P-BLOCK ELEMENTS

Complete JEE Notes

Groups 13 – 18 | Class XI & XII

OVERVIEW OF P-BLOCK ELEMENTS

P-block elements occupy Groups 13–18 of the periodic table. The last electron enters the p-orbital.
These groups together contribute the richest variety of chemistry, allotropy, and acid-base behaviour
tested in JEE.

Group Valence Common OS Key Property Members

e⁻
13 (Boron) 3 +3 Lewis acid character B, Al, Ga, In, Tl
dominant
14 (Carbon) 4 +4, +2, −4 Catenation, allotropy C, Si, Ge, Sn, Pb
15 5 +5 to −3 Lone pair chemistry, N, P, As, Sb, Bi
(Nitrogen) basicity
16 (Oxygen) 6 −2, +4, +6 Strong oxidising agents O, S, Se, Te, Po
17 7 −1 to +7 Highest electronegativity F, Cl, Br, I, At
(Halogens)
18 (Noble) 8 0 (rare +2,+4) Inert, closed shell He, Ne, Ar, Kr, Xe, Rn

[JEE IMPORTANT] Inert pair effect: heavier elements in each group prefer a lower OS (2 less than
group maximum) due to poor shielding by d/f electrons. Pb²⁺ > Pb⁴⁺; Tl⁺ > Tl³⁺; Bi³⁺ > Bi⁵⁺.
GROUP 13 — BORON FAMILY
General Characteristics
• Electronic configuration: ns²np¹
• First element (B) is a metalloid; rest are metals
• Al is the most abundant metal in Earth's crust
• Boron shows anomalous behaviour due to: small size, high charge density, no d-orbitals in
valence shell
[TREND] Trend down the group: metallic character increases. B is non-metallic, Al is amphoteric
metal, Ga/In/Tl are typical metals.

Boron — Unique Chemistry

Structure of Boron Compounds
• Boron forms only 3 bonds (electron deficient) → Lewis acid
• BF₃ sp² hybridised, planar, accepts lone pairs
• Diborane (B₂H₆): banana bonds (3c-2e bonds), bridging H atoms
• Boron cannot expand octet (no d-orbital) — key distinction from Al

Borax (Na₂B₄O₇·10H₂O)
• Contains [B₄O₅(OH)₄]²⁻ ion (not simple BO₃³⁻)
• Hydrolysis: borax + H₂O → boric acid (weak acid) + NaOH
• Borax bead test: dissolves in metal oxide → coloured metaborate beads (used to identify metal
ions)
• Boric acid [B(OH)₃]: planar structure, weak monobasic Lewis acid (accepts OH⁻, not donates H ⁺)
[EXCEPTION] Boric acid is a Lewis acid, NOT a Brønsted acid. It accepts OH⁻ from water: B(OH)₃ +
H₂O → [B(OH)₄]⁻ + H⁺

Aluminium — Key Reactions

• Reaction with NaOH (aq): 2Al + 2NaOH + 2H₂O → 2NaAlO₂ + 3H₂↑ (amphoteric)
• Reaction with HCl: 2Al + 6HCl → 2AlCl₃ + 3H₂↑
• Thermite reaction: 2Al + Fe₂O₃ → Al₂O₃ + 2Fe + heat (used in welding)
• AlCl₃ is a strong Lewis acid (used as Friedel-Crafts catalyst)
• Al₂O₃ (alumina): amphoteric oxide

Alums
• General formula: M⁺M³⁺(SO₄)₂·12H₂O
• Example: Potash alum = KAl(SO₄)₂·12H₂O
• Used in water purification (Al³⁺ hydrolyses → Al(OH)₃ floc)
Comparative Properties — Group 13
Property B Al Ga Tl
Nature Non-metal Metal Metal Metal
Oxide type Acidic Amphoteric Amphoteric Basic
Stable OS +3 +3 +3/+1 +1 (inert pair)
Hybridisation (MX₃) sp² sp³ (in solid) sp³ sp³

[JEE IMPORTANT] Ga has a lower melting point than expected (29.8°C) due to its unique molecular
structure in the solid state. This is an anomaly frequently tested.
GROUP 14 — CARBON FAMILY
General Characteristics
• Electronic configuration: ns²np²
• Tetravalency: forms 4 covalent bonds (sp³, sp², or sp)
• Catenation: C–C bond is strong and extensive → basis of organic chemistry
• Catenation order: C >> Si > Ge ≈ Sn > Pb
[TREND] Metallic character: C (non-metal) → Si/Ge (metalloids) → Sn/Pb (metals). Melting point
decreases down the group (except C→Si increase then drop).

