d & f Block Elements

Complete JEE Mains Notes | 2019–2026 PYQ Analysis

NTA Pattern Analysis | Assertion-Reason Question Bank | April 2026 Ready

Chapter Weight NTA Frequency Avg Qs/Year High-Yield Topics

Oxidation states, KMnO4/K2Cr2O7, Lanthanoid

3-4 Marks Every Year 2-3 Qs contraction

1. INTRODUCTION & POSITION IN PERIODIC TABLE

d-Block (Transition Elements)

The d-block occupies groups 3–12 in the periodic table (the large middle section between s and p blocks). d-orbitals of
the penultimate energy level are progressively filled, giving rise to four series:

Series Elements d Orbital Filled Note

1st (3d) Sc (21) – Zn (30) 3d Most studied in JEE

2nd (4d) Y (39) – Cd (48) 4d Pd: 4d105s0

3rd (5d) La, Hf (72) – Hg (80) 5d Lanthanoid contraction effect

4th (6d) Ac, Rf–Cn 6d Radioactive, synthetic

IUPAC Definition of Transition Metal

A transition metal is one which has incomplete d-subshell either in its neutral atom OR in its commonly
occurring ions.
Zn, Cd, Hg, Cn (d10 always) → NOT transition elements but studied with them (end members).

Sc (3d1 neutral) → IS a transition element; Zn (3d10 in all states) → NOT.

PYQ JEE Mains 2019

Which of the following is NOT a transition element?
Ans: Zn (Z=30) — because Zn2+ also has completely filled 3d10 configuration.

PYQ JEE Mains 2022

Sc (Z=21) is a transition element but Zn (Z=30) is not. Which statement best explains this?
Ans: Sc has incomplete 3d1 in ground state; Zn has 3d10 in ground state AND in Zn2+.

2. ELECTRONIC CONFIGURATIONS
General Formula: (n-1)d1-10 ns1-2
Exception: Pd → 4d105s0 (no s electrons!)

3d Series – Ground State Configurations (MOST IMPORTANT FOR JEE)

Element Z Config M+ M2+ M3+ Key Point

Sc 21 [Ar]3d14s2 3d14s1 3d1 [Ar] Only +3 state

2 2 2 1 2 1
Ti 22 [Ar]3d 4s 3d 4s 3d 3d +2,+3,+4
3 2 3 1 3 2
V 23 [Ar]3d 4s 3d 4s 3d 3d +2 to +5
5 1 5 4 3
Cr 24 [Ar]3d 4s 3d 3d 3d Half-fill 3d

Mn 25 [Ar]3d54s2 3d54s1 3d5 3d4 +2 to +7

6 2 6 1 6 5
Fe 26 [Ar]3d 4s 3d 4s 3d 3d +2,+3 common
7 2 7 1 7 6
Co 27 [Ar]3d 4s 3d 4s 3d 3d +2,+3
8 2 8 1 8 7
Ni 28 [Ar]3d 4s 3d 4s 3d 3d +2 most stable

Cu 29 [Ar]3d104s1 3d10 3d9 – Full 3d

10 2 10 1 10
Zn 30 [Ar]3d 4s 3d 4s 3d – Not transition

MEMORY TRICK – Exceptions in 3d Series

• Cr (Z=24): [Ar] 3d5 4s1 → Gains half-filled d stability (extra exchange energy)

• Cu (Z=29): [Ar] 3d10 4s1 → Gains completely filled d stability

• Pd (Z=46): [Kr] 4d10 5s0 → Only element with NO s-electrons in outer shell

• Rule: When d is about to achieve d5 or d10, one electron shifts from 4s to 3d

PYQ JEE Mains 2020

The electronic configuration of Cu is:
Ans: [Ar] 3d10 4s1 (NOT 3d94s2)

PYQ JEE Mains 2023

When transition metals form ions, which electrons are lost first?
Ans: ns electrons are always lost BEFORE (n-1)d electrons. So Fe → Fe2+: lose both 4s first.

PYQ JEE Mains Jan 2026 Pattern

Electronic configuration of Cr3+ is:
Ans: [Ar] 3d3 — Remove 4s2 first, then 1 from 3d5
 3. GENERAL PHYSICAL PROPERTIES

3.1 Metallic Properties

All transition metals (except Zn, Cd, Hg, Mn) have typical metallic structures at normal temperatures.

They show: High tensile strength, ductility, malleability, high thermal & electrical conductivity, metallic lustre.

High melting/boiling points: Due to involvement of (n-1)d electrons (in addition to ns) in interatomic metallic
bonding. More unpaired d-electrons = stronger bonding.
Exception: Mn and Zn have low melting points. Zn (lowest enthalpy of atomisation = 126 kJ/mol) because its
3d10 electrons do NOT participate in metallic bonding.

Trend: Melting points rise to maximum at d5 config (middle of series) then fall.

3.2 Atomic & Ionic Radii – Key Trends

Trend Explanation Key Examples

New e- enters d-orbital, poor shielding → nuclear charge felt

Across a period: slight decrease more Sc > Ti > V > Cr... but small variation

3d < 4d (increases) More energy levels filled, larger orbitals Fe < Ru

4d ≈ 5d (nearly same!) Lanthanoid contraction compensates expected increase Zr(160pm) ≈ Hf(159pm)

PYQ JEE Mains 2021

Which pair has nearly identical atomic radii due to lanthanoid contraction?
Ans: Zr and Hf — both 160 pm and 159 pm respectively

3.3 Enthalpy of Atomisation

Definition: Energy required to convert solid metal to gaseous atoms.

