Class 12 Chemistry

Unit 8: The d- and f-Block Elements

Complete Notes with CBSE PYQs | Full Marks Edition
1. INTRODUCTION & POSITION IN PERIODIC TABLE
1.1 d-Block Elements
• d-Block occupies groups 3–12 in the periodic table
• d-orbitals of penultimate (n–1) energy level are progressively filled
• Three well-recognised series: 3d (Sc–Zn), 4d (Y–Cd), 5d (La–Hg omitting Ce–Lu)
• Fourth 6d series (starts at Ac) is still incomplete
• Also called Transition Metals (because they bridge s- and p-block)

1.2 f-Block Elements

• 4f and 5f orbitals are progressively filled in the two long periods
• Formally belong to Group 3 but placed separately as f-block
• Also called Inner Transition Metals
• 4f series = Lanthanoids (La to Lu, elements 57–71)
• 5f series = Actinoids (Ac to Lr, elements 89–103)

1.3 Definition of Transition Element

• Strict definition: element with incompletely filled d-orbitals in ground state OR in any common
oxidation state
• Zn, Cd, Hg (Group 12) have d¹⁰ in ground state AND in common oxidation states → NOT considered
transition metals
• However, studied along with transition metals as end members of respective series
⁰Scandium (3d¹) is a transition element; Zinc (3d¹⁰) is not — because Zn's d-orbitals are
completely filled in ground state as well as in Zn²⁺ state.

⭐ CBSE PYQ: Why are Zn, Cd and Hg not regarded as transition elements? (CBSE 2020,
2018, 2016)
Ans: Zn, Cd and Hg have completely filled d¹⁰ configuration in their ground state as well as in their
common oxidation states (M²⁺). Since d-orbitals are always fully filled, they do not satisfy the
definition of a transition element (which requires incompletely filled d-orbitals). Hence they are
excluded.

⭐ CBSE PYQ: On what ground can you say that scandium (Z=21) is a transition element but
zinc (Z=30) is not? (CBSE 2019)
Ans: Scandium (3d¹4s²) has one electron in 3d orbital, which is incompletely filled — hence it is a
transition element. Zinc (3d¹⁰4s²) has completely filled 3d¹⁰ orbitals in ground state as well as in
Zn²⁺ state (3d¹⁰) — hence not a transition element.

2. ELECTRONIC CONFIGURATION
2.1 General Formula
• General configuration: (n-1)d¹⁻¹⁰ ns¹⁻²
• (n-1) = inner d orbitals (1 to 10 electrons); ns = outermost s orbital (1 or 2 electrons)
• Exceptions exist due to very little energy difference between (n-1)d and ns orbitals
• Half-filled and completely filled orbitals are more stable (exchange energy stability)
2.2 Important Exceptions in 3d Series
• Chromium (Cr, Z=24): 3d⁵4s¹ (NOT 3d⁴4s²) — half-filled 3d is more stable
• Copper (Cu, Z=29): 3d¹⁰4s¹ (NOT 3d⁹4s²) — completely filled 3d is more stable

2.3 Series-wise Key Configurations

• 1st series (3d): Sc(3d¹4s²) to Zn(3d¹⁰4s²)
• 2nd series (4d): Y(4d¹5s²) to Cd(4d¹⁰5s²) — many exceptions e.g., Pd: 4d¹⁰5s⁰
• 3rd series (5d): La(5d¹6s²) to Hg(5d¹⁰6s²)
• Zn, Cd, Hg: configuration (n-1)d¹⁰ns² — completely filled, hence not transition metals

⁺CBSE PYQ: Write the electronic configuration of Cr³⁺ and Cu⁺. (CBSE 2020, 2017)
Ans: Cr (Z=24): [Ar]3d⁵4s¹. Cr³⁺: removes 3 electrons (from 4s first, then 3d) → [Ar]3d³. Cu
(Z=29): [Ar]3d¹⁰4s¹. Cu⁺: removes 1 electron from 4s → [Ar]3d¹⁰.

⭐ CBSE PYQ: Why does Cr have the configuration 3d⁵4s¹ instead of 3d⁴4s²? (CBSE 2018)
Ans: Half-filled d orbitals (3d⁵) have extra stability due to symmetrical distribution of electrons and
maximum exchange energy. The energy difference between 3d and 4s is small enough that one
electron shifts from 4s to 3d to achieve this stable half-filled configuration.

3. GENERAL PROPERTIES OF d-BLOCK ELEMENTS

3.1 Physical Properties
• Typical metallic properties: high tensile strength, ductility, malleability, high thermal and electrical
conductivity, metallic lustre
• High melting and boiling points (exceptions: Zn, Cd, Hg, Mn have atypical structures)
• High melting points due to: involvement of (n-1)d electrons along with ns electrons in interatomic
metallic bonding
• In any row, melting points rise to maximum at d⁵ (except anomalous Mn and Tc), then decrease
• High enthalpies of atomisation (maxima near middle of series — one unpaired electron per d orbital is
most favourable)
• Metals of 2nd and 3rd series have greater enthalpies of atomisation than 1st series — explains more
frequent metal–metal bonding in heavier transition metals
• Density increases from Ti to Cu due to decrease in metallic radius and increase in atomic mass

⭐ CBSE PYQ: Why do transition elements have high enthalpies of atomisation? (CBSE
2019, 2016)
Ans: Transition elements have a large number of unpaired electrons in (n-1)d orbitals. These
contribute to stronger interatomic metallic bonding (in addition to ns electrons). Greater number of
unpaired electrons → stronger bonding → higher enthalpy of atomisation. The maxima occur near
middle of series (d⁵ configuration — one unpaired electron per orbital).

