p-BLOCK ELEMENTS & THEIR COMPOUNDS

JEE Main Short Notes ˆ Class 12 Chemistry ˆ Groups 13–18

p-Block: Groups 13–18. General outer config: ns2 np1−6 .

B C N O F
Al Si P S Cl
Ga Ge As Se Br
In Sn Sb Te I
Tl Pb Bi Po At

Across period Electronegativity

Down IE, Oxidising power
∆at H (excl. N2 , O2 , F2 )

Covalent/vdW radius
Metallic character
Enthalpy of atomisation
(Gr.14 only)

⋆ STUDY FLOW – Read sections in this order ⋆

1 2 3 4 5 6 7
Gr. 13 Gr. 14 Gr. 15 Gr. 16 Gr. 17 Gr. 18 Revision
Boron Carbon Nitrogen Oxygen Halogens Noble + Tips
Al rxns Allotropes NH3 ,HNO3 H2 SO4 Reactivity Xe cpds MCQ
Diborane Silicates P oxoacids Hydrides Oxoacids Shapes Traps

GROUP 13 – THE BORON FAMILY GROUP 14 – THE CARBON FAMILY

Config: ns2 np1 General O.S. = +3 Config: ns2 np2 O.S. = +4 (major), +2 (inert pair ↑ down
Inert pair effect: Tl+ > In+ (stability of +1 increases down group)
group) Trend in +2 stability: Ge < Sn < Pb (Pb2+ most stable)

Reactivity Trends (Group 14)

Reactions of Aluminium
∆
With O2 : All −→ MO (monoxide) + MO2 (dioxide)
With acids: steam
2 Al(s) + 6 HCl(aq) −−→ 2 Al3+ – With water (Sn): Sn + 2 H2 O − −−−
→ SnO2 + 2 H2
(aq) + 6 Cl(aq) + 3 H2(g)
With alkali (amphoteric): With halogens: Forms MX2 and MX4 (X = F, Cl, Br, I).
2 Al(s) + 2 NaOH(aq) + 6 H2 O −−→ 2 Na+ [Al(OH)4 ](aq)
– + 3 H2(g)
Stability of dihalides increases down group.
Sodium tetrahydroxoaluminate(III)
With halogens (general Group 13): Catenation
2 E(s) + 3 X2(g) −−→ 2 EX3(s) (X = F, Cl, Br, I)
∆bond H ∆bond H
Bond Bond
C–C 348 Si–Si 297
Boron & Diborane (B2 H6 )
Ge–Ge 260 Sn–Sn 240

Small amines (NH3 , CH3 NH2 , (CH3 )2 NH) → unsymmet-

rical cleavage: Catenation order: C ≫ Si > Ge ≈ Sn; Pb = none
B2 H6 + 2 NH3 −−→ [H2 B(NH3 )2 ]+ + [BH4 ] – Carbon forms p–p π bonds ⇒ allotropes. Si, Ge use d-orbitals
Large amines ((CH3 )3 N, pyridine) → symmetrical cleav- and form only single bonds.
age:
2 (CH3 )3 N + B2 H6 −−→ 2 H3 B · N(CH3 )3
Allotropes of Carbon
With CO:
200◦ C, 20 atm
B2 H6 + 2 CO −−−−−−−−−→ ] 2 BH3 CO (borane carbonyl)
Form Hyb. Structure Key
data
3
Diamond sp 3D tetrahe- C–C =
dral, rigid 154 pm
Boron anomalies: Small size, high charge/radius ratio, no Graphite sp2 Layered C–C =
d-orbitals. hexagonal, 141.5 pm;
BF3 : Lewis acid (accepts lone pair). B forms only 3 bonds conducts gap =
340 pm
(electron deficient).
C60 sp2 12×5 + single
Borax Na2 B4 O7 ·10H2 O → acidic solution (boric acid is 20×6 rings 143.5;
monobasic weak Lewis acid). double
138.3 pm
 5-ring
C C
340 pm GROUP 15 – THE NITROGEN FAMILY
141.5 pm C
C C
C 6-ring

