P – BLOCK ELEMENTS Electronegativity decreases down the group due to increase of

atomic size.
Nitrogen family / Group 15 elements [By Nagendra Kr.]
❖ METALLIC AND NON – METALLIC CHARACTER:
❑ Group 15 contains the following elements:- Metallic character increases down the group due to decrease of
Elements Atomic number Atomic weight ionization energy.
Nitrogen (N) 07 014
N & P are non metals.
Phosphorus (P) 15 031
Arsenic (As) 33 075 As & Sb are semi metals.
Antimony (Sb) 51 121
Bismuth (Bi) 83 209 Bi is metal

❖ ALLOTROPY:-
❖ General electronic configuration:- ns2 n p3
▪ Except nitrogen and bismuth, all the elements of this group
⇒ The electronic configuration is extra stable due to half filled p show allotropy.
– subshell.
ELEMENTS ALLOTROPIC FORMS
❖ PHYSICAL PROPERTIES:- Phosphorus 1. White phosphorus,
2. Red phosphorus,
➢ Atomic radii:- The covalent radii increases down the group 3. Black phosphrus
because of increase in number of one orbit on each step Arsenic 1. Yellow arsenic,
down the group. 2. Grey Arsenic
Antimony 1. Yellow antimony,
⇒ The change in covalent radii is very small from As to Bi due 2. Grey antimony
to completely filled d and f sub – shell in higher members.

➢ Ionization enthalpy:- The ionization enthalpy decreases down ❖ CATENATION:-

the group due to increase in the atomic radii down the
group.
⇒ The ionization energy of group 15 elements are greater
than group 14 or 16 elements of the corresponding
period due to extra stability of the electronic
configuration of the outermost orbit of group 15 elements.
⇒ For an element I.E.1 < I.E.2 < I.E.3
❖ ELECTRONEGATIVITY:
The elements of group 15 also show catenation but less
than group 14.
▪ Nitrogen can form the chain of 2 atoms & phosphorus can
form the chain of 4 atoms.
▪ Nitrogen has smaller tendency of catenation due to weaker N – N
due to high interelectronic repulsion of non bonding electrons
bond than P – P bond.
❖ DENSITY:- ❖ REACTIVITY:-

The density of the elements increases down the group due to In general the reactivity of the elements decreases
increase in atomic mass. down the group.

