P BLOCK

Group 15
1. Electronic configuration: ns2np3

Element Symbol Property

Nitrogen N [He] 2s 2p
2 3 Non metallic
Phosphorus P [Ne] 3s 3p
2 3 Non metallic
Arsenic 2
As [Ar] 4s 4p
3 Semi Metal
Antimony 2
Sb [Kr]5s 5p
3 Semi Metal
Bismuth 2
Bi [Xe] 6s 6p
3 Metal
2. Atomic and Ionic Radii: Both covalent and ionic radii increases. N to P it
increases but from As to Bi a small decrease is observed, due to completely filled d
& f-orbitals which show poor shielding effect. This will increase the effective
nuclear charge which decreases the size.

3. Ionization enthalpy: I.E. decreases down the group, due to increase in size.
Due to extra stable half-filled p orbitals electronic configuration and smaller size,
I.E. is more than group -14 & 16.
4. Electronegativity: It decreases, due to increase in size.
5. Physical Properties: Polyatomic. N2 is diatomic gas and others are solid.
Except N, all show allotropy.
6. Oxidation State:
 Nitrogen show -3 oxidation state in nitrides due to small size and high
electronegativity

 Other elements show covalent nature. For e.g. phosphorus show a formal
oxidation state of -3 and form covalent compounds even with metals.
 The tendency to show +5 oxidation state decreases down the group due to
inert pair effect. Due to large amount of energy needed to lose all the five
valence electrons M+5 ions can’t be formed.
Inert Pair Effect: With E.C. ns2np3, as size increases on moving down the
group, due to poor shielding effect of d and f electrons ns2 electrons do not
participate in the bonding. This is known as inert pair effect.

 Nitrogen shows all the oxidation state from -3 to +5. Due to its small size,
high electronegativity and strong tendency to form pπ-pπ multiple bonds.

Disproportionation: The reaction in which one reactant get oxidized as well

as reduced. Due to inert pair effect the tendency to show disproportionation
decreases down the group.
3HNO2 → HNO3 + 2NO + H2O 3H3PO3 → 3H3PO4 + PH3

Covalency: Nitrogen is restricted to maximum covalency of 4 due to the

absence of d orbital. It can use only 4 orbitals (one s and three p). That is
why nitrogen does not form NF5 or NCl5.
  Anomalous Properties of Nitrogen: 1) Small size 2) High electronegativity

3) Absence of d orbital 4) high ionisation enthalpy.

 Other elements do not form pπ-pπ multiple bonds because of their bigger size
due to which there is no effective overlapping.
 Nitrogen show less catenation because of high inter electronic repulsion
between non-bonding e– in nitrogen N–N < P–P and small bond length. Also
due to absence of d-orbital in N, it cannot form dπ-pπ multiple bonding
which is possible in other element like PCl6–.

Nitrogen Phosphorus
1) Diatomic molecule (N≡N). 1) Tetra-atomic molecule (P ).
4
2) High bond dissociation energy 2) Low bond dissociation energy due
due to the presence of a triple bond. to P-P single bond.
3) Inert and unreactive in elemental 3) Highly reactive.
state.

Chemical Properties: 1. Hydrides:

Property Trends Explanation

Bond angle NH3>PH3>AsH3>SbH3 Force of repulsion between the
adjacent bonds pairs is maximum in
NH3.
Basic NH3>PH3>AsH3>SbH3>BiH3 As the size of the central atom
Nature increases the lone pair of electrons
occupies a larger volume and
tendency to donate a lone pair of
electrons decreases.
Boiling PH3<AsH3<NH3<SbH3 NH3 has higher boiling point due to
point <BiH3 hydrogen bonding. But lower than
SbH3 and BiH3 as van der Waals
forces compensates the H-bonding.
Melting PH3<AsH3<SbH3 <NH3 NH3 has highest melting point due to
point hydrogen bonding. Other hydrides do
not form H –Bonds.
Thermal NH3>PH3>AsH3>SbH3>BiH3 Decrease in bond strength of M–H,
stability due to increase in size of central
atom.
Reducing NH3<PH3<AsH3<SbH3<BiH3 Decrease in thermal stability
Character increases the tendency to liberate
hydrogen increases