Maxima at ~middle of each series (d5) because one unpaired e- per d orbital gives strongest metallic bonding.
Zn has the LOWEST enthalpy of atomisation (126 kJ/mol) in 3d series — 3d10 electrons do not participate in
metallic bonding.

2nd and 3rd d-series have HIGHER enthalpies than 1st series → more frequent metal-metal bonding.
 4. IONISATION ENTHALPIES

Key Features
1. IE increases across the series (L to R) but much LESS steeply than main group elements.

2. Irregular variation due to varying stability of dn configurations.

3. d0, d5, d10 configurations are exceptionally stable → causes irregularities.

4. When d-block elements form ions, ns electrons are lost BEFORE (n-1)d electrons.

Special Cases in 2nd and 3rd Ionisation Enthalpies

Irregularity Element Config Change Reason

Extra stability of half-filled/full-filled d → hard to remove

Unusually HIGH 2nd IE Cr, Cu M+ has d5 or d10 another e-

LOW 2nd IE for Zn Zn Zn+ → Zn2+ removes 4s Gives stable d10 configuration

d5 is extra stable → 3rd IE of Fe is LOW; 3rd IE of Mn is

Break in 3rd IE Fe (vs Mn) Fe2+(d6)→Fe3+(d5) HIGH (d5 → d4)

Mn2+ stable Mn Mn2+ = 3d5 Half-filled d5 gives extra stability

Exchange Energy Concept (Important for JEE)

Exchange energy stabilises states with maximum parallel spins (Hund's rule). Loss of exchange energy =
LOWER stability = HARDER ionisation.

d5 has maximum exchange energy — hence Mn2+(d5) is very stable, Fe3+(d5) is very stable.

No loss of exchange energy at d6 config — Mn+(3d54s1) IE < Cr+(d5)

PYQ JEE Mains 2019

Which of the following has HIGHEST 3rd ionisation enthalpy in 3d series?
Ans: Mn — because Mn2+ has d5 (half-filled, extra stable); removing 3rd e- is very difficult

PYQ JEE Mains 2023

Cr2+ is a strong reducing agent while Mn3+ is a strong oxidising agent, though both have d4 configuration. Why?
Ans: Cr2+(d4) → Cr3+(d3): d3 has half-filled t2g level (stable). Mn3+(d4) → Mn2+(d5): d5 is half-filled (extra
stable). Both changes are favoured.
 5. OXIDATION STATES

Key Rules (NTA loves testing these)

1. Variable oxidation states arise from incomplete filling of d orbitals.

2. Transition metals differ in OS by 1 (e.g., Fe2+, Fe3+), unlike non-transition (differ by 2).

3. Mn (Z=25) shows maximum OS (+2 to +7) — at centre of series with most unpaired electrons.

4. Elements at extremes (Sc, Ti, Cu, Zn) show fewer OS.

5. Maximum OS = sum of s + d electrons (up to Mn group)

6. Highest OS shown in fluorides and oxides only — F and O are strong oxidants.

7. Low OS occur with pi-acceptor ligands: Ni(CO)4 → Ni is 0; Fe(CO)5 → Fe is 0.

Element +1 +2 +3 +4 +5 +6 +7 Most Stable

Sc YES +3 only

Ti YES YES YES +4

V YES YES YES YES +2 to +5

Cr YES YES YES YES +3 (aq)

Mn YES YES YES YES YES YES +2 (aq), +7

Fe YES YES YES +2, +3

Co YES YES +2, +3

Ni YES +2

Cu YES YES +2 (aq), +1

Zn YES +2 only

d-Block vs p-Block: OS Variation in Groups

p-block: Heavier members prefer LOWER OS (inert pair effect).

d-block: OPPOSITE! Heavier members prefer HIGHER OS. Example: Cr(VI) in Group 6 is unstable/strong
oxidant, but Mo(VI) and W(VI) are stable. So MoO3 and WO3 are stable but CrO3 is a strong oxidiser.

PYQ JEE Mains 2020

In the series VO2+ < Cr2O72- < MnO4-, the increasing oxidising power is due to:
Ans: Increasing stability of the lower oxidation state to which they are reduced (V4+, Cr3+, Mn2+ — stability
increases in this order)

PYQ JEE Mains 2022

Which transition metal exhibits only +2 oxidation state?
Ans: Zn — only +2; no variable OS since all d10

PYQ JEE Mains 2024

Highest OS of Mn is +7. Which compound shows this?
Ans: KMnO4 (potassium permanganate) — Mn in +7 state
 6. ELECTRODE POTENTIALS (E° VALUES)

E° (M2+/M) Values – First Row Transition Metals

Element Ti V Cr Mn Fe Co Ni Cu Zn

E°(V) -1.63 -1.18 -0.90 -1.18 -0.44 -0.28 -0.25 +0.34 -0.76

Cu has POSITIVE E° (+0.34V) — most important JEE fact!

Reason: Very high enthalpy of atomisation + low hydration enthalpy. The energy to convert Cu(s) to Cu2+(aq) is
NOT compensated by hydration.

