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.
  The stability of +6 decreases down the group and for +4 increases
due to inert pair effect.

Anomalous Properties of Oxygen: This is due to the: Small size, higher

electronegativity and non-availability of d orbitals.
Main point of differences between oxygen and other elements:
 Oxygen is gas while others are solids.
 Oxygen is diatomic while the other elements are more complex. For e.g. S8.
 Oxygen does not have d orbitals and that is why it cannot extend its octet. It
cannot show variable oxidation state like other members.

 Strong tendency to form pπ-pπ multiple bonds due to its small size.

Chemical Properties: 1. Hydrides:

Property Trends Explanation

Bond angle H2O>H2S>H2Se>H2Te Force of repulsion between the adjacent
bonds pairs is maximum in H2O.
Acidic H2O<H2S<H2Se<H2Te As the atomic size increases down the
Nature group, the distance between the central
atom and hydrogen increases and
cleavage of X-H bond becomes easier.
Volatility H2S>H2Se>H2Te>H2O H2O has least volatility due to hydrogen
bonding. As the size increases, van der
Waals forces increases and volatility
decreases.
Boiling H2S<H2Se<H2Te<H2O H2O has high boiling point due to
point hydrogen bonding. As the size increases,
van der Waals forces increase and boiling
point increases.
Thermal H2O>H2S>H2Se>H2Te Decrease in bond strength of X–H, due to
stability increase in size of the central atom.

Reducing H2O<H2S<H2Se<H2Te Decrease in thermal stability, increases

Character the reducing character.

2. Halides:
(a) Hexahalides:
 Stability of X (Halide) ⇒ F > Cl > Br > I.
 Direct fluorination of S gives SF6 with traces of SF4. SF6 is inert, non-toxic
gas. Its inertness is due to the presence of sterically protected S-atom which
does not allow thermodynamically favourable reaction like
hydrolysis.
SF6 + H2O → No reaction
(b) Tetrahalides: SF4 is gas. It has sp3d hybridisation with Trigonal
Bipyramidal shape with one lone pair and give see-saw geometry.
Sulphur is not sterically protected as it is surrounded by four fluorine
atom and the attack of water molecules becomes easy. SF4 + H2O → 4HF + SO2
  Se forms dichlorides and dibromides. They have sp3 hybridisation with
tetrahedral shape. 2Se2Cl2 → SeCl4 + 3Se
3. Oxides:
1. All element (except Se) forms monoxide.

2. All element forms dioxides in form MO2. The acidic character of oxides decreases
on moving down the group.

3. All elements form MO3 (trioxides) i.e. SO3.

4. SO2 has reducing character because +6 oxidation state is more stable than +4.
As the stability of +6 state decreases down the group due to inert pair effect.
5. TiO2 acts as an oxidising agent.
Dioxygen (O2): Preparation:
1. MnO2
2KClO3  → 2KCl + 3O2
∆

2. Thermal Decomposition:

2Ag2O(s) → 4Ag(s) + O2(g)

2Pb3O4(s) →6PbO(s) + O2(g)

2HgO(s) → 2 Hg(l) + O2(g)

2PbO2(s) → 6PbO + O2(g)

3. 2H2O2 (aq) → 2H2O + O2(g)

4. Large Scale: (a) Electrolysis of water give H2 at cathode & O2 at anode.
(b) Fractional Distillation of liquefied air (Industrial).

Properties:
1. Colourless, odourless gas, liquefies at 90K and freezes at 55K.
2. Solubility is 3.08 cm3 in 100 cm3 water at 293K. Sufficient to support marine
and aquatic life.
3. Isotopes 16O, 17O, 18O all paramagnetic.

4. Reaction of O2 with metals and non-metals. The bond dissociation energy of

dioxygen is high and hence the reactions of dioxygen require initiation by external
heating.