C
154 pm
C
C
C
C
Config: ns2 np3 O.S.: -3, +3, +5 (N also +1,+2,+4 with
Graphite O2 )
Diamond Buckminsterfullerene C60
sp2 hexagonal layers Stability of +5 decreases and +3 increases (inert pair)
sp3 tetrahedral vdW interlayer (340 sp
pm)2 ; 12 pentagons + 20 hexagons
3D rigid network Conducts ∥ layers
60 vertices; each C bonded to 3 others
down group:
Hardest substance Bi3+ >Sb3+ >As3+ ; Bi5+ <Sb5+ <As5+

CO & CO2 Key Reactions Anomalous Properties of Nitrogen

■ No d-orbitals ⇒ cannot form pentahalide (max. cova-
CO (reducing agent): lency = 4)
∆
Fe2 O3 + 3 CO −−→ 2 Fe + 3 CO2 (blast furnace) ■ Very high electronegativity and small size ⇒ strong H-
UV
CO + Cl2 −−→ COCl2 (phosgene; war gas) bonding in NH3
ZnO/Cr O3 ■ Forms p–p π bonds (N2 is triply bonded, very stable)
−−−−◦−2−−
CO + H2 − → CH3 OH (methanol synthesis) ■ Basicity order: NH3 > PH3 > AsH3 > SbH3 ≈ BiH3
300 C
CO2 (acidic oxide): ■ Stability of hydrides decreases, reducing character in-
CO2 + H2 O −−→ H2 CO3 (carbonic acid) creases NH3 →BiH3
CO2 + 2 NaOH −−→ Na2 CO3 + H2 O
Properties of Group 15 Hydrides (EH3 )
CO2 + Ca(OH)2 −−→ CaCO3 ↓ + H2 O (limewater test)
Carbide reactions: NH3 PH3 AsH3 SbH3 BiH3
Property
CaC2 + H2 O −−→ Ca(OH)2 + C2 H2 (acetylene) M.P. (K) 195.2 139.5 156.7 185 –
Al4 C3 + 12 H2 O −−→ 4 Al(OH)3 + 3 CH4 (methane) B.P. (K) 238.5 185.5 210.6 254.6 290
E–H dist. 101.7 141.9 151.9 170.7 –
(pm)
H-E-H (◦ ) 107.8 93.6 91.8 91.3 –
Silicates Classification ∆f H ◦ –46.1 +13.4 +66.4 +145.1 +278
(kJ/mol)
∆diss H(E- 389 322 297 255 –
Type O shared Formula H)

Orthosilicate 0 per Si [SiO4 ]4− (dis-

(A) crete) Trend summary for Gr.15 hydrides:
Pyrosilicate 1 per Si [Si2 O7 ]6− (2 BP & MP: NH3 is anomalously high (H-bonding); rest in-
(B) tetrahedra) crease with MW.
Cyclic (C) 2 per Si [SiO3 ]2n−
n Thermal stability: NH3 >PH3 >AsH3 >SbH3 >BiH3
(ring) Reducing character: NH3 <PH3 <AsH3 <SbH3 <BiH3
Single-chain 2 per Si [Si2 O6 ]4n−
n (py- Basicity: NH3 >PH3 >AsH3 >SbH3 ≈BiH3
(D) roxene)
Double- 2.5 per Si [Si4 O11 ]6n−
n Nitrogen & Its Compounds (Key Reactions)
chain (amphibole)
Sheet (E) 3 per Si [Si2 O5 ]2n−
n Oxides of Nitrogen:
(mica, talc)
O.S.
3D Frame- 4 per Si [SiO2 ]n Oxide Name Nature
work (F) (quartz) N2 O +1 Nitrous ox- Neutral
ide
NO +2 Nitric oxide Neutral
(param.)
O O O
N2 O3 +3 Dinitrogen Acidic
O O O O O O trioxide (HNO2
O O Si O Si O Si
O O O anhydride)
O Si O Si O Si Si O Si O Si
Si Si NO2 +4 Nitrogen Acidic
O O dioxide (brown)
O O O O
O O
N2 O5 +5 Dinitrogen Acidic
(A) Ortho (B) Pyro (D) Single chain
[Si2 O6 ]4n−
(E) Sheet pentoxide (HNO3
[SiO4 ]4− [Si2 O7 ]6− n 2n−
0 O shared 1 O shared 2 O shared [Si2 O5 ]n anhydride)
3 O shared