Consequence: Cu CANNOT liberate H2 from dilute acids. Only oxidising acids (HNO3, hot conc. H2SO4) react with
Cu.

Mn, Ni, Zn: E° more negative than expected from general trend.

Mn2+(d5) and Zn2+(d10): Extra stability lowers E° (harder to reduce). Ni: Highest negative hydration enthalpy.

E° (M3+/M2+) Values
Element Sc Ti V Cr Mn Fe Co Zn

E°(V) Very -ve -0.37 -0.26 -0.41 +1.57 +0.77 +1.97 High+ve

Mn3+ and Co3+ are strongest oxidising agents in aqueous solution (high +ve E°(M3+/M2+)).

Ti2+, V2+, Cr2+ are strong reducing agents (very negative E°) — can liberate H2 from dilute acids.

Low E°(M3+/M2+) for Sc: Sc3+ is noble gas config, very stable. Low for V: V2+ has half-filled t2g.
E° for Mn3+/Mn2+ >> Cr3+/Cr2+ and Fe3+/Fe2+ because Mn2+(d5) is very stable; 3rd IE of Mn is very high.

PYQ JEE Mains 2019

Cu does not dissolve in dilute HCl because:
Ans: E°(Cu2+/Cu) = +0.34V is positive; Cu cannot reduce H+ (E°(H+/H2) = 0.00V). Only oxidising acids dissolve
Cu.

PYQ JEE Mains 2025

Among Ti2+, V2+ and Cr2+, which is the best reducing agent?
Ans: Ti2+ (most negative E° = -1.63V); stronger reductant = more negative E°
 7. MAGNETIC PROPERTIES

Types of Magnetic Behaviour

Type Behaviour Cause Examples

Diamagnetic Repelled by field All electrons paired Sc3+(3d0), Zn2+(3d10), Ti4+

Paramagnetic Attracted by field Unpaired electrons Most transition metal ions

Strongly attracted (extreme

Ferromagnetic paramagnetism) Unpaired + domain alignment Fe, Co, Ni (metals)

Spin-Only Magnetic Moment Formula

µ = √[n(n+2)] BM (Bohr magnetons)

where n = number of unpaired electrons
This formula is valid for FIRST ROW transition metal compounds only (orbital angular momentum is
quenched).

Ion Config n (unpaired) µ calc (BM) µ obs (BM)

Sc3+ 3d0 0 0 0
3+ 1
Ti 3d 1 1.73 1.75
2+ 3
V 3d 3 3.87 3.86
2+ 4
Cr 3d 4 4.90 4.80

Mn2+ 3d5 5 5.92 5.96

2+ 6
Fe 3d 4 4.90 5.3-5.5
2+ 7
Co 3d 3 3.87 4.4-5.2
2+ 8
Ni 3d 2 2.84 2.9-3.4

Cu2+ 3d9 1 1.73 1.8-2.2

2+ 10
Zn 3d 0 0 0

PYQ JEE Mains 2021

Calculate the spin-only magnetic moment of Mn2+(aq) ion.
Ans: Mn2+ has 3d5 → 5 unpaired electrons; µ = √(5×7) = √35 = 5.92 BM

PYQ JEE Mains 2023

Which ion has the highest magnetic moment among: Fe3+, Mn2+, Cr3+, Co2+?
Ans: Both Fe3+ and Mn2+ have d5 (5 unpaired) → µ = 5.92 BM (highest)

PYQ JEE Mains Jan 2026 Pattern

Divalent ion of element with Z=27 (Co2+). Spin only magnetic moment?
Ans: Co2+ = 3d7 → 3 unpaired; µ = √(3×5) = √15 = 3.87 BM
 8. COLOURED IONS

Cause of Colour: d-d transition — electron excited from lower energy d orbital to higher energy d orbital. Energy
absorbed falls in visible region.

Colour observed = complementary colour of light absorbed.

Frequency (and hence colour) depends on the nature of the ligand in the complex.
Colourless ions: Those with d0 (Sc3+, Ti4+) or d10 (Zn2+, Cu+) — NO d-d transition possible.

Ion Config Colour Ion Config Colour

Sc3+ 3d0 Colourless Fe2+ 3d6 Green

Ti4+ 3d0 Colourless Fe3+ 3d5 Yellow

Ti3+ 3d1 Purple Co2+ 3d7 Pink

V4+ 3d1 Blue Co3+ 3d6 Blue

V3+ 3d2 Green Ni2+ 3d8 Green

V2+ 3d3 Violet Cu2+ 3d9 Blue

Cr3+ 3d3 Violet Cu+ 3d10 Colourless

Mn3+ 3d4 Violet Zn2+ 3d10 Colourless

Mn2+ 3d5 Pink Cr2+ 3d4 Blue

PYQ JEE Mains 2022

Which of the following ions will be colourless in aqueous solution? Cu+, Cu2+, Sc3+, Ti3+
Ans: Cu+ (3d10) and Sc3+ (3d0) are colourless — no d-d transition possible

PYQ JEE Mains 2024

Mn2+(aq) solution appears pink because of:
Ans: d-d transitions in 3d5 configuration of Mn2+; energy of transition corresponds to pink/pale red light
absorbed
 9. IMPORTANT COMPOUNDS — K2Cr2O7 & KMnO4

9.1 Potassium Dichromate (K2Cr2O7)

Preparation:

Step 1: 4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2 (fusion with Na2CO3 in air)

Step 2: 2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+ + H2O (acidify with H2SO4)

Step 3: Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl (add KCl; K-salt less soluble, crystallises)

Chromate-Dichromate Equilibrium (pH dependent):

2CrO42- + 2H+ ■ Cr2O72- + H2O (acidic medium → orange dichromate)

Cr2O72- + 2OH- → 2CrO42- + H2O (alkaline medium → yellow chromate)

Chromium OS in both = +6 — no change in oxidation state!