❖ MELTING POINT AND BOILING POINT:- ➢ Reactivity towards H2:-

⇒ Order of m.p. = N < P << As > Sb > Bi The elements of group 15 form hydrides having
⇒ The m.p. of As is very large as compared to P due to fact that general formula MH3 which are as follows
As has most of the properties of metals.
⇒ The m.p. decreases beyond As due to decrease in metallic NH3 (Ammonia)
bond strength down the group. PH3 (Phosphine)
⇒ Order of boiling point: N < P < As < Sb > Bi
AsH3 (Arsine)
❑ CHEMICAL PROPERTIES:-
SbH3 (Astibine)
❖ OXIDATION STATES:-
BiH3 (Bismuthine)
⇒ The elements of group 15 show – 3, +3, +5 oxidation state.
⇒ The tendency to show – 3 oxidation no. decreases down the ▪ All the hydrides are covalent in nature.
group due to increase in size and metallic character.
⇒ The tendency to show +5 oxidation state decreases down ▪ Structure of hydrides:-
the group due to inert pair effect.
⇒ Bi forms only one stable compound BiF5 in which its O.N. is
+5.
⇒ Nitrogen can show +1, +2, +3 and +4 O.N. in its oxides.
⇒ Phosphorus can show +1 and +4 O.N. in some oxoacids. Ex.
H3PO2 (Hypophosphorus acid), H4P2O6(Hypophosphoric
acid)
⇒ All those compounds to nitrogen in which its oxidation
number is +1 to +4 have tendency to show
disproportionation reaction.
3HNO2 HNO3 + H2O + 2NO ▪ The hydrides have pyramidal shape and the central atom of
⇒ In the case of Phosphorus nearly all the the intermediate O.S. gp. 15 are sp3 hybridised.
undergo disproportionation to +5 & - 3 O.S. in alkali. ▪ The bond angles of H – atoms with the central atom
decreases down the group due to increase of the size of
central atom down the group.
▪ NH3 is a good Lewis base due to presence of a loan pair of
electron on the nitrogen which can be donated easily.
▪ NH3 has m.p. and b.p. abnormally higher than the other
hydrides of the group due to formation of H – bonding
among the molecules of ammonia.
▪ Thermal stability of the hydrides decreases in the following
order:-
NH3 > PH3 > AsH3 > SbH3 > BiH3
▪ The hydrides act as reducing agent and the reducing nature
follows the following order:-
NH3 < PH3 < AsH3 < SbH3 < BiH3
▪ Order of basic character:
NH3 > PH3 > AsH3 > SbH3 ≈ BiH3
❖ REACTIVITY TOWARDS HALOGEN:-
▪ All the elements of group 15 form halides of two types :
MX3 and MX5.
▪ Nitrogen does not form the halide of MX5 due to absence of
d orbital in it.
▪ All the trihalides are stable except for the trihalides of nitrogen.
▪ In the case of nitrogen, only NF3 is stable halide.
▪ Trihalides are covalent in nature except BiF 3.
▪ Pentahalides are more covalent than trihalides because in +5
oxidation state the elements has higher polarizing power than in
+3 oxidation number .
▪ Trihalides (BiF3) are predominantly covalent in nature.
❖ REACTIVITY TOWARDS OXYGEN:-
▪ The elements of this group reacts directly or indirectly with
oxygen and form a large number of different types of oxides
of type M2O3 & M2O5. Ex.:- N2O5, P4O10, As2O5.
▪ The oxides in higher oxidation state are more acidic than the
oxides in lower oxidation state.
▪ The acidic character decreases down the group.
▪ All the oxides of nitrogen (except NO & N2O) and
phosphorus are strongly acidic .
▪ The oxides of Arsenic are weakly acidic.
▪ The oxides of antimony are amphoteric.
▪ The oxides of Bismuth are weakly basic.
▪ The change in character from acidic to basic due to increase
of metallic character down the group.
▪ NO2 dimerise due to presence of odd number of electrons.
❖ REACTIVITY TOWARDS THE METALS:-
All the elements of the group reacts with metals to form the
binary compound in which the oxidation no. of the group 15
element is -3. Ex.:- Ca3N2.
❖ ANOMALOUS BEHAVIOUR OF NITROGEN:-
Nitrogen show the following anomalous behaviors:-
▪ Only nitrogen is diatomic molecule while all the elements
are tetra – atomic molecule (Bi).
▪ Nitrogen is the most inert element due to high bond
dissociation energy.
▪ Nitrogen does form penta halide. ▪ It has two stable isotopes:- 7N14, 7N15.

▪ Nitrogen can not show covalency more than 4. ▪ It is sparingly soluble in water.

➢ CAUSE OF THE ANOMALOUS BEHAVIOR:- ▪ It’s m.p. is 63 K & b.p. is 77.2 K.

▪ Very small size of nitrogen. ❖ Chemical properties:-

▪ Absence of d – orbital. It is chemically very inert but reacts at higher

temperature with many metals and non metals to form
▪ Very high bond dissociation energy. covalent nitrides.
▪ High electronegativity. ➢ Reaction with highly electropositive metals (Li / Ca / ..):-
▪ Nitrogen can form pπ – pπ multiple bond with itself. Nitrogen reacts with some active metals at high
❑ DINITROGEN temperature and form the corresponding nitrides
6Li + N2 2Li3N
❖ Preparation:- 3 Ca + N2 Ca3N2
3 Mg + N2 Mg3N2
➢ Commercial method:- Commercially nitrogen can be obtained
by fractional distillation of air at 77.2 K. ➢ Reaction with non – metals (H2 / O2):-
N2 + 3H2 2NH3
➢ Laboratory method:- In laboratory nitrogen can be prepared Ammonia
by treating an aqueous solution of ammonium chloride with N2 + O2 2NO
sodium nitrite. Nitric oxide
NH4Cl (aq) + NaNO2(aq) N2(g) + 2H2O(l) + NaCl (aq) ➢ Reaction with compounds (Al2O3 / CaC2):-
Al2O3 + N2 + 3O 2AlN + 3 CO
➢ From sodium azide or Barium azide:- Very pure nitrogen
Aluminium nitride
can be obtained by thermal decomposition sodium azide or
Barium azide.
CaC2 + N2 CaNCN + C
Ba(N3)2 Ba + 3N2
Calcium cyanamide
➢ From ammonium dichromate:- Nitrogen can also be obtained
❖ Uses of nitrogen:-
by thermal decomposition of ammonium dichromate.
(NH4)2Cr2O7 N2 + 4H2O + Cr2O3 ▪ The main use of nitrogen is in the manufacture of ammonia
and other industrial nitrogenous compound.
❑ Physical properties:-
▪ It is used to create the inert atmosphere.
▪ Nitrogen is a colourless odourless, tasteless & non – toxic gas.
▪ Liquid nitrogen is used as refrigerant to preserve the Flow diagram:
biological material, food , cryosurgery etc.