⭐ CBSE PYQ: Why is the enthalpy of atomisation of zinc the lowest (126 kJ/mol) in the 3d
series? (CBSE 2018, 2020)
Ans: In Zn (3d¹⁰4s²), all 3d orbitals are completely filled. No d electrons are available for metallic
bonding — only 4s electrons contribute. This results in weak interatomic bonding and hence the
lowest enthalpy of atomisation in the series.
3.2 Atomic and Ionic Radii (Lanthanoid Contraction)
• In a given series: ionic radii of same charge decrease with increasing atomic number
• New electron enters d orbital but shielding by d electrons is poor → net nuclear attraction increases →
radius decreases
• Variation within a series is small (d electrons shield poorly)
• From 1st (3d) to 2nd (4d) series: radii increase
• From 2nd (4d) to 3rd (5d) series: radii virtually the SAME — due to Lanthanoid Contraction
• Lanthanoid Contraction: The regular decrease in size of lanthanoid atoms/ions (La to Lu) due to
poor shielding of 4f electrons from each other as nuclear charge increases
• Shielding by 4f electrons is LESS effective than by d electrons → greater net nuclear pull → steady
decrease in size
• Net result: Zr (160 pm) ≈ Hf (159 pm) → same period 4d and 5d elements have nearly identical radii
→ similar physical and chemical properties
📌 Consequence of Lanthanoid Contraction: (1) 4d and 5d elements in same group have similar
properties. (2) Difficult to separate Zr and Hf. (3) Elements after lanthanoids are denser and less
reactive than expected.

⭐ CBSE PYQ: What is lanthanoid contraction? What are its consequences? (CBSE 2020,
2019, 2017, 2015)
Ans: Lanthanoid contraction is the steady decrease in atomic and ionic radii of lanthanoid
elements from La to Lu (Z=57 to Z=71). It occurs because 4f electrons shield each other very
poorly. As nuclear charge increases across the series, the effective nuclear charge felt by outer
electrons increases progressively, causing a gradual but steady decrease in size. Consequences:
(1) Elements of 2nd and 3rd transition series in same group have very similar radii (e.g., Zr 160
pm, Hf 159 pm) and hence similar properties. (2) Very difficult to separate these pairs (e.g., Zr/Hf,
Nb/Ta). (3) Density of 5d elements is higher than expected.

3.3 Ionisation Enthalpies

• General trend: ionisation enthalpy increases from left to right across a series (due to increasing
nuclear charge)
• Successive enthalpies do NOT increase as steeply as in main group elements
• Irregular variations due to varying stability of d configurations (d⁰, d⁵, d¹⁰ are extra stable)
• Cr (first IE): lower than expected — removal of electron from 3d⁵ without disrupting the configuration
• Zn (first IE): higher than expected — electron removed from 4s level
• Second IE: unusually high for Cr and Cu — disruption of d⁵ and d¹⁰ configurations of M⁺ ions
• Third IE: very high for all; marked break between Mn²⁺ (d⁵) and Fe²⁺ — d⁵ stability of Mn²⁺
• High third IEs for Cu, Ni, Zn explain why they do not easily show oxidation state > +2

⭐ CBSE PYQ: Explain irregular variation of first and second ionisation enthalpies in 3d
transition series. (CBSE 2018, 2016)
Ans: The irregular variation is due to varying stability of different 3d configurations. Configurations
d⁰, d⁵ and d¹⁰ are exceptionally stable due to symmetrical electron distribution and maximum
exchange energy. Thus: (1) Cr has lower first IE than expected because removal of one electron
maintains the stable d⁵ configuration. (2) Zn has higher first IE because electron is removed from
the 4s level, not 3d. (3) The second IE of Cr and Cu is abnormally high because disruption of d⁵
and d¹⁰ configurations of M⁺ involves loss of extra stability (exchange energy).
4. OXIDATION STATES
4.1 Variable Oxidation States — Key Points
• Most characteristic feature of transition metals — exhibit wide variety of oxidation states
• Arises because both (n-1)d and ns electrons can participate in bonding
• Oxidation states differ by a unit of ONE (e.g., V²⁺, V³⁺, V⁴⁺, V⁵⁺) — unlike main group (differ by 2)
• Elements near the MIDDLE of series (e.g., Mn) show maximum number of oxidation states
• Mn shows +2 to +7 — ALL oxidation states from 2 to 7
• Sc (too few d electrons) — only +3; Zn (too many d electrons, d¹⁰) — only +2

4.2 Stability Trends

• Maximum oxidation state = sum of s and d electrons (up to Mn)
• TiO₂ (+4), VO₂⁺ (+5), CrO₄²⁻ (+6), MnO₄⁻ (+7) — all correspond to group number
• After Mn: abrupt decrease in stability of higher oxidation states → Fe(II,III), Co(II,III), Ni(II), Cu(I,II),
Zn(II)
• In d-block groups: HEAVIER members show MORE stable higher oxidation states (opposite to p-
block inert pair effect)
• Example: Mo(VI) and W(VI) more stable than Cr(VI); CrVI is a strong oxidant, but MoO₃ and WO₃ are
not
• Low oxidation states found in complexes with π-acceptor ligands (e.g., Ni(CO)₄ — Ni is 0; Fe(CO)₅
— Fe is 0)

⭐ CBSE PYQ: Name a transition element which does NOT exhibit variable oxidation states.
Why? (CBSE 2019, 2017)
Ans: Scandium (Sc, Z=21) does not exhibit variable oxidation states. It only shows +3 state
because after losing 3 electrons (4s² and 3d¹), it acquires the stable noble gas (Ar) configuration. It
has too few d electrons to show lower states, and further ionisation requires very high energy.