Structure:

CrO42-: Tetrahedral. Cr2O72-: Two tetrahedra sharing one corner; Cr-O-Cr angle = 126°

Oxidising Action (acidic medium):

Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O (E° = +1.33V)

Oxidises: I- → I2, Sn2+ → Sn4+, H2S → S, Fe2+ → Fe3+

Full example: Cr2O72- + 14H+ + 6Fe2+ → 2Cr3+ + 6Fe3+ + 7H2O

Use: Primary standard in volumetric analysis (acidimetry).

9.2 Potassium Permanganate (KMnO4)

Preparation:

Step 1: 2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O (fusion with KOH, air/KNO3 as oxidant → dark green
manganate)

Step 2: 3MnO42- + 4H+ → 2MnO4- + MnO2 + 2H2O (disproportionation in acidic/neutral)

Commercial: Electrolytic oxidation of MnO42- → MnO4-

Lab: 2Mn2+ + 5S2O82- + 8H2O → 2MnO4- + 10SO42- + 16H+ (oxidised by peroxodisulphate)

Structure: Tetrahedral (MnO4-). Mn=O bonds via p-orbital overlap with d-orbitals of Mn.

KMnO4 crystals: Dark purple (almost black), isostructural with KClO4, diamagnetic (Mn in +7 = d0).

2KMnO4 → K2MnO4 + MnO2 + O2 (decomposes at 513 K)

KMnO4 Oxidising Reactions (Most Tested!)

Medium Reaction / Half-equation E° (V) Products

Strongly acidic MnO4- + 8H+ + 5e- → Mn2+ + 4H2O +1.52 Mn2+ (colourless/pale pink)

Neutral/faint alk. MnO4- + 4H+ + 3e- → MnO2 + 2H2O +1.69 MnO2 (brown ppt)

Strongly alkaline MnO4- + e- → MnO42- +0.56 MnO42- (green)

 KMnO4 – Important Oxidation Reactions in Acidic Medium

• 10I- + 2MnO4- + 16H+ → 2Mn2+ + 8H2O + 5I2

• 5Fe2+ + MnO4- + 8H+ → Mn2+ + 4H2O + 5Fe3+

• 5C2O42- + 2MnO4- + 16H+ → 2Mn2+ + 8H2O + 10CO2 (requires heating at 333K)

• 5H2S + 2MnO4- + 6H+ → 2Mn2+ + 8H2O + 5S (S precipitates)

• 5SO32- + 2MnO4- + 6H+ → 2Mn2+ + 3H2O + 5SO42-

• 5NO2- + 2MnO4- + 6H+ → 2Mn2+ + 5NO3- + 3H2O

KMnO4 – Reactions in Neutral/Alkaline Medium

• 2MnO4- + H2O + I- → 2MnO2 + 2OH- + IO3- (iodide → iodate)

• 8MnO4- + 3S2O32- + H2O → 8MnO2 + 6SO42- + 2OH- (thiosulphate → sulphate)

• IMPORTANT: Do NOT use HCl in permanganate titrations — HCl gets oxidised to Cl2!

PYQ JEE Mains 2019

In the preparation of KMnO4, MnO2 is fused with KOH and then oxidised. The green intermediate formed is:
Ans: K2MnO4 (potassium manganate) — Mn in +6 state, green coloured

PYQ JEE Mains 2021

KMnO4 reacts with oxalic acid in acidic medium to give products including:
Ans: Mn2+ (Mn reduced from +7 to +2), CO2, H2O. Equation: 5C2O42- + 2MnO4- + 16H+ → 2Mn2+ + 8H2O +
10CO2

PYQ JEE Mains 2024

In the reaction of KMnO4 with FeSO4 in acidic medium, the n-factor of KMnO4 is:
Ans: 5 (Mn goes from +7 to +2, gain of 5 electrons per Mn)

PYQ JEE Mains Jan 2026

Chromate and dichromate ions are interconvertible in aqueous solution. Which statement is correct?
Ans: In acidic medium: chromate → dichromate. In basic medium: dichromate → chromate. The OS of Cr (+6)
does NOT change in this conversion.
 10. CATALYTIC, INTERSTITIAL & ALLOY PROPERTIES

Catalytic Properties
Reason: Ability to adopt multiple oxidation states + form complexes.

Surface catalysis: Reactant molecules bond to surface of metal (via 3d + 4s electrons), increasing concentration
and weakening bonds (lowering activation energy).

Catalyst Process Reaction

V2O5 Contact Process 2SO2 + O2 → 2SO3 (H2SO4 manufacture)

Fe (finely divided) Haber's Process N2 + 3H2 → 2NH3

Ni Catalytic Hydrogenation Oils + H2 → Fats (vanaspati)

PdCl2 Wacker Process CH2=CH2 + O2 → CH3CHO

Fe3+ (ion) Redox catalysis 2I- + S2O82- → I2 + 2SO42-

TiCl4/Al(CH3)3 Ziegler-Natta Polymerisation of ethylene (polyethylene)

Interstitial Compounds
Definition: Formed when small atoms (H, C, N) are trapped inside crystal lattices of metals.