• Si atom • terminal O • bridging O Ostwald Process (HNO3 ):

Pt/Rh
4 NH3 + 5 O2 −−−◦−→ 4 NO + 6 H2 O
800 C

Silicones 2 NO + O2 −−→ 2 NO2

3 NO2 + H2 O −−→ 2 HNO3 + NO
Precursors for silicones: HNO3 as oxidizing agent:
(i) R3 SiCl (ii) R2 SiCl2 (iii) RSiCl3 Cu + 8 HNO3(dil) −−→ 3 Cu(NO3 )2 + 2 NO + 4 H2 O
Linear silicone from (CH3 )3 SiCl hydrolysis: Cu + 4 HNO3(conc) −−→ Cu(NO3 )2 + 2 NO2 + 2 H2 O
2 (CH3 )3 SiCl + H2 O −−→ 2 (CH3 )3 Si – OH −−→ S + 2 HNO3(conc) −−→ H2 SO4 + 2 NO
(CH3 )3 Si – O – Si(CH3 )3 + H2 O Brown ring test for NO− 3 :
Chain silicone from (CH3 )2 SiCl2 hydrolysis: FeSO4 + NO −−→ [Fe(H2 O)5 (NO)]2+ (brown ring; FeII )
n(CH3 )2 SiCl2 + nH2 O −−→ [(CH3 )2 SiO]n + 2 nHCl NH3 reactions:
Cross-linked polymer from CH3 SiCl3 : complex 3D NH3 + H2 O −−→ NH4 + + OH – (weak base)
network. 8 NH3 + 3 Cl2 −−→ N2 + 6 NH4 Cl (excess NH3 )
Hydrocarbon layer → water-repellent property. NH3 + 3 Cl2(excess) −−→ NCl3 + 3 HCl (excess Cl2 )
 Phosphorus – Allotropes & Compounds Anomalous Behaviour of Oxygen
■ Small size + high electronegativity + no d-orbitals ⇒
Allotropes (Stability): Black > Red > White
White → Red: heat at 573 K in CO2 atm max covalency = 4 (vs. S: up to 6)
Red → Black: sealed tube at 803 K ■ H2 O forms strong H-bonds (anomalously high BP/MP)
White → α-Black: heat at 473 K under high pressure ■ Catenation: S (S8 , S–S important in proteins) ≫ O (only
H2 O 2 )
PCl3 hydrolysis: PCl3 + 3 H2 O −−→ H3 PO3 + 3 HCl Oxygen Compounds – Key Reactions
PCl5 hydrolysis: PCl5 + 4 H2 O −−→ H3 PO4 + 5 HCl
P4 O10 + H2 O: P4 O10 + 6 H2 O −−→ 4 H3 PO4 silent el. discharge
Ozone (O3 ) preparation: 3 O2 −−−−−−−−−−−−→ 2 O3
SbCl3 /BiCl3 hydrolysis (oxychloride): O3 as oxidising agent:
SbCl3 + H2 O −−→ SbOCl v(orange) + 2 HCl PbS + 4 O3 −−→ PbSO4 + 4 O2
BiCl3 + H2 O −−→ BiOCl v(white) + 2 HCl 2 KI + H2 O + O3 −−→ I2 + 2 KOH + O2 (starch–I2 test →
blue)
Oxoacids of Phosphorus Bleaching powder:
Formula O.S. 3 Ca(OH)2 + 2 Cl2 −−→ Ca(OCl)2 · Ca(OH)2 · CaCl2 · 2 H2 O
Name Key bonds Prep.