⭐ CBSE PYQ: Why does Mn exhibit the greatest number of oxidation states in the first
transition series? (CBSE 2020, 2018)
Ans: Manganese (Z=25, 3d⁵4s²) is near the middle of the 3d series and has the maximum number
of unpaired electrons (7 total — 5 in 3d and 2 in 4s). All these electrons can potentially participate
in bonding. Hence Mn shows all oxidation states from +2 to +7, the widest range in the first
transition series.

⭐ CBSE PYQ: The variability of oxidation states of transition metals differs from that of
non-transition metals. Explain. (CBSE 2016)
Ans: In transition metals: (1) Both (n-1)d and ns electrons participate in bonding. (2) The energy
difference between successive oxidation states is small. (3) Oxidation states differ by ONE (e.g.,
Fe²⁺, Fe³⁺). In non-transition metals (p-block): (1) Only ns electrons typically participate. (2)
Oxidation states differ by TWO (inert pair effect) e.g., Sn²⁺ and Sn⁴⁺, Pb²⁺ and Pb⁴⁺.

⁺CBSE PYQ: Why is Cr²⁺ a reducing agent while Mn³⁺ is an oxidising agent, though both
have d⁴ configuration? (CBSE 2020, 2018, 2015)
Ans: Cr²⁺ (d⁴) acts as reducing agent because it tends to lose one more electron to form Cr³⁺ (d³),
which has a half-filled t₂g level (extra stability). This transformation (d⁴ → d³) is energetically
favourable, hence Cr²⁺ is a good reducing agent. Mn³⁺ (d⁴) acts as oxidising agent because it
tends to gain one electron to form Mn²⁺ (d⁵), which has extra stability (half-filled d subshell). This
transformation (d⁴ → d⁵) is energetically favourable.
5. STANDARD ELECTRODE POTENTIALS
5.1 M²⁺/M Electrode Potentials
• General trend: E° values become less negative across the series (left to right) — related to increase in
first and second ionisation enthalpies
• Cu has POSITIVE E° (+0.34 V) — unique among first row transition metals
• Cu cannot liberate H₂ from dilute acids — only oxidising acids (HNO₃, hot conc. H₂SO₄) react with
Cu
• High enthalpy of atomisation of Cu + low hydration enthalpy of Cu²⁺ → overall positive E° value
• E° for Mn, Ni, Zn are MORE negative than expected from general trend
• Mn²⁺ (d⁵ — half-filled, extra stable) and Zn²⁺ (d¹⁰ — fully filled) contribute to their more negative E°
values
• E° for Ni: most negative hydration enthalpy

⁺CBSE PYQ: The E° (M²⁺/M) value for copper is +0.34 V. What is the reason? (CBSE 2019,
2017)
Ans: Copper has a high enthalpy of atomisation (ΔₐH° = 339 kJ/mol) and relatively low hydration
enthalpy of Cu²⁺. The energy required to convert solid Cu to Cu²⁺(aq) is not adequately
compensated by the energy released during hydration. Hence the overall process is not
spontaneous enough, resulting in a positive E° value. This also explains why Cu cannot displace
H₂ from dilute acids.

5.2 M³⁺/M²⁺ Electrode Potentials

• Sc³⁺/Sc²⁺ — very low E° (Sc³⁺ has noble gas configuration, extremely stable)
• Zn²⁺/Zn⁺ — very high E° (disrupts stable d¹⁰ of Zn²⁺)
• Mn³⁺/Mn²⁺ — high positive E° (+1.57 V) — Mn²⁺ is d⁵, particularly stable
• Fe³⁺/Fe²⁺ — comparatively low (+0.77 V) — Fe³⁺ is d⁵, extra stable
• V²⁺/V³⁺ — low value related to stability of V²⁺ (half-filled t₂g)
• Mn³⁺ and Co³⁺ are strongest oxidising agents in aqueous solution
• Ti²⁺, V²⁺, Cr²⁺ are strong reducing agents — liberate H₂ from dilute acids

⁺CBSE PYQ: Why is Mn³⁺/Mn²⁺ E° value much more positive than Cr³⁺/Cr²⁺ or Fe³⁺/Fe²⁺?
(CBSE 2019, 2018)
Ans: Mn²⁺ has d⁵ configuration (half-filled, extra stable due to maximum exchange energy and
symmetrical distribution). The third ionisation enthalpy of Mn (converting Mn²⁺ to Mn³⁺, i.e., d⁵ →
d⁴) is very high. Hence Mn³⁺ is difficult to form and is a strong oxidising agent. This also explains
why +3 state of Mn has little importance compared to +2 state.

6. MAGNETIC PROPERTIES
• Three types: Diamagnetic (repelled), Paramagnetic (attracted), Ferromagnetic (strongly attracted —
extreme form of paramagnetism)
• Paramagnetism arises from unpaired electrons — each has spin and orbital magnetic moments
• For 1st series transition metals: orbital angular momentum contribution is quenched (negligible)
• Magnetic moment calculated using SPIN-ONLY FORMULA:
μ = √n(n+2) BM (where n = number of unpaired electrons)
• 1 unpaired electron → μ = 1.73 BM
• Magnetic moment INCREASES with increasing unpaired electrons
• Maximum unpaired electrons in Mn²⁺/Fe³⁺ (3d⁵, 5 unpaired) → μ = 5.92 BM
• Zn²⁺ (3d¹⁰, 0 unpaired) → μ = 0 (diamagnetic)
 • Sc³⁺ (3d⁰) → μ = 0 (diamagnetic)

📌 Key μ values: 1 unpaired = 1.73 BM | 2 = 2.84 BM | 3 = 3.87 BM | 4 = 4.90 BM | 5 = 5.92 BM

⁺CBSE PYQ: Calculate the spin-only magnetic moment of Mn²⁺ (Z=25). (CBSE 2020, 2019,
2018)
Ans: Mn (Z=25): [Ar]3d⁵4s². Mn²⁺: loses 2 electrons from 4s → [Ar]3d⁵. 3d⁵ has 5 unpaired
electrons. μ = √n(n+2) = √5(5+2) = √35 = 5.92 BM.