Nature: Non-stoichiometric, neither ionic nor covalent. Examples: TiC, Mn4N, Fe3H, VH0.56, TiH1.7

Properties: (1) High MP (higher than pure metal), (2) Very hard (some borides approach diamond), (3) Retain
metallic conductivity, (4) Chemically inert.

Alloy Formation
Alloys form readily because transition metals have similar atomic radii (within ~15% of each other).

Ferrous alloys: Cr, V, W, Mo, Mn → steel and stainless steel.

With non-transition metals: Brass (Cu-Zn), Bronze (Cu-Sn).

Mischmetall: ~95% lanthanoid + ~5% Fe + traces of S, C, Ca, Al → used in Mg-alloy for bullets, shells, lighter
flints.
 11. f-BLOCK ELEMENTS

11.1 Lanthanoids (4f series)

Elements: La (57) to Lu (71) — 15 elements (La + 14 lanthanoids). General symbol: Ln.

Electronic config: [Xe] 4f0-14 5d0-1 6s2

Common OS: +3 (most stable for all). Irregularly +2 and +4 due to extra stability of f0, f7, f14.
Ce4+: Favoured by noble gas config (f0). Strong oxidant (E° = +1.74V), oxidises water but slowly. Good
analytical reagent.

Eu2+: Formed by losing 2s electrons → f7 config. Strong reductant → goes back to +3.

Yb2+: f14 config → reductant.

Physical: Silvery white soft metals. Tarnish in air. Hardness increases with Z (Sm is steel hard). MP: 1000-1200K
(Sm: 1623K). Good thermal/electrical conductors.

Lanthanoid Contraction — Most Important f-Block Topic!

Definition: Gradual decrease in atomic and ionic radii from La to Lu (despite increasing Z).

Cause: Imperfect shielding of one 4f electron by another (f-electrons shield poorly). As Z increases, effective
nuclear charge felt by outer electrons increases → radius decreases.

Shielding: 4f-4f shielding < d-d shielding (4f orbitals are diffuse, poor mutual shielding).
Consequence 1: 4d ≈ 5d series radii. Zr (160pm) ≈ Hf (159pm) → occur together in nature, hard to separate!

Consequence 2: 2nd and 3rd d-series have very similar physical and chemical properties.

Consequence 3: Density increases from Ti to Cu (metallic radius decreases, mass increases).

Coloured Lanthanoid Ions: Due to f-f transitions (absorption bands narrow because excitation within f level).

La3+(f0) and Lu3+(f14) are COLOURLESS. Ce4+(f0) also colourless.

All other Ln3+ ions are coloured AND paramagnetic (except f0 and f14 types).

Sm3+(f5), Eu3+(f6), Gd3+(f7), Tb3+(f8)... all coloured.

11.2 Actinoids (5f series)

Elements: Ac (89) to Lr (103) — 15 elements (Ac + 14 actinoids).

Electronic config: [Rn] 5f0-14 6d0-2 7s2

All radioactive. Early members have long half-lives; later members can only be prepared in nanogram quantities.

OS: All show +3. Early actinoids (Th-Np) show wide range: Th(+4), Pa(+5), U(+6), Np(+7). Later actinoids behave
more like lanthanoids (+3 dominates).

Why wide OS in actinoids? 5f, 6d and 7s levels have comparable energies — easy to involve different number of
electrons.
5f vs 4f: 5f orbitals are NOT as buried as 4f → 5f electrons can participate in bonding more. Hence actinoids
can form bonds using 5f electrons (unlike lanthanoids).

Actinoid contraction > lanthanoid contraction (per element) because 5f electrons provide even poorer shielding
than 4f.
Lanthanoids vs Actinoids — Comparison Table
Property Lanthanoids Actinoids

f orbital filled 4f (more buried) 5f (less buried, can bond)

OS range Mainly +3; rarely +2, +4 +3 to +7 (early); mainly +3 (later)

Radioactivity Non-radioactive (mostly) ALL radioactive

Contraction Lanthanoid contraction Actinoid contraction (GREATER per element)

Colour Many coloured (f-f transitions) Many coloured; more complex magnetic behaviour

Complex formation Less tendency Greater tendency (5f can bond)

Chemistry Smooth, predictable Complex, uneven (especially early members)

Separation Very difficult (similar properties) Difficult but some differences exist

IE Higher (4f buried) Lower (early members) — 5f easier to remove

PYQ JEE Mains 2020

Lanthanoid contraction is caused by:
Ans: Imperfect/poor shielding of one 4f electron by another 4f electron from increasing nuclear charge

PYQ JEE Mains 2022

Actinoid contraction is GREATER than lanthanoid contraction because:
Ans: 5f electrons provide even poorer shielding from nuclear charge compared to 4f electrons

PYQ JEE Mains 2025

Which lanthanoid exhibits +4 oxidation state and why?
Ans: Cerium (Ce, Z=58) — Ce4+ has f0 configuration (noble gas config), extra stability

PYQ JEE Mains 2024

The last element of actinoid series is:
Ans: Lawrencium (Lr, Z=103); config = [Rn] 5f14 6d1 7s2; shows +3 OS (stable)
 12. DISPROPORTIONATION & Cu+ INSTABILITY

Disproportionation: When a particular OS becomes less stable relative to other OS (one lower, one higher), it
spontaneously converts to those two states.