2Ca + O2 → 2CaO P4 + 5O2 → P4O10 C + O2 → CO2

CH4 + 2O2 → CO2 + 2H2O 4Al + 3O2 → 2Al2O3 2ZnS + 3O2 → 2ZnO + 2SO2
V2O5
2SO2 + O2  → 2SO3

Simple Oxides: O2 combines with other elements and form binary oxides of
different types like acidic, basic, amphoteric and neutral.
CuCl2
4HCl + O2  → 2Cl2 + 2H2O
1. Acidic Oxides: An oxide that combines with water to give acid. Eg. SO2,
Cl2O7, CO2, N2O5.

i.e SO2 + H2O → H2SO3

Mostly non-metal oxides are acidic is nature but some of metals of higher
oxidations states also form acidic oxides like Mn2O7, CrO3, V2O5.
2. Basic Oxides: Metal oxides which gives base with water. Eg. Na2O, CaO,
BaO. i.e. CaO + H2O → Ca(OH)2

3. Neutral Oxides: Oxides which neither show acidic and basic character. Eg.
CO, NO, N2O, etc.
4. Amphoteric Oxides: Metal oxides which slow both acidic and basic nature.
Eg. Al2O3,

Ozone (O3): It is an allotropic form of oxygen which lies at 20km above the sea
level. It protects us from harmful UV radiations.
Preparation:

Silent electrical discharge prevents its decomposition as the process is

Silent Electrical
3O2 Discharge
→ 2O3 ∆H = +142 kJ / mol. endothermic.

Two O-O bond lengths are similar due to resonance.

Properties:
1. Pure O3 is pale blue gas, dark, blue liquid and violet-black solid, characteristic
smell.
2. In excess it is harmful in body and may cause headache and nausea.

3. O3 is thermodynamically unstable and give O2 with large ∆H = –ve and ∆S = +ve.

This give ∆G = highly –ve, so its high concentration can be dangerously explosive.

4. O3 → O2 + [O], due to liberation of nascent oxygen, it acts as powerful oxidising

agent.

E.g.: PbS (s) + 4O3 (g) → PbSO4(s) + 4O2(g)

2KI (aq) + H2O(l) + O3(g) → 2 KOH(aq) + I2(s) + O2(g)

The I2 liberated is titrated with sodium thiosulphate, used for estimating O3 gas.

5. Exhaust of supersonic jet planes give nitrogen oxides (NO) which reacts with O3
and is depleting its amount. NO(g) + O3(g) → NO2(g) + O2(g)

6. Use of freons as aerosol sprays and as refrigerant is also depleting its amt.

Sulphur: Allotropes: 1. Rhombic (S8):

 (i) Most stable and common form of S at 96°C.

(ii) Known as alpha (α) – S.

(iii) Exist as S8 molecule in form of puckered ring.

2. Monoclinic (S8 and S6):

(i) Stable above 96°C.

(ii) Beta (b) – S.

(iii) It has different symmetry from rhombic but has

a puckered ring.
 In vapor state sulphur partly exists as S2
molecule which has two unpaired electrons in
the antibonding π* orbitals like O2 and, hence, exhibits paramagnetism.
 Sulphur exhibits greater catenation property than Se because down the
group atomic size increases and the strength of Se−Se bond becomes weaker
than S−S.

Sulphur Dioxide (SO2): Preparation:

(i) S(s) + O2 (g) → SO2 (g)

(ii) SO23− (aq)+ H2SO4 → H2O( ) + SO2 [In lab.]

Sulphite

(iii) 4FeS2 (s) + 11O2 (g) → 2Fe2O3 (s) + 8SO2 (g) [Industrial]

Due to resonance, the two π bonds are equal. Two of the three sp2 orbitals form two
σ bond while the third contains the lone pair of electrons. S is now left with one
half filled p-orbitals and one half filled d–orbitals. These form one p π -p π and p π -
d π double bond with oxygen atom. Thus SO2 has bent structure.
Properties:

1. Colourless gas, pungent smell, soluble in water, liquefies at room temp. under
pressure of 2 atm and boils at 263 K.
2. It is acidic in nature. It dissolves in water to form sulphurous acid.

SO2 + H2O → H2SO3 2NaOH + SO2 → Na2SO3 + H2O

Na2SO3 + H2O + SO2 →2NaHSO3

3. It also turns lime water into milky due to the formation of insoluble calcium
sulphite. SO2 + Ca(OH)2 → CaSO3 + H2O

But if large amount of gas is passed for a long time, milkiness disappears due to
the formation of calcium bisulphite. SO2 + CaSO3 + H2O→ Ca(HSO3)2 + H2O

4. It is reducing in nature in the presence of moisture. The reducing character is

due to the evolution of nascent hydrogen. SO2 + 2H2O → H2SO4 + 2[H]

5. It is a mild bleaching agent which is due to the reduction of the vegetable

colouring matter by nascent hydrogen liberated in the presence of moisture.
 Vegetable colouring matter + [H] → Colourless

This bleaching is temporary because it regains its colour by oxidation whenever

exposed to air.