⁺CBSE PYQ: Calculate the spin-only magnetic moment of Co²⁺ (Z=27). (CBSE 2017, 2016)
Ans: Co (Z=27): [Ar]3d⁷4s². Co²⁺: [Ar]3d⁷ (3 unpaired electrons). μ = √3(3+2) = √15 = 3.87 BM.

⁺CBSE PYQ: Calculate the spin-only magnetic moment of Fe²⁺ (Z=26). (CBSE 2020)
Ans: Fe (Z=26): [Ar]3d⁶4s². Fe²⁺: [Ar]3d⁶ (4 unpaired electrons in d⁶). μ = √4(4+2) = √24 = 4.90
BM.

7. FORMATION OF COLOURED IONS

• Transition metal compounds/ions are coloured due to d-d electronic transitions
• When ligands are present, d orbitals split into two energy levels (Crystal Field Splitting)
• An electron from lower d orbital is excited to higher d orbital by absorbing visible light
• Energy of absorbed light = hν, frequency falls in visible region
• Colour observed = complementary colour of light absorbed
• Nature of ligand determines the frequency (and hence colour) of light absorbed
• Ions with d⁰ (Sc³⁺, Ti⁴⁺) or d¹⁰ (Zn²⁺) configurations are COLOURLESS (no d-d transition possible)

⁺Colours: Ti³⁺(d¹)=purple, V²⁺(d³)=violet, Cr³⁺(d³)=violet, Mn²⁺(d⁵)=pink, Fe³⁺(d⁵)=yellow,

Fe²⁺(d⁶)=green, Co²⁺(d⁷)=pink, Ni²⁺(d⁸)=green, Cu²⁺(d⁹)=blue, Zn²⁺(d¹⁰)=colourless

⁺CBSE PYQ: Why do transition metal compounds exhibit colour? Why is Zn²⁺ colourless?
(CBSE 2020, 2019, 2018, 2016)
Ans: Transition metal ions have incompletely filled d orbitals. When ligands (like water) surround
the metal ion, the d orbitals split into two energy levels. An electron absorbs energy from visible
light and moves from lower to higher d level (d-d transition). The colour observed is the
complementary colour of light absorbed. Zn²⁺ has d¹⁰ configuration — all d orbitals are completely
filled, so no d-d transition is possible. Hence Zn²⁺ is colourless.

⁺CBSE PYQ: Which of these will be coloured in aqueous solution? Ti³ ⁺, V³ ⁺, Cu ⁺, Sc³⁺,
Mn²⁺, Fe³⁺, Co²⁺. (CBSE 2018, 2017)
Ans: Coloured: Ti³⁺ (d¹, purple), V³⁺ (d², green), Mn²⁺ (d⁵, pink), Fe³⁺ (d⁵, yellow), Co²⁺ (d⁷, pink).
Not coloured: Cu⁺ (d¹⁰ — fully filled, no d-d transition) and Sc³⁺ (d⁰ — no d electrons, no d-d
transition). All coloured ions have partially filled d orbitals enabling d-d transitions.

8. FORMATION OF COMPLEX COMPOUNDS

• Transition metals form a large number of complex compounds
 • Reasons: (1) Small ionic size → high charge density, (2) High ionic charges, (3) Availability of d
orbitals for bond formation (accepting lone pairs from ligands)
• Examples: [Fe(CN)₆]³⁻, [Fe(CN)₆]⁴⁻, [Cu(NH₃)₄]²⁺, [PtCl₄]²⁻
• Ligands donate electron pairs to central metal ion (Lewis acid-base interaction)

9. CATALYTIC PROPERTIES
• Transition metals and their compounds are important catalysts
• Two reasons: (1) Ability to adopt multiple oxidation states, (2) Ability to form complexes
• Heterogeneous catalysis: reactants adsorb on catalyst surface → bonds weaken → reaction faster →
products released
• V₂O₅: Contact process (SO₂ → SO₃, for H₂SO₄ manufacture)
• Fe (finely divided): Haber's process (N₂ + H₂ → NH₃)
• Ni: Catalytic hydrogenation of oils/fats
• PdCl₂: Wacker process (ethyne → ethanal)
• TiCl₄ + Al(CH₃)₃: Ziegler-Natta catalyst (polyethylene manufacture)
• Fe³⁺: Catalyses reaction between I⁻ and S₂O₈²⁻

⭐ CBSE PYQ: Why do transition metals act as good catalysts? (CBSE 2019, 2017)
Ans: Transition metals act as good catalysts due to two reasons: (1) Variable oxidation states —
they can form intermediate compounds with reactants in one oxidation state and then return to
original state by releasing products. E.g., Fe³⁺ + 2I⁻ → Fe²⁺ + I₂; Fe²⁺ + S₂O₈²⁻ → Fe³⁺ +
2SO₄²⁻. (2) Ability to adsorb reactants on their surface, increasing concentration and weakening
bonds (lowering activation energy). Both d and s electrons participate in forming bonds with
reactants.