Example 1: Mn(VI) in acidic solution: 3MnO42- + 4H+ → 2MnO4- + MnO2 + 2H2O

Example 2: Cu(I) in aqueous solution: 2Cu+(aq) → Cu2+(aq) + Cu(s) [E° for this is favourable]

Why is Cu+ unstable in water? The hydration enthalpy of Cu2+ is MUCH more negative than Cu+, which more
than compensates for the higher 2nd IE of Cu. So Cu2+ is thermodynamically preferred over Cu+ in aqueous
solution.
Note: CuI compounds are stable in solid state and with non-polar ligands; Cu+ disproportionates only in
aqueous solution.

PYQ JEE Mains 2023

Cu2+ is more stable in aqueous solution than Cu+. Reason:
Ans: Hydration enthalpy of Cu2+ is much more negative than Cu+, which more than compensates for the
higher 2nd ionisation enthalpy of Cu.
 13. NTA PATTERN ANALYSIS 2019–2026

Topic-wise Frequency of Questions in JEE Mains

Topic 2019 2020 2021 2022 2023 2024 2025 Jan26 Total

Oxidation states 1 1 1 2 1 1 1 1 9

KMnO4 / K2Cr2O7 1 1 1 1 1 2 1 1 9

Electronic config exceptions 1 1 1 1 1 1 1 1 8

Magnetic moment 1 0 1 1 1 1 1 1 7

Electrode potentials 1 1 0 1 1 1 1 1 7

Lanthanoid contraction 0 1 0 1 1 0 1 1 5

Coloured ions 0 0 1 1 0 1 1 0 4

Catalytic properties 0 1 0 0 1 1 0 0 3

Actinoids 0 0 0 1 0 1 1 0 3

Interstitial/Alloys 0 0 1 0 0 0 0 1 2

NTA Key Observations (Based on Pattern Analysis)

• Highest priority: Oxidation states + KMnO4/K2Cr2O7 chemistry — almost GUARANTEED every attempt

• Electronic configurations (Cr, Cu exceptions) asked every year — memorise these

• Magnetic moment calculations — numerical type (Integer/Decimal questions common)

• Electrode potential comparisons (Cu+ positive E°, Cu+ vs Cu2+ stability)

• Jan 2026 shift: More conceptual reasoning, less formula-based; statement-type questions increasing

• Lanthanoid contraction consequences (Zr/Hf pair) — popular in Jan shift

• Assertion-Reason type questions increasing since 2022

 14. ASSERTION-REASON QUESTION BANK (April 2026)

Standard Answer Choices:

(A) Both A and R are true, and R is the correct explanation of A

(B) Both A and R are true, but R is NOT the correct explanation of A

(C) A is true but R is false

(D) A is false but R is true

ASSERTION-REASON TYPE

Assertion (A): Cu cannot displace H2 from dilute HCl.

Reason (R): E° (Cu2+/Cu) = +0.34V which is positive.

Correct Answer: (A) — Both true. Positive E° means Cu is less reactive than H+; it cannot reduce H+ to H2.
Topic: Electronic config & electrode potentials

ASSERTION-REASON TYPE

Assertion (A): Cr has electronic configuration [Ar] 3d5 4s1 and not [Ar] 3d4 4s2.

Reason (R): Half-filled d orbitals (d5) have extra stability due to symmetrical distribution and maximum exchange
energy.
Correct Answer: (A) — Both true. R correctly explains A.
Topic: Electronic configurations

ASSERTION-REASON TYPE

Assertion (A): Zn is not considered a transition element.

Reason (R): Zn2+ has completely filled d10 configuration, not an incomplete d subshell.
Correct Answer: (A) — Both true. R correctly explains A. (IUPAC definition: incomplete d in neutral or common
ion required)
Topic: Definition of transition elements

ASSERTION-REASON TYPE

Assertion (A): Mn2+ compounds are more stable than Fe2+ compounds towards oxidation to +3 state.

Reason (R): Mn2+ has 3d5 (half-filled, extra stable) while Fe2+ has 3d6.
Correct Answer: (A) — Both true. R correctly explains A. Fe3+ has 3d5 (stable), so Fe2+→Fe3+ is easier.
Topic: Stability of oxidation states

ASSERTION-REASON TYPE

Assertion (A): KMnO4 is a stronger oxidising agent in acidic medium than in alkaline medium.

Reason (R): In acidic medium, MnO4- gains 5e- (Mn: +7→+2); in alkaline, only 1e- (Mn: +7→+6).
Correct Answer: (A) — Both true. R correctly explains A. E°acid (+1.52V) > E°alk (+0.56V).
Topic: KMnO4 reactions
ASSERTION-REASON TYPE

Assertion (A): Cu+ ion is unstable in aqueous solution and undergoes disproportionation.

Reason (R): The hydration enthalpy of Cu2+ is much more negative than that of Cu+.
Correct Answer: (A) — Both true. R correctly explains A. More negative hydration enthalpy of Cu2+ drives the
disproportionation.
Topic: Disproportionation

ASSERTION-REASON TYPE

Assertion (A): Transition metals generally form coloured compounds.