Carbon — Allotropes
Diamond
• 3D tetrahedral network: each C sp³ bonded to 4 others
• Hardest natural substance, electrical insulator, poor thermal conductor

Graphite
• Layered hexagonal sheets: each C sp² bonded to 3 others
• Delocalised π electrons between layers → good electrical conductor
• Weak van der Waals forces between layers → soft, lubricant

Fullerenes
• C₆₀ (Buckminsterfullerene): soccer ball structure, 12 pentagons + 20 hexagons
• C atoms: sp² hybridised; no true graphite-like conductivity due to incomplete delocalisation

Oxides of Carbon
Carbon Monoxide (CO)
• Colourless, odourless, highly toxic gas
• Bonds with haemoglobin (250× stronger than O₂) — CO poisoning
• Strong reducing agent: Fe₂O₃ + 3CO → 2Fe + 3CO₂ (blast furnace)
• Isoelectronic with N₂ (both 10 electrons, triple bond)

Carbon Dioxide (CO₂)

• Linear molecule (sp), non-polar
• Acidic oxide: CO₂ + H₂O → H₂CO₃ (carbonic acid, diprotic, weak)
• CO₂ + NaOH (excess) → Na₂CO₃ + H₂O; CO₂ + NaOH (limited) → NaHCO₃
Silicon and Its Compounds
Silicon Dioxide (SiO₂)
• Giant covalent 3D structure (unlike CO₂ which is molecular)
• Acidic oxide: SiO₂ + NaOH → Na₂SiO₃ + H₂O
• SiO₂ + HF → SiF₄ + H₂O (HF etches glass — unique reaction)

Silicones
• Polymers with Si–O–Si backbone and organic groups on Si
• Hydrophobic, thermally stable, used in lubricants, sealants

Silicates
• Basic unit: [SiO₄]⁴⁻ tetrahedral unit
• Types by sharing: ortho (0), pyro (1), single chain (2), double chain (2.5), sheet (3), 3D
framework (4)

Tin and Lead

• Sn: +2 and +4 OS; Sn²⁺ is a reducing agent
• Pb: stable +2 OS (inert pair); PbO₂ is an oxidising agent
• Pb₃O₄ (red lead/minium): mixed oxide = 2PbO·PbO₂
[JEE IMPORTANT] PbO₂ acts as an oxidising agent; Sn²⁺ (stannous) acts as a reducing agent. Both
tested via reaction with HCl, H₂SO₄.
GROUP 15 — NITROGEN FAMILY
General Characteristics
• Electronic configuration: ns²np³ — half-filled p subshell, extra stability
• Lone pair present → Lewis base character
• OS range: −3 to +5
• N cannot expand octet (no d-orbital); P, As, Sb, Bi can
[TREND] Basicity of hydrides (MH₃): NH₃ >> PH₃ > AsH₃ > SbH₃. Decreases because lone pair
availability decreases down the group.

[TREND] Stability of hydrides decreases down the group; reducing power of hydrides increases down
the group.

Nitrogen
Dinitrogen (N₂)
• Triple bond (N≡N), bond enthalpy = 941 kJ/mol — very stable
• Used as inert atmosphere; liquid N₂ as coolant

Oxides of Nitrogen
Oxide OS of N Nature Key Feature
N₂O +1 Neutral Laughing gas; supports combustion; linear N–N–O
NO +2 Neutral Colourless, paramagnetic (odd electron), toxic
N₂O₃ +3 Acidic Anhydride of HNO₂; unstable
NO₂ +4 Acidic Brown, paramagnetic; dimerises to N₂O₄
N₂O₅ +5 Acidic Anhydride of HNO₃; solid

Nitric Acid (HNO₃)

• Prepared: Ostwald Process — N₂ → NH₃ → NO → NO₂ → HNO₃
• Concentrated HNO₃ passivates Fe, Al, Cr (forms protective oxide layer)
• Aqua regia: 3 HCl : 1 HNO₃ (conc.) — dissolves noble metals (Au, Pt)
• Dilute HNO₃ + metals → NO; concentrated HNO₃ + metals → NO₂
• HNO₃ + Cu (dilute): 3Cu + 8HNO₃(dil) → 3Cu(NO₃)₂ + 2NO + 4H₂O
• HNO₃ + Cu (conc): Cu + 4HNO₃(conc) → Cu(NO₃)₂ + 2NO₂ + 2H₂O
[EXCEPTION] HNO₃ does NOT react with noble metals (Au, Pt) alone. Aqua regia is needed. Gold
dissolves by forming [AuCl₄]⁻.