6. SO2 is reducing as well as oxidizing agent. In SO2, S is in +4 oxidation state,

therefore, it can not only increase its oxidation state by losing electrons but not
also decrease its oxidation state by gaining electrons.

Reducing agent: Detection of SO2 gas.

2Fe3+ + SO2 + 2H2O → 2Fe2+ + SO24− + 4H+

Moist

5SO2 + 2MnO4− + 2H2O → 5SO24− + 4H+ + 2Mn2+ → Test for SO2 Gas
Dark Pink Colourless

Uses: 1.Refining of Petroleum sugar.

2. As an anti-chlor, disinfectant and preservative.

Oxo-acids of Sulphur:

Sulphuric Acid (H2SO4):

It is manufactured by contact process at 2bar pressure and 720K which involves
3 stages:
𝑉𝑉2𝑂𝑂5
1. S or S2– ore is burned in O2 to give SO2 gas. 2SO2 + O2 �⎯⎯� 2SO3
2. This SO2 gas reacts with more O2 in presence of V2O5 (as catalyst) to form SO3
gas.
3. This SO3 gas is absorbed by conc. H2SO4 to form oleum (H2S2O7) which combines
with H2O to give desired H2SO4.

SO3 + H2SO4 → H2S2O7; H2S2O7 + H2O → 2 H2SO4

In accordance with Le chatelier’s principle, to maximize the yield of H2SO4, a low

temperature (720 K to has optimum rate), a high pressure (2 bar) and V2O5 is used
as a catalyst (to increase the rate at 720 K).

Physical Properties:
1. It is colourless but commercial acid is yellow in colour due to impurities.

2. It's density is 1.84 g/cc.

3. High boiling point of 611K due to hydrogen bonding and freezes at 283K.
4. Its dilution in H2O is highly exothermic in nature. (Acid is added to water).

Chemical Properties:
1. Acidic Nature: It turn blue litmus to red and gives H+ ions
H2SO4 → H+ + HSO4− Ka1 > 10 very large

H2SO4− → H+ + SO24− Ka 2 > 1.2 × 10 −2

Ka2 is less than Ka1 because the negatively charged HSO4– ion has much less
tendency to donate a proton to H2O as compared to neutral H2SO4.
2. Dehydrating Nature: It is a powerful dehydrating agent. It is shown due to its
following properties.

(a) Drying of Gases: Gases like SO2, CO2, Cl2, HCl can be dried by passing
through H2SO4 because these gases do not react with H2SO4.
(b) Charring: Conc. H2SO4 reacts with, wood, sugar, etc. to form black mass
called charring.

C12H22O11 + H2SO4 → 11H2O + 12C

3. Oxidising Action: It is a strong oxidising agent.

C + 2H2SO4 → 2H2O + CO2 + 2SO2 ↑

S + 2H2SO4 → 2H2O + 3SO2

Cu + 2H2SO4 → CuSO4 + SO2 + 2H2O

4. Reactions with Salts:

H2SO4 + Na2CO3 → Na2SO4 + H2O + CO2

H2SO4 + Na2S → Na2SO4 + H2S

H2SO4 + Na2SO3 → Na2SO4 + H2O + SO2

H2SO4 + CaCl2 → CaSO4 + 2HCl ↑

H2SO4 + 2KNO3 → K2SO4 + 2HNO3

Uses:
1. As an acid in lab, industries, as dehydrating agent.

2. In prep. of HCl, HNO3, sulphates, ethers, dyes, paints, etc.

3. In fertilizers industries, in prep of (NH4)3PO3/sulphate /superphosphates of
lime, etc.
4. As a lab. reagent in mixture analysis and drying of gases.

Group 17(Halogens):
1. Electronic configuration: ns2np3
 Element Colour State Property
Fluorine (F) Pale yellow Gas Non
metal
Chlorine (Cl) Greenish Gas Non
yellow metal
Bromine (Br) Reddish Liquid Non
green metal
Iodine (I) Dark violet Solid Metal
Astatine (At) Black Solid (Rd.) Metal
Melting & Boiling point increase down the group.