Reason (R): Transition metals have partially filled d orbitals which allow d-d electronic transitions in the visible
region.
Correct Answer: (A) — Both true. R correctly explains A.
Topic: Coloured ions

ASSERTION-REASON TYPE

Assertion (A): Zr and Hf have nearly identical atomic radii (160 pm and 159 pm).

Reason (R): The filling of 4f orbitals before 5d in lanthanoids causes a regular decrease in atomic radii called
lanthanoid contraction.
Correct Answer: (A) — Both true. R correctly explains A. Lanthanoid contraction compensates expected
increase from Zr to Hf.
Topic: Lanthanoid contraction

ASSERTION-REASON TYPE

Assertion (A): Actinoid contraction is greater per element than lanthanoid contraction.

Reason (R): 5f electrons provide poorer shielding from nuclear charge than 4f electrons.
Correct Answer: (A) — Both true. R correctly explains A.
Topic: Actinoid contraction

ASSERTION-REASON TYPE

Assertion (A): Mn shows the maximum number of oxidation states (+2 to +7) in the first transition series.

Reason (R): Mn (Z=25) has the maximum number of unpaired electrons (5) available in its neutral atom.
Correct Answer: (A) — Both true. R correctly explains A. All 3d and 4s electrons can be involved.
Topic: Oxidation states

ASSERTION-REASON TYPE

Assertion (A): Sc3+ and Zn2+ solutions are colourless.

Reason (R): Both Sc3+ (3d0) and Zn2+ (3d10) have no partially filled d orbitals, so d-d transitions are not possible.
Correct Answer: (A) — Both true. R correctly explains A.
Topic: Coloured ions
ASSERTION-REASON TYPE

Assertion (A): Ti2+, V2+ and Cr2+ can liberate H2 from dilute acids.

Reason (R): These ions have very negative standard electrode potentials (E°).
Correct Answer: (A) — Both true. R correctly explains A. More negative E° = stronger reducing agent.
Topic: Chemical reactivity

ASSERTION-REASON TYPE

Assertion (A): Chromate and dichromate ions have the same oxidation state for chromium.

Reason (R): CrO42- and Cr2O72- are interconvertible by changing pH and this involves change in oxidation state.
Correct Answer: (C) — A is true (Cr is +6 in both), but R is FALSE (the interconversion does NOT involve
change in OS).
Topic: K2Cr2O7 chemistry

ASSERTION-REASON TYPE

Assertion (A): Enthalpies of atomisation of transition metals are high.

Reason (R): Transition metals use d electrons (along with s electrons) in metallic bonding, and large number of
unpaired d electrons lead to stronger bonds.
Correct Answer: (A) — Both true. R correctly explains A.
Topic: Physical properties

ASSERTION-REASON TYPE

Assertion (A): In p-block, heavier elements prefer lower oxidation states, but in d-block, heavier elements prefer
higher oxidation states.

Reason (R): In p-block, inert pair effect operates, while in d-block the opposite trend (stabilisation of higher OS) is
observed.
Correct Answer: (A) — Both true. R correctly explains A. Example: Cr(VI) unstable, Mo(VI)/W(VI) stable.
Topic: Oxidation states - group trend

ASSERTION-REASON TYPE

Assertion (A): Ce4+ is a good oxidising agent.

Reason (R): Ce4+ has f0 configuration (noble gas) and readily accepts electrons to revert to Ce3+(f1).
Correct Answer: (C) — A is true. But R is partially incorrect: Ce3+ has f1 not noble gas, and Ce4+ is strong
oxidant because it reverts to more stable Ce3+. The REAL reason is Ce3+ is very stable. Ans: (B) both true but
R is not exact correct explanation.
Topic: Lanthanoids - oxidation states

ASSERTION-REASON TYPE

Assertion (A): KMnO4 decomposes on heating.

Reason (R): 2KMnO4 → K2MnO4 + MnO2 + O2 at 513K

Correct Answer: (A) — Both true. R correctly explains A.
Topic: KMnO4 properties
ASSERTION-REASON TYPE

Assertion (A): In the ferrous alloys, transition metals like Cr, V, W are added to iron.

Reason (R): These metals have similar atomic radii to Fe and form homogeneous solid solutions.
Correct Answer: (A) — Both true. R correctly explains A. Atomic radii within 15% of each other.
Topic: Alloy formation
 15. QUICK REVISION — MUST-KNOW FACTS

Key Numerical Values (JEE Favourite)

Quantity Value Element/Ion Significance

Lowest enthalpy of atomisation 126 kJ/mol Zn 3d10 not in metallic bonding

E°(Cu2+/Cu) +0.34 V Cu Only positive E° in 3d series → noble behaviour

E°(Mn3+/Mn2+) +1.57 V Mn Mn2+(d5) very stable; Mn3+ strong oxidant

E°(Co3+/Co2+) +1.97 V Co Co3+ strong oxidant; Co2+ stable in water

E° Cr2O72- in acid +1.33 V Cr2O72- Strong oxidant in acidic medium

Cr-O-Cr bond angle 126° Cr2O72- Two tetrahedra sharing one corner

µ for Mn2+(d5) 5.92 BM Mn2+, Fe3+ Maximum spin-only µ in 3d series

6.4 g/100g
KMnO4 solubility water KMnO4 Low solubility; decomposes at 513 K

Zr atomic radius 160 pm Zr Nearly same as Hf (159 pm) — lanthanoid contraction

Eu E°(Ln3+/Ln) -2.0 V Eu Less negative than others (-2.2 to -2.4V)