Ammonia (NH₃)
• Haber Process: N₂ + 3H₂ ⇌ 2NH₃; 400–500°C, 200 atm, Fe catalyst with K₂O/Al₂O₃ promoter
 • Pyramidal geometry, sp³ hybridised, one lone pair
• Strong H-bonding → high boiling point for its MW
• Weak base: NH₃ + H₂O ⇌ NH₄⁺ + OH⁻

Phosphorus
Allotropes of Phosphorus
• White P: P₄ tetrahedral units, waxy solid, highly reactive, stored in water
• Red P: polymeric chains of P₄ units, less reactive, stable in air
• Black P: layered structure, most stable thermodynamically

Oxoacids of Phosphorus
Acid Formula OS of P Basicity Reducing?
Hypophosphor H₃PO₂ +1 Monobasic Yes (2 P–H bonds)
ous
Phosphorous H₃PO₃ +3 Dibasic Yes (1 P–H bond)
acid
Phosphoric H₃PO₄ +5 Tribasic No (no P–H bond)
acid
Pyrophosphori H₄P₂O₇ +5 Tetrabasic No
c

[JEE IMPORTANT] Rule: Only P–OH bonds are acidic. P–H bonds are NOT acidic but make the acid
a reducing agent. Count P–OH bonds to find basicity.
GROUP 16 — OXYGEN FAMILY (CHALCOGENS)
General Characteristics
• Electronic configuration: ns²np⁴ — two electrons short of noble gas
• OS: −2 common; +4 and +6 for heavier elements (d-orbital expansion)
• O has no d-orbitals, so max OS of O in compounds = −1 (peroxides) or 0 (F₂O, OF₂)
[TREND] Acidic character of oxoacids: H₂SO₄ > H₂SeO₄ > H₂TeO₄. Stability of hydrides: H₂O >>
H₂S > H₂Se > H₂Te. Reducing character: H₂O < H₂S < H₂Se < H₂Te.

Oxygen
Allotropes of Oxygen
• Dioxygen (O₂): paramagnetic (2 unpaired electrons), bond order = 2
• Ozone (O₃): bent molecule, O–O–O angle ≈ 117°, diamagnetic, bond order = 1.5

Ozone (O₃)
• Preparation: electrical discharge through dry O₂
• Oxidising agent: O₃ → O₂ + [O] (nascent oxygen is the active species)
• Ozone + PbS → PbSO₄ (used to test for O₃)
• Ozone + KI + H₂O → KOH + I₂ + O₂ (used in iodometric titration)
• Depletion: O₃ + NO → NO₂ + O₂; CFCs also destroy ozone layer
[EXCEPTION] O₃ is diamagnetic; O₂ is paramagnetic. Do not confuse. O₃ has delocalised bonds;
pure single/double bond structure is incorrect.

Sulphur
Allotropes of Sulphur
• Rhombic (α-S): stable below 96°C, crown S₈ rings
• Monoclinic (β-S): stable 96–119°C
• Plastic (amorphous) S: formed by pouring molten S into cold water, chain structure

Oxides of Sulphur
• SO₂: acidic, V-shape, bond angle 119°, can act as oxidising or reducing agent
• SO₃: planar, sp² hybridised, strongly acidic, anhydride of H₂SO₄

Sulphuric Acid (H₂SO₄) — Contact Process

• S → SO₂ (burning S or roasting pyrite) → SO₃ (V₂O₅ catalyst, 450°C, 2 atm) → H₂SO₄
• SO₃ absorbed in H₂SO₄ → oleum (H₂S₂O₇) then diluted — NOT direct in water (too
exothermic)
• Dilute H₂SO₄: strong diprotic acid; reacts with metals
 • Concentrated H₂SO₄: strong oxidising acid, dehydrating agent
• Hot conc. H₂SO₄ + Cu: Cu + 2H₂SO₄ → CuSO₄ + SO₂ + 2H₂O
• Hot conc. H₂SO₄ + C: C + 2H₂SO₄ → CO₂ + 2SO₂ + 2H₂O
• Concentrated H₂SO₄ + NaCl → NaHSO₄ + HCl (dehydrating → liberates HCl)