Hypophos- H3 PO2 +1 1P-OH, 2P- White H2 O2 (reducing with KMnO4 ):
phorous H, 1P=O P4 +alkali 5 H2 O2 + 2 KMnO4 + 3 H2 SO4 −−→ 2 MnSO4 + K2 SO4 +
Ortho- H3 PO3 +3 2P-OH, 1P- P2 O3 +H2 O 8 H2 O + 5 O2
phosphorous H, 1P=O
Pyrophos- H4 P2 O5 +3 2P-OH, 2P- PCl3 +H3 PO3 H2 O2 (oxidising with KI):
phorous H, 2P=O H2 O2 + 2 KI −−→ 2 KOH + I2
Hypophos- H4 P2 O6 +4 4P-OH, Red
phoric 2P=O, 1P- P4 +alkali
P
Ortho- H3 PO4 +5 3P-OH, P4 O10 +H2 O
Sulphur Compounds & Oxoacids
phosphoric 1P=O
Pyrophos- H4 P2 O7 +5 4P-OH, heat H3 PO4 Contact process (H2 SO4 ):
phoric 2P=O, 1P- V O
2 5
O-P −−−
2 SO2 + O2 ↽ −−−−
⇀− 2 SO3
◦
Meta- (HPO3 )3 +5 3P-OH, P-acid+Br2 450 C
phosphoric 3P=O, 3P- SO3 + H2 SO4 −−→ H2 S2 O7 (oleum)
O-P
H2 S2 O7 + H2 O −−→ 2 H2 SO4
SO2 reactions:
P-H bond ⇒ reducing property. H3 PO2 (2 P-H) is strong SO2 + H2 O −−→ H2 SO3 (reducing/bleaching agent)
reducer; H3 PO3 (1 P-H) is moderate. H3 PO4 (0 P-H) is NOT SO2 + 2 H2 S −−→ 3 S + 2 H2 O (Wackenroder)
a reducing agent. Halide stability: SF6 exceptionally stable (steric protec-
Basicity = number of P-OH bonds (ionisable H). tion)
Dimeric halides: S2 F2 , S2 Cl2 , Se2 Cl2 , Se2 Br2
2 Se2 Cl2 −−→ SeCl4 + 3 Se (disproportionation)
Metal binary compounds (O.S. = -3):
3 Ca + N2 −−→ Ca3 N2 (calcium nitride)
3 Ca + 2 P −−→ Ca3 P2 (calcium phosphide) Oxoacids of Sulphur (Key)
6 Na + 2 As −−→ 2 Na3 As (sodium arsenide) Formula O.S.
Name Key feature
Sulphurous H2 SO3 +4 reducing;
SO2 +H2 O
GROUP 16 – THE OXYGEN FAMILY Sulphuric H2 SO4 +6 diprotic; dehy-
drating
Peroxomono- H2 SO5 +6 1 peroxide O-O
Config: ns2 np4 O.S.: -2, +2, +4, +6 (+4, +6 most com- sulphuric link
mon for S, Se, Te) (Caro)
Po is radioactive (t1/2 = 13.8 days); O & S = non-metals, Se Peroxodisulphuric H2 S2 O8 +6 2 peroxide links
Pyrosulphuric H2 S2 O7 +6 S-O-S bridge
& Te = metalloids, Po = metal (oleum)
Thiosulphuric H2 S2 O3 +2 Na2 S2 O3 = hypo
Dithionic H2 S2 O6 +5 S-S bond
Properties of Group 16 Hydrides (H2 E)
H2 O H2 S H2 Se H2 Te
Property O O O O O