10. INTERSTITIAL COMPOUNDS

• Formed when small atoms (H, C, N) are trapped inside crystal lattices of transition metals
• Generally non-stoichiometric — not typically ionic or covalent
• Examples: TiC, Mn₄N, Fe₃H, VH₀.₅₆, TiH₁.₇
• Formulas don't correspond to normal oxidation state of metal

Properties of Interstitial Compounds

• High melting points — higher than pure metals
• Very hard (some borides approach diamond in hardness)
• Retain metallic conductivity
• Chemically inert

⭐ CBSE PYQ: What are interstitial compounds? Why are they well known for transition
metals? (CBSE 2019, 2018)
Ans: Interstitial compounds are formed when small atoms like H, C, or N are trapped inside the
crystal lattice of transition metals without disrupting the metallic lattice. They are well known for
transition metals because transition metals have large atomic radii and open crystal structures
(bcc, hcp, ccp) with sufficient interstitial spaces to accommodate small atoms. Properties: (1) Very
high melting points. (2) Very hard (some borides ≈ diamond). (3) Retain metallic conductivity. (4)
Chemically inert. Examples: TiC, Mn₄N, Fe₃H.
11. ALLOY FORMATION
• Alloys are homogeneous solid solutions formed by mixing component metals
• Transition metals form alloys readily because they have similar atomic radii (within ~15% of each
other)
• Alloys are hard and have high melting points
• Ferrous alloys (contain iron): Cr, V, W, Mo, Mn used to produce variety of steels and stainless steel
• Alloys with non-transition metals: Brass (Cu-Zn), Bronze (Cu-Sn) — industrially important

12. IMPORTANT COMPOUNDS OF TRANSITION ELEMENTS

12.1 Potassium Dichromate (K₂Cr₂O₇)
Preparation
• Step 1: Fusion of chromite ore (FeCr₂O₄) with Na₂CO₃ in air at high temperature:
4FeCr₂O₄ + 8Na₂CO₃ + 7O₂ → 8Na₂CrO₄ + 2Fe₂O₃ + 8CO₂
• Step 2: Filter yellow Na₂CrO₄ solution; acidify with H₂SO₄:
2Na₂CrO₄ + 2H⁺ → Na₂Cr₂O₇ + 2Na⁺ + H₂O
• Step 3: Treat Na₂Cr₂O₇ with KCl:
Na₂Cr₂O₇ + 2KCl → K₂Cr₂O₇ + 2NaCl
• Orange crystals of K₂Cr₂O₇ crystallise out

Chromate–Dichromate Equilibrium
• Chromate (CrO₄²⁻) and dichromate (Cr₂O₇²⁻) are interconvertible depending on pH
• In acidic medium (add H⁺): chromate → dichromate (orange)
2CrO₄²⁻ + 2H⁺ ⇌ Cr₂O₇²⁻ + H₂O
• In alkaline medium (add OH⁻): dichromate → chromate (yellow)
Cr₂O₇²⁻ + 2OH⁻ ⇌ 2CrO₄²⁻ + H₂O
• Oxidation state of Cr is +6 in BOTH chromate and dichromate
• Structure: CrO₄²⁻ is tetrahedral; Cr₂O₇²⁻ consists of two tetrahedra sharing one corner (Cr–O–Cr
bond angle = 126°)

Oxidising Properties of K₂Cr₂O₇

• Strong oxidising agent, especially in acidic medium
Cr₂O₇²⁻ + 14H⁺ + 6e⁻ → 2Cr³⁺ + 7H₂O (E° = +1.33 V)
• Oxidises iodides to iodine: 6I⁻ → 3I₂ + 6e⁻
• Oxidises Fe²⁺ to Fe³⁺: 6Fe²⁺ → 6Fe³⁺ + 6e⁻
• Oxidises H₂S to S: 3H₂S → 6H⁺ + 3S + 6e⁻
• Oxidises Sn²⁺ to Sn⁴⁺: 3Sn²⁺ → 3Sn⁴⁺ + 6e⁻
• Full ionic equation with Fe²⁺: Cr₂O₇²⁻ + 14H⁺ + 6Fe²⁺ → 2Cr³⁺ + 6Fe³⁺ + 7H₂O
• Used as primary standard in volumetric analysis; used in leather industry and organic synthesis

⭐ CBSE PYQ: Describe preparation of K₂Cr₂O₇ from chromite ore. What is effect of
increasing pH? (CBSE 2020, 2019, 2018, 2017, 2016, 2015)
Ans: Preparation: (1) Fuse FeCr₂O₄ with Na₂CO₃/K₂CO₃ in air: 4FeCr₂O₄ + 8Na₂CO₃ + 7O₂
→ 8Na₂CrO₄ + 2Fe₂O₃ + 8CO₂. (2) Acidify yellow Na₂CrO₄ with H₂SO₄: 2Na₂CrO₄ + 2H⁺ →
Na₂Cr₂O₇ + 2Na⁺ + H₂O. (3) Treat with KCl: Na₂Cr₂O₇ + 2KCl → K₂Cr₂O₇ + 2NaCl. Orange
crystals crystallise out. Effect of increasing pH: As pH increases (solution becomes alkaline),
dichromate (Cr₂O₇²⁻, orange) converts to chromate (CrO₄²⁻, yellow): Cr₂O₇²⁻ + 2OH⁻ ⇌
 2CrO₄²⁻ + H₂O.