▪ It is used in gas filled mercury thermometer used for

measuring high temperature.

❑ AMMONIA

❖ Chemical formula:- NH3

❖ PREPERATION:-

▪ Ammonia is found in small amount in air and soil where it

is formed by decay of nitrogenous organic matter like urea.
CO(NH2)2 + 2H2O (NH4)2CO3 ⇄ 2NH3 + 2H2O + CO2
✓ Favorable condition for the high yield of ammonia:-
➢ By heating ammonia salt with strong bases:-
1. Low temperature.
When ammonium salt of non volatile acids such as
ammonium sulphate, ammonium chloride are heated with 2. High pressure.
caustic soda or lime , we get ammonia.
3. Catalyst
2NH4Cl + Ca(OH)2 2NH3 + 2H2O + CaCl2
❖ PHYSICAL PROPERTIES OF AMMONIA:-
(NH4)2SO4 + 2NaOH 2NH3 + 2H2O + Na2SO4
▪ It is a colourless gas with a characteristic pungent smell.
➢ Industrial preparation by Haber’s Process:-
▪ It causes tears in eyes.
In this method the nitrogen is directly combined with
▪ It is lighter than air.
hydrogen and produces ammonia.
200atm /700K/ FeO/Mo ▪ It is extremely soluble in water.
N2 (g) + 3H2 (g) 2NH3 (g)
▪ It liquefies on cooling under pressure to liquid ammonia.
∆H = -93.6 KJ /mol
▪ Its freezing point is 202 K and b.p. 239.6 K.

❖ CHEMICAL PROPERTIES:-

➢ Basic nature:-
 Aqueous solution of ammonia is basic in nature ▪ Ammonia is used to produce various nitrogenous fertilizers
because it can release OH- ion in aqueous solution , so turns as given below:
red litmus blue.
(1) Ammonium nitrate.
NH3 + H2O NH4+ + OH-
(2) Urea.
➢ Complex formation:-
(3) Ammonium phosphate.
Ammonia has a loan pair of electron so it can form complex
with various metal ions. (4) Ammonium sulphate.
Ag⁺ + 2NH3 ⇄ [Ag (NH3)2]+ ▪ It is used in the manufacture of various inorganic
(Colourless) compounds like nitric acid.

Cu2+ + 4NH3 ⇄ [Cu(NH3)4]2+ ▪ Liquid ammonia is used as refrigerant.

(Deep blue) ❖ TESTS OF AMMONIA:-

Cd2+ + 4NH3 ⇄ [Cd(NH3)4]2+ ▪ It turns moist turmeric paper brown.

▪ Due to tendency of complex formation white ppt. of AgCl
dissolve in aquous solution of ammonium hydroxide.
AgCl + NH4OH ⇄ [Ag(NH3)2]Cl + H2O
▪ Precipitation of heavy metal ions from the aqueous solution
of their salts:-
Heavy metal ions like Zn2+, Fe3+ are precipitated from
their aqueous salt solution
▪ It gives brown ppt. with Nesseler’s reagent.
▪ It gives dense white fumes with a drop of HCl.
It gives deep blue solution with a solution of Cu2+ sulphate
due the formation of [Cu(NH3)4]SO4
➢ Structure of ammonia

ZnSO4 (aq.) + 2NH4OH (aq.) Zn(OH)2 + (NH4)2 SO4

(aq.) (White ppt.)