Reactivity: F > Cl > Br > I

2. I. E.: They have very high I. E. & it decrease down the group.
3. Colour: They all are coloured. They have unpaired electrons in their valence
p orbital. These electrons absorb light and get promoted to higher orbitals. When
they return back to their ground state, they emit light in the visible region.
4. Oxidation State: They will form –1 or +1 ions.

 F is most electronegative and it cannot share its electron with an element

more electronegative than itself and hence it cannot show positive oxidation
state.
 Other shows +1, +3, +5, and +7 in addition to -1 which is most common.
 They are good oxidizing agent (F is strongest).

F2 + 2X– → 2F– + X2 (X = Cl, Br or I)

5. Reaction with water:

2F2(g) + 2H2O(l) → 4H+(aq) + 4F–(aq) + O2(g)

X2(g) + H2O(l) → HX(aq) + HOX(aq)

4I–(aq) + 4H+(aq) + O2(g) → 2I2(s) + 2H2O(l)

Reaction of I2 with water is non-spontaneous but I– can be oxidized by O2 in

acidic medium. (Reverse of F).

6. Atomic Radius: Smallest atomic radius due to max ENC. In a period they
have smallest size, but down the group size increase as atomic no. increase.
7. Electron Gain Enthalpy.: Max –ve electron gain enthalpy in period, due to
smallest size but down the group electron gain enthalpy becomes less –ve
(but –ve E.G.E. of F is less than that of Cl, due to very small size of F which
increase screening for incoming e–).
8. Electro-vity: High electro-vity, but decreases in group. F has maximum.
Fluorine is a stronger oxidizing agent than chlorine. (i) low enthalpy of
dissociation of F-F bond. (ii) high hydration enthalpy of F–.
Chemical Properties:
Anomalous Behaviour of F: Due to its small size, highest electro-vity, low F-F
dissociations, absence of d-orbital, it shows anomalous behaviour.
  All reaction are exothermic, due to small and strong bond of F with others
and form only one oxo-acid HOF.
1. Hydrides: They form volatile hydrides HX, except for HF which is liquid due to
intermolecular hydrogen bonding.
Acidic Strength: HF < HCl < HBr < HI
Since H–I bond is weakest, therefore it is the strongest acid.
Thermal Stability: HF > HCl > HBr > HI.
2. Halides:

(a) With metals of low I.E. (Na, K, Mg) they form ionic halides having high B.p and
M.p. M–F > M–Cl > M– Br > M–I
(b) With metals of high I.E. of Sn, Pb, Sb, etc. form covalent halide
(c) With non-metals like P, As, S, they form covalent halides.
3. Reducing Character: Reducing character increase down the group, because the
strength of H-X bond decreases from HF to HI.
4. Oxides: Halogen do not combine directly with O2 but they are formed indirectly.
 F forms OF2 (stable) and O2F2 (unstable) and are strong fluorinating agents.
Eg. O2F2 oxidise Pu to PuF6 and is removed from nuclear fuel.
 All oxides are powerful oxidising agents, insoluble solids & decomposes
explosively on heating.
Preparation of Chlorine: It is prepared by heating of HCl by MnO2/ KMnO4

(i) MnO2 + 4HCl → MnCl2 + H2O + Cl2

4NaCl + MnO2 + 4H2SO4 → MnCl2 + 4NaHSO4 + 2H2O + Cl2

(ii) 2KMnO4 + 16HCl → 2KCl + 2MnCl2 + 8H2O + 5Cl2

Manufacturing of Chlorine:

1. Electrolytic Process: Commercially Cl is obtained at anode by electrolysis

of natural or aq. brine solution.
E.C.
NaCl(s) + H2O( )  → NaOH(aq) + H2 (g) + Cl2 (g)

2. Deacon's Process (Oxdn of HCl): 4HCl + O2 

CuCl
723 K
→ 2Cl2 + 2H2O
2

Properties:
1. Greenish yellow gas with pungent smell and suffocating odour, soluble in water.
2 – 5 times heavier then air. Boiling point 239 K.