M.P. (K) 273 188 208 222 bridge O–O

OH S OH OH S O S OH OH S O O S OH
B.P. (K) 373 213 232 269
H–E dist. 96 134 146 169 O
(pm)
H2 SO4 H2 S2 O7 (oleum) H2 S2 O8
H-E-H (◦ ) 104 92 91 90 O.S. +6 O.S. +6; S–O–S bridge O.S. +6; peroxide O–O
∆f H ◦ –286 –20 +73 +100 2 OH + 2 S=O
(kJ/mol)
∆diss H(H-E) 463 347 276 238
Ka 1.8×10−16 1.3×10−7 1.3×10−4 2.3×10−3
GROUP 17 – THE HALOGEN FAMILY

H2 O has anomalously high MP/BP due to H-bonding. Config: ns2 np5 F: only O.S. = –1; Cl, Br, I: –1, +1, +3,
Acidic character: H2 O < H2 S < H2 Se < H2 Te (as H–E +5, +7
bond strength decreases, easier ionisation) Physical states: F2 & Cl2 = gas, Br2 = liquid, I2 = solid
Reducing character: H2 S < H2 Se < H2 Te (H2 O has none) X–X bond energy: Cl–Cl > Br–Br > F–F > I–I (F–F weak
Thermal stability: H2 O > H2 S > H2 Se > H2 Te > H2 Po due to lone-pair repulsion)
 Key Reactions ■ Very high ionization enthalpy
■ Highly positive electron gain enthalpy
F2 with water (only oxidises):
Xenon Compounds (after Bartlett, 1962)
2 F2 + 2 H2 O −−→ 4 H+ + 4 F – + O2
Cl2 /Br2 with water (disproportionation): −
Bartlett’s discovery: O+2 PtF6 ⇒ IE(O2 ) ≈ IE(Xe) ≈ 1170
X2 + H2 O ↽ −−
−⇀
− HX + HOX (X = Cl, Br) kJ/mol
I− oxidised by O2 : ∴ Xe + PtF6 → Xe+ PtF− 6 (first noble gas compound)
4 I – + 4 H+ + O2 −−→ 2 I2 + 2 H2 O
XeF2 formation:
Cl2 with NaOH (cold, dilute): 200◦ C / Ni
cold Xe + F2 −−−−−−→ XeF2 (Xe in excess)
Cl2 + 2 NaOH −−→ NaCl + NaOCl + H2 O
XeF4 :
Cl2 with NaOH (hot, conc.): 400◦ C
hot Xe + 2 F2 −
−−−−→ XeF4
3 Cl2 + 6 NaOH −−→ 5 NaCl + NaClO3 + 3 H2 O 6 atm, 1

Bleaching powder: XeF6 :

300◦ C
3 Ca(OH)2 + 2 Cl2 −−→ Ca(OCl)2 · Ca(OH)2 · CaCl2 · 2 H2 O Xe + 3 F2 −−−−−−−−−−→ XeF6
60 atm, Xe excess
Halogen displacement (reactivity): Hydrolysis of XeF4 :
Cl2 + 2 KBr −−→ 2 KCl + Br2 (Cl displaces Br) 2 XeF4 + 4 H2 O −−→ 2 Xe + 4 HF + O2 + XeO2 F2
Br2 + 2 KI −−→ 2 KBr + I2 (Br displaces I) XeO3 from XeF6 :
HX acids strength: HF < HCl < HBr < HI (H–X bond XeF6 + 3 H2 O −−→ XeO3 + 6 HF
strength ↓) XeF2 hydrolysis:
Interhalogen compounds: XX’, XX’3 , XX’5 , XX’7 2 XeF2 + 2 H2 O −−→ 2 Xe + 4 HF + O2
E.g.: ClF, BrF3 , IF5 , IF7 ; more reactive than halogens.
Pseudohalides: CN− (cyanide), SCN− (thiocyanate), N− 3 LP Angle
Cpd. Shape Hyb.
(azide)
XeF2 Linear sp3 d 3 180◦
Oxoacids of halogens: XeF4 Sq. planar sp3 d2 2 90◦
XeF6 Dist. oct. sp3 d3 1 <90◦
O.S. Cl Br I Acid strength XeO3 Pyramidal sp3 1 –
+1 HOCl HOBr HOI weakest
XeOF4 Sq. pyram. sp3 d2 1 –
+3 HClO2 – – –
+5 HClO3 HBrO3 HIO3 strong
+7 HClO4 – HIO4 strongest 180◦ F
90◦ 1 LP
2 LP(axial)
Acid strength: HClO4 > HClO3 > HClO2 > HClO Xe
F Xe F F Xe F
O O
GROUP 18 – NOBLE GASES O
F
XeF2 – Linear XeF4 – Square planar XeO3 – Pyramidal
2 6 2 sp3 d — 3 LP sp3 d2 — 2 LP sp3 — 1 LP
Config: ns np (He: 1s ) All monatomic, colourless,
odourless, tasteless
Abundance in air: Ar > Ne > Kr > He > Xe (most Clathrate compounds: Xe atoms trapped in cavities of ice
abundant = Ar) crystal structure. Used to store radioactive isotopes of Kr &
Only weak dispersion forces (London) ⇒ very low MP/BP Xe from nuclear reactors.
Superfluid He(II): At 2.2 K. Climbs walls, very high ther-
Why Noble Gases are Inert mal conductivity, near-zero viscosity.
He(I): normal liquid at 4.2 K; He(II): superfluid below 2.2 K.
■ Completely filled ns2 np6 valence shell (He: 1s2 )

