iodides

Hydrobromic and hydroiodic acids are liberated from bromides and iodides respectively. This is te laboratory
preparation of HBr and HI.
3NaBr + H3PO4  Na3PO4 + 3HBr
3NaI + H3PO4  Na3PO4 + 3HI

(g) Reaction with magnesium salt

Magnesium slats combine with orthophosphoric acid in presence o ammonium chloride nd ammonium hydroxide
to form a white precipitate of magnesium ammonium phosphate.
MgSO4 + NH4Cl + H3O4  Mg(NH4)PO4 + H2SO4 + HCl
This reaction is used to test Mg2+ ion.

(h) On heating orthophosphoric acid is presence of nitric acid with ammonium molybdate a canary yellow ppt. of
ammonium phosphomolybdate is formed.
H3PO4 + 21 HNO3 + 12 (NH4)2 MoO4  ( NH 4 )3 PO 412MoO3 + 21 NH4NO3 + 12 H2O
Ammoniumphosp hom olybdate

This reaction is used to test PO 4

3–
ion.

Structure of orthophosphoric acid

Orthophosphoric acid is a tribasic. i.e. 3 hydroxyl groups are present. The structure of the acid is thus represented
as:

Phosphorus atom lies in sp3 hybrid state.

*****

Bansal Classes Nitrogen Family [31]