2. Rxn with Elements:

2Al + 3Cl2 → 2AlCl3 2Fe + 3Cl2 → 2FeCl3 2Na + Cl2 → 2NaCl,

S8 + 4Cl2 → 4S2Cl2 P4 + 6Cl2 → 4PCl3

3. Rxn with H2: H2 + Cl2 → 2HCl H2S + Cl2 → 2HCl + S

 C H10 16 +8Cl2 → 16HCl +10C
Terpentine oil

4. Rxn with NH3:

8NH3 + 3Cl2 → 6NH4Cl + N2 NH3 + 3Cl2 → NCl3 + 3HCl
Excess Excess

5. Rxn with Alkalis:

2NaOH+ Cl2 → NaCl + NaOCl + H2O

Cold & dil. Sod. Hypochlorite

6NaOH + 3Cl2 →  5NaCl + NaClO + 3H2O

3
Hot & conc. Sodium chlorate

6. Rxn with Hydrocarbons: uv

CH4 + Cl2  → CH3Cl + HCl

7. Bleaching Action of Cl2: Cl2 + H2O → 2HCl + [O]

2 Ca ( OH )2 + 2Cl2 →  Ca(OCl)2 + CaCl2 + 2H2O
Calcium hypochlorite

Coloured Matter + [O] → Colourless

Cl2 water on standing loses its yellow colour due to the formation of HCl & HOCl.
HOCl gives [O] responsible for oxidising and bleaching properties. It is permanent.
8. Oxidising Nature of Cl2:

2FeSO4 + H2SO4 + Cl2 → Fe2(SO4)3 + 2HCl

Na2SO3 + Cl2+ H2O → Na2SO4 + 2HCl

SO2 + 2H2O + Cl2 → H2SO4 + 2HCl

I2 + 6H2O + 5Cl2 → 2HIO3 + 10HCl

Uses of Cl2:

1. Used in sterilisations of drinking water, bleaching paper, pulp & textiles.

Extraction of gold and platinum.

2. Used in manufacturing of inorganic chemical like HCl, PCl3, PCl5 and bleaching
powder [Ca(OCl)2.CaCl2.Ca(OH)2.2H2O.
 Two poisonous gases which can be prepared from Cl2 are:
(i) Phosgene (ii) Mustard gas.

Manufacturing of HCl: Preparation:

823 K 420 K
NaHSO4 + NaCl  → Na 2SO4 + HCl NaCl + H2SO4  → NaHSO4 + HCl

Properties:
1. Colourless, pungent smell. Easily liquefies and freezes to a white crystalline
solid.

HCl(g) + H2O (l) → H3O+ (aq) + Cl– (aq) Ka = 107

2. Rxn with NH3: NH3 + HCl → NH4Cl

3. When three parts of HCl is mixed with one part of HNO3 it forms aqua regia
which is used to dissolve metals like Au, Pt. etc.

Au + 4H+ + NO3– + 4Cl– → AuCl4– + NO + 2H2O

3Pt + 16H+ + 4NO3– + 18Cl– → 3PtCl62– + 4NO + 8H2O

4. Rxn with Salts:

Na2CO3 + 2HCl → 2NaCl + H2O + CO2 NaHCO3 + 2HCl → 2NaCl + H2O + CO2

Na2SO3 + 2HCl → 2NaCl + H2O + SO2

 When HCl reacts with finely powdered iron, it forms ferrous chloride and not
ferric chloride. Fe + 2HCl → FeCl2 + H2. Liberation of hydrogen prevents the
formation of ferric chloride.

Oxoacids: F form only one acid i.e. fluoric (I) acid or hypofluorous acid HOF (with
+1). With increase in oxdn state the strength of acid increases.
Structures of Haloacids:

Acid strength and oxidising power:

1. Acidic strength of hypo-halous acids: HOCl > HOBr > HOI

Oxygen is more electronegative than halogens therefore it attracts electrons of the

oxygen halogen bond towards itself. Electron-density on the oxygen atom increases
from Cl to I and the OH bond breaks easily in HOCl.