Oxoacids of Sulphur
Acid Formula OS of S Key Feature
Sulphurous H₂SO₃ +4 Unstable, exists only in solution
Sulphuric H₂SO₄ +6 Strong diprotic, dehydrating agent
Thiosulphuric H₂S₂O₃ +2 Reducing agent; S in two OS: 0 and +4 (avg
+2)
Pyrosulphuric H₂S₂O₇ +6 Oleum; very strong dehydrating acid
Peroxodisulphuric H₂S₂O₈ +7 avg Contains peroxy linkage (–O–O–)

[JEE IMPORTANT] Na₂S₂O₃ (sodium thiosulphate) reacts with I₂: 2Na₂S₂O₃ + I₂ → Na₂S₄O₆ +
2NaI. This is the basis of iodometric titration. S OS goes from +2 to +2.5.
GROUP 17 — HALOGENS
General Characteristics
• Electronic configuration: ns²np⁵ — one electron short of noble gas
• Most electronegative group; F is the most electronegative element
• OS: −1 most common (F only); Cl, Br, I can show +1, +3, +5, +7
• Exist as diatomic X₂; bond dissociation: F₂ << Cl₂ > Br₂ > I₂
[TREND] Oxidising power: F₂ > Cl₂ > Br₂ > I₂. A halogen can displace a heavier halide from its salt
solution. F₂ displaces Cl⁻, Br⁻, I⁻; Cl₂ displaces Br⁻, I⁻; Br₂ displaces only I⁻.

Fluorine — Anomalous Properties

• Cannot exhibit positive OS (most electronegative)
• HF is a weak acid (strong H-bonding), unlike HCl (strong acid)
• F₂ + H₂O → HF + O₂ + OF₂ (F oxidises O in water)
• F₂ reacts with all noble gases (Xe, Kr, Rn) under suitable conditions
• Smallest atomic radius → highest charge density → anomalous properties
[EXCEPTION] OF₂ is oxygen difluoride, not fluorine oxide. Oxygen has OS +2 here because F is
more electronegative than O. This is a common JEE trap.

Hydracids (HX)
Property HF HCl HBr HI
Acid strength Weak Strong Strong Strongest
Reducing Lowest Low Moderate Highest
power
Bond strength Highest High Moderate Lowest
Thermal Highest High Moderate Lowest
stability

Oxoacids of Chlorine
Acid Formula OS of Cl Strength Oxidising Power
Hypochlorous HOCl +1 Weakest Highest
Chlorous HOClO +3 Weak High
Chloric HOClO₂ +5 Strong Moderate
Perchloric HOClO₃ +7 Strongest Lowest (conc.)

[JEE IMPORTANT] Acid strength of oxoacids ∝ OS of Cl (more O atoms pull electron density → more
 acidic). Oxidising power ∝ lower OS (thermodynamic instability drives oxidation).

Interhalogen Compounds (XY, XY₃, XY₅, XY₇)

• Formed between two different halogens
• More reactive than the parent halogens
• ClF₃: T-shaped; ClF₅: square pyramidal; IF₇: pentagonal bipyramidal
• Central atom: heavier halogen (lower electronegativity)

Bleaching Powder
• Composition: Ca(OCl)Cl or Ca(ClO)Cl
• Preparation: Ca(OH)₂ + Cl₂ → Ca(OCl)Cl + H₂O (at <40°C)
• Bleaching action: due to nascent oxygen [O] from HOCl
• Cannot bleach dry substances — moisture is needed
GROUP 18 — NOBLE GASES
General Characteristics
• Closed-shell configuration: ns²np⁶ (He: 1s²)
• Extremely low chemical reactivity; high ionisation enthalpy
• Monoatomic; low boiling points (He lowest, Rn highest)
• He has the lowest boiling point of any element (−269°C)
[TREND] Reactivity increases down the group: He, Ne, Ar form no stable compounds. Kr forms a few;
Xe forms several stable compounds (XeF₂, XeF₄, XeF₆, XeO₃, XeO₄).

Xenon Compounds
Compound Shape Hybridisation Lone pairs on Xe
XeF₂ Linear sp³d 3 lone pairs (equatorial)
XeF₄ Square planar sp³d² 2 lone pairs (axial)
XeF₆ Distorted sp³d³ 1 lone pair
octahedral
XeO₃ Pyramidal sp³ 1 lone pair
XeO₄ Tetrahedral sp³ 0 lone pairs

• XeF₂ + H₂O → Xe + 2HF + ½O₂ (hydrolysis)

• XeF₄ + H₂O → Xe + O₂ + HF (disproportionation)
• XeF₆ + H₂O → XeO₃ + HF
[JEE IMPORTANT] XeF₂ is the most stable xenon fluoride. Reason: two bond pairs + three lone pairs
→ linear geometry (VSEPR). All xenon fluorides are strong fluorinating agents.