12.2 Potassium Permanganate (KMnO₄)

Preparation
• Step 1: Fusion of MnO₂ with KOH and KNO₃ (oxidising agent) — gives dark green K₂MnO₄:
2MnO₂ + 4KOH + O₂ → 2K₂MnO₄ + 2H₂O
• Step 2: Disproportionation of manganate in neutral/acidic solution:
3MnO₄²⁻ + 4H⁺ → 2MnO₄⁻ + MnO₂ + 2H₂O
• Commercially: alkaline oxidative fusion of MnO₂ followed by electrolytic oxidation of MnO₄²⁻ to
MnO₄⁻
• In laboratory: Mn²⁺ + peroxodisulphate (S₂O₈²⁻) → MnO₄⁻

Properties
• Dark purple (almost black) crystals; isostructural with KClO₄
• Sparingly soluble in water (6.4 g/100 g at 293 K)
• Decomposes at 513 K: 2KMnO₄ → K₂MnO₄ + MnO₂ + O₂
• MnO₄⁻ ion is tetrahedral; permanganate is DIAMAGNETIC (despite Mn being in +7 state)
• Manganate (MnO₄²⁻) is paramagnetic with 1 unpaired electron
• π-bonding in MnO₄⁻: overlap of p orbitals of O with d orbitals of Mn

Oxidising Reactions of KMnO₄

In Acidic Solution (MnO₄⁻ → Mn²⁺)

MnO₄⁻ + 8H⁺ + 5e⁻ → Mn²⁺ + 4H₂O (E° = +1.52 V)
• Oxidises I⁻ to I₂: 10I⁻ + 2MnO₄⁻ + 16H⁺ → 2Mn²⁺ + 8H₂O + 5I₂
• Oxidises Fe²⁺ to Fe³⁺: 5Fe²⁺ + MnO₄⁻ + 8H⁺ → Mn²⁺ + 4H₂O + 5Fe³⁺
• Oxidises oxalate to CO₂: 5C₂O₄²⁻ + 2MnO₄⁻ + 16H⁺ → 2Mn²⁺ + 8H₂O + 10CO₂
• Oxidises H₂S: 5S²⁻ + 2MnO₄⁻ + 16H⁺ → 2Mn²⁺ + 8H₂O + 5S
• Oxidises SO₃²⁻ to SO₄²⁻: 5SO₃²⁻ + 2MnO₄⁻ + 6H⁺ → 2Mn²⁺ + 3H₂O + 5SO₄²⁻
• Oxidises NO₂⁻ to NO₃⁻: 5NO₂⁻ + 2MnO₄⁻ + 6H⁺ → 2Mn²⁺ + 5NO₃⁻ + 3H₂O

In Neutral/Faintly Alkaline Solution (MnO₄⁻ → MnO₂)

MnO₄⁻ + 4H⁺ + 3e⁻ → MnO₂ + 2H₂O (E° = +1.69 V)
• Oxidises I⁻ to IO₃⁻: 2MnO₄⁻ + H₂O + I⁻ → 2MnO₂ + 2OH⁻ + IO₃⁻
• Oxidises thiosulphate to sulphate: 8MnO₄⁻ + 3S₂O₃²⁻ + H₂O → 8MnO₂ + 6SO₄²⁻ + 2OH⁻

In Strongly Alkaline Solution (MnO₄⁻ → MnO₄²⁻)

MnO₄⁻ + e⁻ → MnO₄²⁻ (E° = +0.56 V)

📌 Note: Permanganate titrations with HCl are UNSATISFACTORY because HCl is itself oxidised
to Cl₂ by KMnO₄.

⁺CBSE PYQ: Describe preparation of KMnO₄ and its oxidising action with (i) Fe²⁺ ions (ii)
SO₂ (iii) oxalic acid in acidic medium. (CBSE 2020, 2019, 2018, 2017)
Ans: Preparation: (1) Fusion: 2MnO₂ + 4KOH + O₂ → 2K₂MnO₄ + 2H₂O. (2) Disproportionation
in acid: 3MnO₄²⁻ + 4H⁺ → 2MnO₄⁻ + MnO₂ + 2H₂O. OR electrolytic oxidation (commercially).
Oxidising reactions in acid (MnO₄⁻ + 8H⁺ + 5e⁻ → Mn²⁺ + 4H₂O): (i) 5Fe²⁺ + MnO₄⁻ + 8H⁺ →
Mn²⁺ + 4H₂O + 5Fe³⁺. (ii) 5SO₂ + 2MnO₄⁻ + 2H₂O → 2Mn²⁺ + 5SO₄²⁻ + 4H⁺. (iii) 5C₂O₄²⁻ +
2MnO₄⁻ + 16H⁺ → 2Mn²⁺ + 8H₂O + 10CO₂.
13. THE LANTHANOIDS (4f Series)
13.1 Electronic Configuration
• Fourteen elements following Lanthanum (La, Z=57): Ce (58) to Lu (71)
• General symbol: Ln
• All have 6s² common; variable occupancy of 4f level
• All tripositive ions (Ln³⁺) have configuration 4fⁿ (n = 1 to 14)
• La: 5d¹6s² (no 4f electron initially), then 4f fills from Ce onwards
• Gd and Lu have one 5d electron each (due to stability of half-filled and filled 4f)

13.2 Lanthanoid Contraction

• Steady decrease in atomic and ionic radii from La to Lu
• Cause: 4f electrons shield each other very poorly → effective nuclear charge increases → radius
decreases
• Shielding by 4f electrons < shielding by d electrons
• M³⁺ ionic radii decrease regularly from 106 pm (La³⁺) to 86 pm (Yb³⁺)
• Atomic radii decrease is less regular than M³⁺ ionic radii