Notes: 1) As we move from ammonia to bismuthine, the electronegativity of the

central atom decreases and the bond pairs of electrons lie away from the central
atom on going down the group and therefore bond pair-bond pair is maximum in
NH3 and minimum in SbH3.
2) The basic nature is explained on the behalf of electron density on the central
atom. The atomic size of N is much smaller than that of Bi, therefore, electron
density on the N-atom is much higher than that of Bi-atom.
2. Halides: (a) Penta-Halides: N can't form pentahalides due to the absence of
vacant d-orbitals.

(i) Have less thermal stability as compared to trihalides.

(ii) Pentahalides are Lewis acids.

Since elements in the +5 oxidation state have less tendency to lose electrons
than in the +3 oxidation state, they have high polarizing power and therefore,
pentahalides are more covalent than trihalides.

(b) Tri Halides:

(i) Mainly covalent except for BiF3 (ionic).
(ii) Ionic character increase down the group.

(iii) They have pyramidal shape.

(iv) Can be easily hydrolysed except for NX3. The product of hydrolysis of NCl3
and PCl3 are different: The water molecule attacks on the chlorine atom and
not on the N atom due to the absence of d-orbital and forms HOCl. But in
the case of PCl3, the water molecule attacks on the Phosphorus atom
because P-O bond is much stronger than Cl-O and form H3PO3 and HCl.
3. Rxn with metals: They form binary compounds with metals with -3
oxidation state E.g: Ca3N2, Ca3P2, Na3As2 (Sodium Arsenide) Zn3Sb2 (Zinc Stibide),
Mg3Bi2 (Magnesium Bismuthide).
4. Oxides:
 All oxides of N2 (except NO & N2O) & phosphorus are strongly acidic, oxides
of arsenic are weakly acidic, antimony are amphoteric and those of bismuth
are weakly basic.
 They form oxides of type E2O3 & E2O5. Oxidation state or electronegativity
increases, acidic nature of oxide increases. But acidic nature of oxides
decreases down the group.
Nitrogen (N2): Preparation:
1. Commercially by fractional distillation of liquid air (b.pt.-77.2 K).
2. Laboratory Preparation:

NH4Cl (aq.) + NaNO2(aq.)→N2(g)+2H2O(l) + NaCl (aq.)

NO & HNO3 as impurities are removed by passing the gas through H2SO4 (aq.)
having K2Cr2O7.

3. (NH4)2 Cr2O7 → N2(g) + 4H2O + Cr2O3

4. Ba(N3)2 → Ba + 3N2

2NaN3 → 2 Na + 3N2, this is used to inflate the air bags for safety devices in
some cars.
Physical Properties: Colourless, tasteless, non-toxic gas, isotopes are 14N & 15N,
slightly soluble is water, low freezing and boiling point. It is adsorbed by activated
charcoal.

Chemical Properties: Inert at room temperature, due to high bond enthalpy of

N ≡ N bond, but reactivity increases with increase in temp.

1. Reaction with Metals: Form Covalent nitrides.

6Li + N2 →2Li3N

3Mg + N2 →Mg3N2

2. Reaction with H2 (Haber’s Process):


N2 (g) + 3H2 (g) ←
773K , Fe
→ 2NH3 (g) ∆ f HO– =
 −46.1kJmol –1

3. Reaction with O2:

2 2
→ 2NO(g)
N (g) + O (g) ←
2000 K

Nitric oxide

Uses: Manufacture of NH3, industrial chemical. Provides inert atmosphere in iron

and steel industry. As refrigerant to preserve food items and biological materials.
Ammonia (NH3): Preparation:

1. NH2CONH2 + 2H2O → (NH4)2CO3 + 2NH3 + H2O + CO2

2. NH4Cl + Ca(OH)2 → 2NH3 + 2H2O + CaCl2 Small Scale

(NH4)2SO4 + 2NaOH → 2NH3 + 2H2O + Na2SO4

3. Haber's Process: N2 (g) + 3 H2 (g) → 2 NH3 (g) Large Scale

Conditions:
1) Low temperature of around 700 K because the reaction is exothermic which
favors the formation of ammonia.
2) High pressure of 200 × 105 Pa. As the forward reaction occurs with the decrease
in volume, by le Chatelier's principle.
3) Catalyst: Iron oxides with small amount of K2O and Al2O3 and molybdenum is
used as a promoter.