Ce4+/Ce3+ E° +1.74 V Ce Can oxidise water (but kinetically slow)

Oxides of 3d Metals — Key Points

Highest OS in oxides matches group number (Sc2O3 to Mn2O7)

Beyond Group 7: No oxide of Fe above Fe2O3 (FeO4)2- in alkaline only, decomposes)

As OS increases: ionic character decreases; acidic character predominates

Mn2O7 = covalent green oil; CrO3 = low MP; V2O5 = amphoteric (mainly acidic)

CrO3 gives H2CrO4 and H2Cr2O7; Mn2O7 gives HMnO4

Common Mistakes to Avoid in JEE

1. Cr config is 3d5 4s1 NOT 3d4 4s2 — always write the exception correctly!

2. When forming ions: REMOVE ns FIRST, then (n-1)d. Fe2+ = 3d6 (NOT 3d4 4s2 minus... wrong approach)

3. Zn is NOT a transition element — d10 in both ground state AND Zn2+

4. Colourless means d0 or d10 — Cu+ is colourless (d10), Cu2+ is blue (d9)

5. In Cr2O72- ■ CrO42- equilibrium, OS of Cr does NOT change (stays +6)

6. KMnO4 is diamagnetic — Mn is +7 = d0, no unpaired electrons!

7. Permanganate titrations CANNOT use HCl — HCl itself gets oxidised to Cl2

8. Lanthanoid contraction: Zr/Hf similar, NOT Zr/Nb or similar groups

9. Higher OS more stable in HEAVIER d-block members (opposite of p-block inert pair effect)

10. µ = sqrt[n(n+2)] is SPIN-ONLY formula — valid only for first row transition metal compounds
Last-Minute Revision Checklist (April 2026)

• Cr = [Ar]3d5 4s1 ; Cu = [Ar]3d10 4s1 ; Pd = [Kr]4d10 5s0

• Mn: highest OS range (+2 to +7) in 3d series

• Cu: only POSITIVE E° in 3d series (+0.34V) → does NOT dissolve in dilute acids

• Mn2+/Fe3+ (both d5): extra stability → Mn3+ is strong oxidant, Fe3+ is stable

• Cr2O72- in acid + 6e- → 2Cr3+ + 7H2O (E° = +1.33V)

• MnO4- + 8H+ + 5e- → Mn2+ + 4H2O (E° = +1.52V)

• µ formula: sqrt[n(n+2)]; Mn2+ = 5.92 BM (maximum for 3d)

• Zr (160pm) ≈ Hf (159pm): consequence of lanthanoid contraction

• Lanthanoid contraction: poor shielding of 4f by 4f electrons

• Actinoid contraction > lanthanoid contraction: 5f shields even worse than 4f

• Ce4+: f0 config, strong oxidant (E° = +1.74V). Eu2+: f7, reducing agent.

• KMnO4 is dark purple (almost black), diamagnetic crystals

• Mischmetall = 95% Ln + 5% Fe (lighter flint alloy)

• V2O5 (Contact process), Fe (Haber), Ni (hydrogenation), PdCl2 (Wacker)

 16. HALIDES & OXIDES SUMMARY + MISCELLANEOUS
FACTS

Key Facts About Halides

Highest OS in halides: TiX4, VF5, CrF6 (+6 state)

+7 state for Mn NOT in simple halides; but MnO3F is known.

Beyond Mn: no trihalide except FeX3 and CoF3.

Fluorine stabilises HIGHEST OS: due to higher lattice energy (e.g., CoF3) or higher bond enthalpy (e.g., VF5,
CrF6).

Cu2I2 (CuI): Cu2+ CANNOT exist with I- → Cu2+ oxidises I- to I2: 2Cu2+ + 4I- → Cu2I2 + I2

All Cu2+ halides known EXCEPT CuI2. All CuX (Cu+halides): CuCl, CuBr, CuI — stable.

Fluorides UNSTABLE in low OS: VX2 (X=Cl, Br, I) → VF2 less stable; fluorine prefers high OS.

Applications of d and f Block Elements

Element/Compound Application

Fe, Cr, Mn, V (alloys) Steels and stainless steel (structural materials)

TiO2 Pigment industry (white paint)

MnO2 Dry battery cells (depolariser)

Zn, Ni/Cd Battery industry

AgBr Photographic industry (light-sensitive)

Ag, Au Coinage metals (restricted now to collection items)

Th, Pa, U (actinoids) Nuclear energy (fuel for nuclear reactors)

Lanthanoid oxides Phosphors in TV screens and fluorescent surfaces

Mixed Ln oxides Catalysts in petroleum cracking

Mischmetall Lighter flints; Mg-based alloy for bullets, shells

PYQ JEE Mains 2024

Which catalyst is used in Ziegler-Natta polymerisation?
Ans: TiCl4 with Al(CH3)3 — used to manufacture polyethylene

PYQ JEE Mains 2025

Which of the following statements about interstitial compounds is INCORRECT?
Ans: They are stoichiometric (WRONG) — interstitial compounds are NON-stoichiometric

d & f Block Elements | JEE Mains Notes | Based on NCERT + NTA Pattern 2019-2026