2. Acidic strength of per-halic acids: HClO4 > HBrO4 > HIO4

As the electronegativity of the halogen decreases, the tendency to withdraws
electrons of the OH bond towards itself decreases and hence the acid strength
deceases.
3. Acidic strength of oxo-acids: HClO4 > HClO3 > HClO2> HClO.
This is based on the stability of conjugate base. Greater the number of oxygen
atoms in the anion, greater will be the dispersal of the negative charge through pπ-
pπ back bonding.

Interhalogen Compounds:
The compounds formed between halogen itself are interhalogen compounds. They
are of 4 types: XX’ , XX3’ , XX5’ and XX7’
They are prepared directly by combing halogens.
437 K
Cl2 + F2  → 2ClF I2 + 3Cl2 → 2ICl3 Br + 3F
2 2 → 2BrF3
(excess ) Diluted with water

hν
ClF3 + F2  → ClF5 I2 + Cl2 → 2ICl
Characteristics:

1. More reactive than constituent halogen due to electronegativity difference the X–

X' bond is polar in nature and therefore it is easy to break the bond.

2. Undergo hydrolysis: XX' + H2O → HX' + HOX

573 K
Cl2 + 3F2  → 2ClF3 Br2 + 5F2 → 2BrF5
(excess ) (excess )

3. According to VSEPR theory, these will occupy the corners of a trigonal

bipyramidal. The two lone pairs will occupy the equatorial positions to minimize
repulsions. In addition, the axial fluorine atoms will be bent towards the equatorial
fluorine in order to minimize the lone-pair-lone pair repulsions. The shape would
be that of a slightly bent ‘T’.

Group 18(Noble Gases):

1. Electronic configuration: ns2np6

ELEMENT CONFIGURATION
Helium (He) 1s
2

Neon ( Ne) [He]2s 2p

2 6

Argon (Ar) 2
[Ne]3s 3p
6

Krypton (Kr) 10
[Ar]3d 4s 4p
2 6

Xenon (Xe)[Kr]4d 5s 5p
10 2 6

2. Monatomic Nature: Noble gases being monoatomic have no interatomic

forces except weak dispersion forces and therefore, they are liquefied at very low
temperatures. Hence, they have low boiling points.
3. I.E.: It is highest in a period due to their stability and it decrease as moving
down.

4. Atomic Radius: Increases down the group with increase in atomic no.
5. E.G.E.: Large +ve EGE, as they have inert gas configuration they don’t have any
tendency to gain an electron.
Important Compounds of Noble Gases:

In 1962 Neil Bartlett prepared a red compound O2+PtF6–. Since ionization enthalpy of
Xe is almost same as that of O2 as well as low therefore it can also form compounds
under certain conditions and made Xe+PtF6–. Similarly other are KrF2 and RnF2.
Preparation:
 573 K 143 K
Xe + 3F2 
60 −70 bar
→ XeF6 XeF4 + O2F2 → XeF6 + O2
(1:20)

873 K
Xe + 2F2 
7 bar
→ XeF4
(1:5 ratio)

But on hydrolysis: XeF2 + 2H2O → 2Xe + 4HF + O2

XeF2 + PF5 → [XeF]+[PF6]– XeF4 + SbF5 → [XeF3]+[SbF6]–

II. Xe–O2 Compounds: Hydrolysis of Xe-F compound gives:

673 K
Xe + F2 
1 bar
→ XeF2 (s) 6XeF4 + 12H2O → 4Xe + 2XeO3 + 24HF + 3O2
(Excess )

XeF6 + 3H2O → XeO3 + 6HF

But partial hydrolysis give: XeF6 + H2O → XeOF4 + 2HF

XeF6 + 2H2O → XeO F 2 2 + 4HF

Xe Dioxydifluoride

The hydrolysis of XeF6 is not a redox reaction. The products of hydrolysis are
XeOF4 and XeO2F2 where the oxidation states of all the elements remain the same
as it was in the reacting state.

Uses of He:1. Filling balloon as is light and non-inflammable and for diving
apparatus due to its inert nature.

2. It is used to produce and sustain powerful superconducting magnets which form

an essential part of modern NMR spectrometers and MRI for clinical diagnosis.
Neon: Discharge Tubes & fluorescent lamp.

Argon: Creates inert atmosphere in welding & metallurgical operations.

Krypton: Kr & Xe are used in some tubes for high speed photography.
Radon: Radioactive Researches. Normal treatment of cancer & other malignant
growth.