Physical Properties: Colourless, pungent smelling, bring tears is eyes, lighter than
air, soluble in water easily liquefies and is basic is nature.


NH3 (g) + H2O( ) ←→ NH4+ (aq) + OH− (aq)

Chemical Properties: 1. Reaction with Acids:

FeCl3 (aq) + NH4OH(aq) → Fe2O3 .xH2O(s)+ 3NH4Cl(aq)
Brown ppt.

ZnSO4 (aq) + 2NH4OH(aq) → Zn(OH)2 (s)+ (NH4 )2 SO4 (aq)

White ppt.

2. Reaction as Lewis Base: Due to presence of a lone pair of e– on N-atom, it

can donate its lone pair and acts as Lewis base. NH3 + BF3 → H3N → BF3
 2+
 
Cu2+ (aq) + 4NH3 (aq) → Cu(NH3 )4  (aq)
Blue  Deep Blue 

 
Ag + (aq) + Cl − (aq) → AgCl(s) AgCl(s) + 2NH3 (aq) →  Ag(NH3 )2  Cl(aq)
White ppt. White point  colourless 

Uses: For nitrogenous fertilizes, for preparing HNO3 (Ostwald's process), for sod.
carbonate (Solvay's process). Refrigerant, cleaning agent, lab. Reagent.

Oxides of Nitrogen:

Notes: 1) NO2 contains odd number of valence electrons. It behaves as a typical

odd molecule. On dimerization, it is converted to stable N2O4 molecule with even
number of electrons.
2) In N2O5, the covalency of N is 4 as it form only 4 bonds due to absence of d-
orbitals.

3) NCl3 get easily hydrolysed but NF3 does not. This is due to the absence of d
orbital in fluorine. But chlorine has vacant d-orbital which accept the lone pair of
electrons donated by oxygen atom of H2O molecules.
4) NCl3 is endothermic compound because of its high enthalpy of formation due to
large difference in sizes of N and Cl atoms. This large difference makes N-Cl bond
weak, while in NF3 the sizes of atoms are not so different, therefore N-F bond is
strong and thus it is an exothermic compound.

5) The N−O bond in NO2− is shorter than in the NO3−. This is because the N—O
bond in NO2 – is an average of a single bond and a double bond whereas the N—O
bond in NO3 – is an average of two single bonds and a double bond.

Nitric Acid (HNO3): Nitrogen forms oxoacids like H2N2O2

(hyponitrous acid), HNO2 (nitrous acid) and HNO3. Due to
resonance, N—O bond length is the average of single and double bond whereas N—
OH bond is purely single bond.
Preparation:

1. NaNO3 + H2SO4 → NaHSO4 + HNO3 [In Lab.]

2. Ostwald's Process: On large scale is based upon catalytic oxidation of NH3

by atmospheric O2.
Pt/Rh gauge Catalyst
4NH3 (g) + 5O2 (g)  → 4NO(g) + 6H2O(g)
500K, 9bar


2NO(g) + O2 (g) ←→ 2NO2 (g)

3NO2 (g) + H2O (l) → 2HNO3 (aq.) + NO(g)

NO formed can be recycled and aq. HNO3 can be conc. by distillation upto ~68% by
mass. Also conc. to 98% can be achieved by dehydration with conc. H2SO4.
Properties:

1. Colourless liquid. In lab. used as 68% (by mass) and has density 1.5 g/ml. It is a
planar molecule is gaseous state.

2. Strong acid but in aq. medium. HNO3 (aq) + H2O(l) → H3O+(aq) + NO3–(aq)

3. Strong Oxidising Agent in conc. and dil. forms, as it gives [O].

2HNO3(conc.) → H2O + 2NO2 + [O]