13.3 Oxidation States

• Principal oxidation state: +3 (most stable for all lanthanoids)
• Occasionally +4 and +2 also observed
• +4 states: Ce⁴⁺ (f⁰, noble gas configuration — favoured), Pr⁴⁺, Nd⁴⁺, Tb⁴⁺, Dy⁴⁺ (only in oxides MO₂)
• Ce⁴⁺ is a strong oxidant (E° for Ce⁴⁺/Ce³⁺ = +1.74 V); used as analytical reagent
• +2 states: Eu²⁺ (f⁷ — half-filled), Yb²⁺ (f¹⁴ — fully filled), Sm²⁺, Tm²⁺
• Eu²⁺ and Yb²⁺ are strong reducing agents (tend to revert to +3)
• Tb⁴⁺ has half-filled f orbitals → acts as oxidant

13.4 General Characteristics

• Silvery white, soft metals that tarnish rapidly in air
• Hardness increases with atomic number (Sm is steel hard)
• Melting points 1000–1200 K (Sm melts at 1623 K)
• Good conductors of heat and electricity
• Earlier members react like Ca; later members behave like Al
• E° values for Ln³⁺/Ln are in range –2.2 to –2.4 V (Eu: –2.0 V)
• Many Ln³⁺ ions are coloured (due to f electrons); absorption bands are narrow (f–f transitions)
• La³⁺ (f⁰) and Lu³⁺ (f¹⁴) are colourless
• All Ln³⁺ ions except f⁰ (La³⁺, Ce⁴⁺) and f¹⁴ (Yb²⁺, Lu³⁺) are paramagnetic
• Paramagnetism maximum in neodymium

13.5 Uses of Lanthanoids

• Production of alloy steels for plates and pipes
• Mischmetall alloy: ~95% lanthanoid metal + ~5% iron + traces of S, C, Ca, Al — used in Mg-based
alloy for bullets, shells, lighter flints
• Mixed lanthanoid oxides as catalysts in petroleum cracking
• Individual Ln oxides as phosphors in TV screens

⭐ CBSE PYQ: Name a lanthanoid which exhibits +4 oxidation state. Why? (CBSE 2019,
 2018, 2017)
Ans: Cerium (Ce, Z=58) is well known to exhibit +4 oxidation state. Ce has the configuration
[Xe]4f¹5d¹6s². When it loses 4 electrons, it forms Ce⁴⁺ with configuration [Xe] (f⁰) — noble gas
configuration, which is exceptionally stable. However, Ce⁴⁺ is a strong oxidant (E° = +1.74 V) and
readily reverts to +3 state. Other examples showing +4 only in oxides: Pr, Nd, Tb, Dy.

14. THE ACTINOIDS (5f Series)

14.1 Electronic Configuration
• Fourteen elements from Th (Z=90) to Lr (Z=103)
• All have 7s² with variable occupancy of 5f and 6d subshells
• Fourteen electrons formally added to 5f (though Th starts with 6d²7s²)
• Irregularities related to stability of f⁰, f⁷ and f¹⁴ occupancies
• Am: [Rn]5f⁷7s²; Cm: [Rn]5f⁷6d¹7s²
• 5f orbitals are NOT as buried as 4f orbitals → 5f electrons can participate in bonding far more

14.2 Oxidation States

• General +3 oxidation state (like lanthanoids)
• MUCH wider range than lanthanoids: +2 to +7 observed
• First half of series: frequently exhibit higher oxidation states
• Maximum oxidation state increases from +4 (Th) to +5 (Pa), +6 (U), +7 (Np, Pu)
• Then decreases in succeeding elements
• +3 and +4 ions tend to hydrolyse
• Chemistry cannot be reviewed simply in terms of oxidation states (too uneven distribution)

14.3 General Characteristics

• All silvery in appearance but display variety of structures (irregular metallic radii)
• Highly reactive metals, especially when finely divided
• Boiling water gives mixture of oxide and hydride
• React with most non-metals at moderate temperatures
• HCl attacks all actinoid metals; most slightly affected by HNO₃ (protective oxide layer)
• Alkalies have no action on actinoids
• Magnetic properties more complex than lanthanoids; lanthanoids have higher magnetic susceptibility
values
• All actinoids are RADIOACTIVE — earlier members have relatively long half-lives; later ones very
short
• Lawrencium (Z=103) has half-life of only 3 minutes
• Later members available only in nanogram quantities — study is very difficult

14.4 Actinoid Contraction

• Gradual decrease in size of atoms/M³⁺ ions across the series (like lanthanoid contraction)
• Contraction is GREATER from element to element than in lanthanoids
• Reason: 5f electrons provide POORER shielding from nuclear charge than 4f electrons

⭐ CBSE PYQ: Actinoid contraction is greater element to element than lanthanoid

contraction. Why? (CBSE 2020, 2019, 2018)
Ans: In actinoids, 5f electrons are being added. These 5f electrons provide poorer shielding from
nuclear charge than 4f electrons of lanthanoids. As nuclear charge increases across the actinoid
series, each newly added 5f electron is unable to effectively shield the outer electrons from the
increasing nuclear charge. This results in a greater decrease in size from one element to the next
compared to lanthanoids.