QUICK REVISION TABLE – p-BLOCK ELEMENTS

Concept Key Fact

Strongest oxidizing halogen F2 (highest electronegativity)
Weakest X–X bond F–F (lone pair repulsion; not I–
I)
Catenation order (Gr.16) S ≫ O (only H2 O2 , O3 )
Most thermodynamically Black P > Red P > White P
stable P allotrope
Non-reducing oxoacid of P H3 PO4 (zero P-H bonds)
Basicity of H3 PO2 1 (only 1 P-OH ionisable;
monobasic)
Basicity of H3 PO3 2 (dibasic)
Noble gas in highest abun- Ar (most abundant); He (light-
dance in air est)
First noble gas compound Xe+ PtF−6 (1962)
(Bartlett)
XeF2 shape & hyb. Linear, sp3 d, 3 LP
XeF4 shape & hyb. Square planar, sp3 d2 , 2 LP
XeF6 shape Distorted octahedral (1 LP)
Oxide acidity order (Gr.15) Acidic (+5) > Acidic (+3) >
Basic (Bi)
JEE MCQ TRAPS & TIPS – p-BLOCK
ˆ F–F bond is weaker than Cl–Cl (lone pair repulsion
in small F atom), hence F2 reacts violently despite
large bond enthalpy advantage
ˆ HF is weakest hydrohalic acid (strongest H–F
bond), but HF is a strong reducing agent compared
to other HX
ˆ N cannot form NF5 (no d-orbitals); P can form
PCl5 (d-orbitals)
ˆ H3 PO2 is strongest reducing agent among P
oxoacids (2 P-H bonds)
ˆ H3 PO3 is dibasic (2 ionizable OH), NOT tribasic
ˆ Reducing character of hydrides increases going
down Group 15 & 16
ˆ Thermal stability of hydrides decreases down both
Gr.15 & Gr.16
ˆ Graphite conducts electricity along the layer
(delocalised π electrons), not perpendicular
ˆ C60 has 12 five-membered rings + 20 six-membered
rings; each C is sp2
ˆ SO2 is reducing agent; TeO2 is oxidising agent
(Gr.16 dioxides)
ˆ ˆ Oxygen max. covalency = 4 (no d-orbitals);
Sulphur max. covalency = 6 (uses d-orbitals)
ˆ Noble gas abundance: Ar > Ne > Kr > He > Xe
(Ar is most abundant ≈ 0.93% of air)
ˆ He(II) = superfluid below 2.2 K; climbs walls, zero
viscosity
ˆ Oxoacid strength increases with more O atoms on
central atom (inductive effect)
ˆ Bleaching powder =
Ca(OCl)2 ·Ca(OH)2 ·CaCl2 ·2H2 O (NOT just
Ca(OCl)2 )
ˆ P white → red at 573 K in CO2 ; red → black at
803 K in sealed tube
ˆ All 3D silicates: all 4 O shared ⇒ [SiO2 ]n (quartz)
ˆ SbCl3 hydrolyses to orange SbOCl; BiCl3 to white
BiOCl (oxychlorides)

Source: p-Block Elements (NCERT Class 12 Chemistry) | Compiled for JEE Main Preparation | Groups 13–18 & d-Block intro