2HNO3(dil.) → H2O + 2NO + 3 [O]

4. Rxn with metals:

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

Cu + 4HNO3 (conc.) → Cu (NO3)2 + 2NO2 + 2H2O

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

Zn + 4HNO3 (conc.) → Zn (NO3)2 + 2H2O + 2NO2

Metals like Au, Pt do not get attacked & metals like Cr, Al, Pt, do not dissolve in
conc. HNO3 as they form stable layer of its oxide.
5. Rxn with Non-metals:

I2 + 10HNO3 →2HIO3 + 10NO2 + 4H2O

C + 4HNO3 → CO2 + 2H2O + 4NO2

S8 + 48 HNO3 (conc.) → 8H2SO4 + 48NO2 + 16H2O

P4 + 20 HNO3 (conc.) → 4H3PO4 + 20NO2 + 4H2O

Brown Ring Test: Add conc. H2SO4 through the wall of test tube, slowly which has
a soln of nitrate along with FeSO4 (aq). The appearance of dark brown rings at the
junctions of 2 layers indicate the presence of NO3− ion. It is because Fe2+ reduces
NO3– to NO which then reacts with Fe2+ to form a brown complex.
 NO3– + 3Fe2+ + 4H+ → NO + 3Fe3+ + 2 H2O
[Fe(H2O)62+ + NO → [Fe(H2O)5 NO]2+ + H2O
Pentaaquanitrosoniumiron (I)
Brown

Phosphorus: Allotropy: It is the existence of an element in physical state with

same chemical properties but different physical properties.
Phosphorus has 3 allotropes: white, red & black.

White Phosphorus:
1. Translucent white waxy solid, poisonous, insoluble is water but soluble is CS2,
glows in dark (chemiluminescence).
P4 + 3NaOH + 3H2O → PH3 + 3NaH2PO2
Sod. Hypophosphite

2. Less stable, more reactive due to the presence of angle strain

of 60o.

3. Catches fire and burns in air. P4 + 5O2 → P4O10

Red Phosphorus:
1. Obtain by heating white phosphorus in inert atmosphere. But on heating red P
at high T, it forms Black P.

2. Has iron greyish colour, odourless, non-

poisonous, insoluble in water and CS2.
3. Less reactive then white phosphorus and does
not glow in dark.
4. It is polymeric with chain of tetrahedral
molecule (P4).

Black Phosphorus:

1. It has 2 forms α and β.

2. α black is formed when red phosphorus is heated in a steel tube at 803 K. It can
sublime in air, opaque monoclinic or rhombohedral crystals. It does not oxidise in
air.

3. β black is prepared by heating white phosphorus at 473K under high pressure. It

does not burn in air upto 673K.
Phosphine (PH3):

1. Ca3P2 + 6H2O → 3Ca(OH)2 + 2PH3

2. Ca3P2 + 6HCl → 3CaCl2 + 2PH3

3. In inert atmosphere of CO2

P4 + 3NaOH + 3H2O → PH3 + 3NaH2PO2 [In Lab.]

Properties:
1. Colourless, rotten fish smell, highly poisonous.

2. Explodes when in contact with O. A. like HNO3, Cl2 & Br2 vapours.
3. Soluble in water. When pure non-inflammable but becomes flammable due
to the presence of P2H4 or P4 Vapours.
For Purification : PH4I + KOH → KI + H2O+ PH3
Phosphonium Iodide

4. Weakly basic: PH3 + HBr → PH4Br (Phosphonium Bromide)

Due to lone pair on phosphorus atom, PH3 is acting as a Lewis base in the
above reaction.