15. COMPARISON: LANTHANOIDS vs ACTINOIDS

Property Lanthanoids Actinoids
Orbitals filled 4f (and some 5d) 5f (and some 6d, 7s)
Oxidation states Mainly +3; +2, +4 occasionally +3, +4, +5, +6, +7 — much wider
range
Radioactivity Only Pm is radioactive ALL are radioactive
Ease of study Easier to study Difficult — short half-lives,
radioactivity
Contraction Lanthanoid contraction (smaller Actinoid contraction (greater per
per step) step)
5f vs 4f orbitals 4f orbitals buried inside atoms 5f not as buried; can participate in
bonding
Ionisation enthalpy Higher for early members Lower for early members (5f less
shielded)
Magnetic properties More complex calculations Even more complex; lower μ
values
Complex formation Less tendency Greater tendency (5f participates in
bonding)
Colour Many Ln³⁺ ions are coloured Many actinoid ions are also
coloured
Reactivity React like Ca (early) or Al (later) Highly reactive, esp. finely divided

⭐ CBSE PYQ: Compare chemistry of actinoids with lanthanoids with reference to: (i)
electronic config (ii) oxidation states (iii) chemical reactivity. (CBSE 2020, 2019, 2018, 2017)
Ans: (i) Electronic config: Lanthanoids fill 4f orbitals (4fⁿ6s²); Actinoids fill 5f orbitals (5fⁿ7s²). 4f is
buried inside; 5f is not — can participate in bonding. (ii) Oxidation states: Lanthanoids mainly +3;
+4 and +2 occasionally. Actinoids show +3 to +7 — much wider range due to comparable
energies of 5f, 6d, 7s levels. (iii) Chemical reactivity: Lanthanoids less reactive; actinoids are
highly reactive especially when finely divided. Actinoids react with water, HCl attacks all; nitric acid
passivates (oxide layer). All actinoids are radioactive; only Pm among lanthanoids is radioactive.

16. DISPROPORTIONATION
• Disproportionation: when an oxidation state is less stable relative to one lower AND one higher → it
simultaneously oxidises and reduces itself
• Example 1: Cu⁺ in aqueous solution → 2Cu⁺(aq) → Cu²⁺(aq) + Cu(s)
• Cu⁺ is unstable in aqueous solution; Cu²⁺ is more stable due to much more negative ΔhydH° of Cu²⁺
vs Cu⁺
• Example 2: Mn(VI) in acidic solution: 3MnO₄²⁻ + 4H⁺ → 2MnO₄⁻ + MnO₂ + 2H₂O

⭐ CBSE PYQ: What is disproportionation? Give an example. (CBSE 2019, 2018, 2017)
Ans: Disproportionation is the process by which an element in a particular oxidation state
simultaneously undergoes oxidation (to a higher state) and reduction (to a lower state) because
that particular state is less stable than adjacent ones. Example: 3MnO₄²⁻ + 4H⁺ → 2MnO₄⁻ +
MnO₂ + 2H₂O. Here Mn(VI) in acidic solution disproportionates to Mn(VII) (permanganate) and
Mn(IV) (MnO₂). Another example: 2Cu⁺(aq) → Cu²⁺(aq) + Cu(s).

17. QUICK REVISION — KEY FACTS FOR CBSE

Key Point Value/Explanation
Cr electronic config 3d⁵4s¹ (not 3d⁴4s²) — half-filled d stability
Cu electronic config 3d¹⁰4s¹ (not 3d⁹4s²) — fully filled d stability
Cr³⁺ config [Ar]3d³
Cu⁺ config [Ar]3d¹⁰
Mn shows max oxidation states +2 to +7 (7 states) — d⁵4s² allows all 7 e⁻
Spin-only formula μ = √n(n+2) BM
Mn²⁺ magnetic moment 5 unpaired e⁻ → μ = 5.92 BM
Fe³⁺ magnetic moment 5 unpaired e⁻ → μ = 5.92 BM
Co²⁺ magnetic moment 3 unpaired e⁻ → μ = 3.87 BM
Cu²⁺ colour Blue (d⁹)
MnO₄⁻ colour Purple/violet
K₂Cr₂O₇ colour Orange
K₂CrO₄ colour Yellow
E° of Cu²⁺/Cu +0.34 V (positive — Cu cannot displace H₂)
Oxidation state in CrO₄²⁻ and Cr₂O₇²⁻ +6 in both
Cr₂O₇²⁻ in acid (half reaction) Cr₂O₇²⁻ + 14H⁺ + 6e⁻ → 2Cr³⁺ + 7H₂O (E°=+1.33V)
MnO₄⁻ in acid (half reaction) MnO₄⁻ + 8H⁺ + 5e⁻ → Mn²⁺ + 4H₂O (E°=+1.52V)
MnO₄⁻ structure Tetrahedral; diamagnetic
Zr and Hf have similar radii Due to lanthanoid contraction (160 pm vs 159 pm)
Lanthanoid contraction cause Poor shielding by 4f electrons
Actinoid contraction > lanthanoid 5f electrons shield even less effectively than 4f
Ce well-known +4 state Ce⁴⁺ = f⁰ (noble gas config); E°(Ce⁴⁺/Ce³⁺)=+1.74V
Eu well-known +2 state Eu²⁺ = f⁷ (half-filled, extra stable)
Mischmetall ~95% lanthanoid + ~5% Fe; used in Mg alloy, lighter
flints
V₂O₅ catalyst use Contact process — oxidation of SO₂ to SO₃
Fe catalyst use Haber process — N₂ + H₂ → NH₃
Ni catalyst use Hydrogenation of fats/oils
Interstitial compounds TiC, Mn₄N, Fe₃H — hard, high mp, metallic
conductivity, chemically inert
Brass Cu-Zn alloy
Bronze Cu-Sn alloy

✦ Best of Luck for CBSE Board Exam! ✦