Uses of Noble Gases

• He: airships, balloons, deep-sea diving (with O₂), cryogenics, MRI cooling
• Ne: advertising/neon signs (red-orange light)
• Ar: inert atmosphere in welding and metallurgy, filling electric bulbs
• Kr: fluorescent lighting
• Xe: photoflash lamps, anaesthesia
• Rn: radiotherapy (radioactive)
QUICK REVISION — HIGH-YIELD JEE FACTS
Important Industrial Processes
Process Product Catalyst / Conditions Key Reaction
Haber Process NH₃ Fe; 400–500°C; 200 atm N₂ + 3H₂ ⇌ 2NH₃
Ostwald Process HNO₃ Pt/Rh gauge; 800°C 4NH₃ + 5O₂ → 4NO +
6H₂O
Contact Process H₂SO₄ V₂O₅; 450°C; 2 atm 2SO₂ + O₂ → 2SO₃
Solvay Process Na₂CO₃ NH₃/CO₂ in NaCl brine NaCl + NH₃ + CO₂ +
H₂O → NaHCO₃↓
Hall-Héroult Al Cryolite electrolyte Electrolysis of Al₂O₃

Shapes and Hybridisation — Frequent JEE Molecules

Molecule Shape Hybrid. Lone Pairs Special Feature
NH₃ Pyramidal sp³ 1 Lone pair involved in H-
bonding
PCl₅ Trig. bipyramidal sp³d 0 Axial bonds longer
SF₄ See-saw sp³d 1 VSEPR: equatorial LP
ClF₃ T-shaped sp³d 2 Two equatorial LPs
SF₆ Octahedral sp³d² 0 All bonds equal length
XeF₄ Square planar sp³d² 2 Axial LPs cancel dipoles
SO₃ Trigonal planar sp² 0 Resonance; bond order
1.33
ClO₃⁻ Pyramidal sp³ 1 Cl–O bond order > 1
I₃⁻ Linear sp³d 3 3 equatorial LPs on I
NO₂ Bent sp² 0 (odd e⁻) Paramagnetic;
dimerises

Anomalous Behaviour Summary

• Boron: No d-orbitals; max valency 4 (not 6 like Al); forms 3c-2e bonds in B₂H₆
• Carbon: Strongest catenation; multiple bonding (pπ-pπ); CO₂ is molecular, SiO₂ is covalent
solid
• Nitrogen: No d-orbitals; cannot form 5 bonds; N₂ extremely stable (triple bond)
• Oxygen: Only −2 and −1 OS (except OF₂: +2); no d-orbitals; H₂O has anomalously high BP
• Fluorine: Always −1; most electronegative; HF is weak acid; F₂ attacks noble gases
Diagonal Relationships
Diagonal relationships occur because elements diagonally adjacent in the periodic table have similar
charge/radius ratios.
Element Diagonal Partner Similarities
Li Mg Both form carbonate/nitride; Li₂CO₃ and MgCO₃
decompose on heating
Be Al Both amphoteric; both form bridged M₂X₆ dimers;
passive with HNO₃
B Si Both form covalent hydrides; both oxides are acidic and
glassy

Key Colour and Physical Facts

• F₂: Pale yellow gas
• Cl₂: Greenish-yellow gas
• Br₂: Reddish-brown liquid (only non-metallic liquid at room temperature)
• I₂: Violet-black solid; violet vapour; gives blue-black with starch
• NO₂: Brown gas; dimerises to colourless N₂O₄
• O₃: Pale blue gas; pungent smell
• S: Yellow solid; rhombic most stable at room temp
• P (white): Waxy, pale yellow; luminescent in dark

[JEE IMPORTANT] Isoelectronic species frequently asked: CO & N₂ (10e, triple bond); NO⁺ & N₂ &
CO (10e); SO₂ & O₃ (18e, bent); CO₃²⁻ & NO₃⁻ & SO₃ (planar, 24e valence shell); NH₄⁺ & PH₄⁺ &
BH₄⁻ (tetrahedral, 18e for BH₄⁻).

— End of P-Block JEE Notes —