5. 3 CuSO4 + 2PH3 → Cu3P2 + 3H2SO4

6. 3HgCl2 + 2PH3 → Hg3P2 + 6HCl

7. P in PH3 is sp3-hybridized. Due to stronger lone pair-bond pair repulsions

than bond pair-bond pair repulsions, the tetrahedral angle decreases. PH4+
ion which has four bond pairs and lone pair-bond pair repulsion.
Uses:

1. As Holme's signals in deep sea and ocean for danger points.

2. For smoke screens.
Phosphorus Halides:
Forms two types of halides i.e. PX3 (X = F, Cl, Br, I) & PX5 (X = F, Cl, Br).
1. PCl3: Preparation:

1. P + 6Cl2 → 4PCl3

4
(White)

2. P + 8SOCl2 → 4PCl3 + 4SO2 + S2Cl2

4
(White) Thionyl Chloride Sulphur
monochloride
Properties:

1. Colourless oily liquid.

2. Hydrolysed in moisture and produce fumes of HCl: PCl3 + 3H2O → H3PO3 + 3HCl

3. 3C2H5OH + PCl3 → 3C2H5Cl + H3PO3

3CH3COOH + PCl3 → 3CH3COCl + H3PO3

2. Phosphors Pentachloride (PCl5):
Preparation:

1. P4 + 10Cl2 →4PCl5

2. P4 + 10SO2Cl2 →4PCl5 + 10SO2

Properties:

1. Yellowish white powder.

2. Hydrolysis: PCl5 + H2O → POCl3 + 2HCl

POCl3 + 3H2O → H3PO4 + 3HCl

3. Decomposition: PCl5 → PCl3 + Cl2

4. C2H5OH + PCl5 → C2H5Cl + POCl3 + HCl

5. CH3COOH + PCl5 → CH3COCl + POCl3 + HCl

6. 2 Ag + PCl5 → 2 AgCl + PCl3 Sn + 2PCl5 → SnCl4 + 2PCl3

7. In its shape, 3P-Cl bond are short/strong equatorial bond

while 2P-Cl bond are long/weak axial bonds which suffers
more repulsion.
8. In solid state it exists as an ionic solid, [PCl4] +
[PCl6] – in which the cation [PCl4] + is tetrahedral and
anion [PCl6]– is octahedral.
Oxoacids of phosphorus:

Oxoacids with +3 oxidation state tends to disproportionate to higher and lower

oxidation state. E.g. 4H3PO3 → 3H3PO4 + PH3

Acids with P – H are good reducing agent i.e.

4AgNO3+ 2H2O + H3PO2 → 4Ag + 4HNO3 + H3PO4

In oxoacids, P–H has non-ionisable H+ but the H-atom attached to P–OH is

ionisable i.e. H3PO3 is dibasic & H3PO4 is tribasic.
The structure of H3PO4 is tetrahedral. It has three ionizable P–OH bonds, therefore,
H3PO4 is tribasic (Basicity = 3).
Group-16 (Chalcogens):
1. Electronic configuration: ns2np3

Element Symbol Property

Oxygen O [He] 2s 2p
2 4 Non metallic
Sulphur S
2
[Ne] 3s 3p
4 Non metallic
Selenium 2
Se [Ar] 4s 4p
4 Semi Metal
Tellurium 2
Te [Kr]5s 5p
4 Semi Metal
Polonium Po [Xe] 6s 6p
2 Radioactive
4

2. Atomic and Ionic Radii: Increases down the group but size of O-atom is
exceptionally small. This is due to high electronegativity, the attraction between the
outermost electrons and nucleus increases.
3. Ionization Enthalpy: Decreases down the group but have lower value of I.E.
than group –15, due to their stability with half-filled stable configuration.

4. Electron gain Enthalpy:

 Oxygen has the least negative electron gain enthalpy due to its small size,
there is an inter-electronic repulsions in the 2p subshell.
 Sulphur has more negative value than oxygen due to the large size of 3p
subshell and there is no inter-electronic repulsions.
5. Electronegativity:
 O-atoms has 2nd highest electronegativity.
 Electronegativity decreases with increase in atomic number.
6. Physical Properties: Metallic character increases down the group. They are
less metallic due to their high ionization values.
7. Oxidation State:

 Oxygen shows negative oxidation state of – 2(H2O) & –1 (in H2O2), 0 (in O2)
and +2 (in OF2). Other elements shows O.S. of +2, +4, +6, because of
availability of empty d-orbital.