FeCl3 (aq.) + NH4OH (aq.) Fe2O3 . x H2O + NH4Cl

(aq.) (Brown ppt.)
❑ NITRIC ACID:-
❖ Uses of ammonia:-
➢ Molecular formula:- HNO3
➢ Structure:
❖ Preparation:-
➢ Laboratory preparation:- In laboratory, nitric acid can be
prepared by heating NaNO3 / KNO3 with conc. Sulphuric acid
in glass retort and the vapours of nitric acid condensed.
NaNO3 + conc. H2SO4 NaHSO4 + HNO3
▪ MANUFACTURE BY OSTWALD PROCESS:-
The main steps involved in the manufacture of nitric
acid by Ostwald process are as follows:-
➢ Catalytic oxidation ammonia:- A gaseous mixture of pure
and dry ammonia and dry air in the ratio of 1:10 by
volume is passed through a steel shell or Al converter
containing Pt at 1100 K
➢ Ammonia is oxidized to nitric oxide.
4NH3 + 5O2 4NO + 6H2O
➢ Oxidation of nitric oxide:- The obtained nitric oxide is cooled
and passed into oxidizing chamber. The nitric oxide is
oxidized to nitrogen dioxide.
2NO + O2 2NO2
➢ Absorption of nitrogen dioxide:- The nitrogen dioxide gas is
now passed into the absorption tower packed with acid
proof stones.
➢ Water sprayed from the top dissolves the nitrogen dioxide
in the presence of oxygen and forms 60% aqueous mixture
of nitric acid
4NO2 + 2H2O + O2 4HNO3 (Nitric acid)
➢ The nitric acid obtained by the above process can be
further concentrated to 98% by dehydration with conc.
H2SO4.
➢ Flow diagram for manufacture of Ostwald process:
➢ PHYSICAL PROPERTIES:-
▪ It is colourless when pure but yellow when impure due
presence of nitrogen dioxide.
▪ It is corrosive to skin and produces painful blisters.
▪ Its boiling point is 359 K and m.p. is 231 K.
➢ CHEMICAL PROPERTIES:-
(1) Acidic nature:- When nitric acid is dissolved in water, it
completely ionized to form H3O+ & NO3- ion.
HNO3 (aq.) + H2O (l) H3O+ (aq.) + NO3- (aq.)
(2) Action on Copper:- When nitric acid reacts with Copper
the following products are formed in different conditions
(a) When copper reacts with dilute HNO 3, releases NO gas.
3Cu + 8HNO3 (dil.) 3Cu(NO3)2 + 2NO + 4H2O
 (b) When copper reacts with conc. HNO 3 nitrogen dioxide is
formed.
Cu + 4HNO3 (conc.) Cu(NO3)2 + 2NO2 + 2H2O
(3) Action on Zinc:- When nitric acid reacts with Zinc the
following products are formed in different conditions
▪ When Zn reacts with dilute HNO3, releases N2O gas.
4Zn + 10 HNO3 (dil.) 4 Zn (NO3)2 + N2O + 5H2O
▪ When Zn reacts with conc HN O3 , nitrogen dioxide is formed.
P4 + 20 HNO3(aq.) 3H3PO4 + 20 NO2 + 4H2O
(Phosphoric acid)
❖ Uses of nitric acid:-
▪ It is used to prepare ammonium nitrate for the manufacture
of fertilizer.
▪ It is used to prepare some compounds used in explosive.
▪ It is used in the preparation of nitroglycerin, nitro toluene,
and other organic nitro compounds.
▪ It is also used in etching of metals .
▪ It is used as an oxidizer in rocket.

❑ BROWN RING TEST FOR NITRATE:-

Zn + 4HNO3 (conc.) Zn (NO3)2 + 2NO2 + 2H2O
When freshly prepared dilute Ferrous Sulphate is added
▪ Some metals like Al do not dissolve in conc. Nitric acid to an aqueous solution containing nitrate ion , followed by
because of the formation of a passive film of oxide on the careful addition of Conc. Sulphuric acid along the sides of
surface. test tube so that separate layer is formed , a brown ring is
formed at the interface of the sulphuric acid.

(4) Reaction with non metals:- Dilute nitric acid has no

action on non metals like C / Sulphur / Phosphorus etc.

Many non metals are oxidized by conc. Nitric acid as

given below:

▪ Conc. Nitric acid oxidizes iodine to iodic acid.

I2 + 10 HNO3 2 HIO3 + 10 NO2 + 4 H2O

(Iodic acid)
▪ Conc. Nitric acid oxidizes carbon to carbon dioxide.
C + 4 HNO3 CO2 + 4 NO2 + 2 H2O

▪ Conc. Nitric acid oxidizes Sulphur to sulphuric acid.

1/8 S8 + 6HNO3 H2SO4 + 6 NO2 + 2 H2O

▪ Conc. Nitric acid oxidizes Phosphorus to phosphoric acid.