d-Block Elements (Transition Elements)
Introduction
1. d-Block elements are known as transition elements because they lie between s-block
and p-block elements.
2. They show transitional properties between reactive s-block metals (ionic
compounds) and p-block elements (covalent compounds).
3. Definition: An element whose atom in ground state or common oxidation state has a
partly filled d-subshell (1 to 9 electrons in d).
4. Group 12 elements (Zn, Cd, Hg) have filled d-orbitals even in their common
oxidation states and are not considered transition elements.
5. General electronic configuration: (n−1)d1−10ns1−2(n-1)d^{1-10}ns^{1-
2}(n−1)d1−10ns1−2. Exception: Pd – [Kr]4d^{10}5s^0.
6. Common properties:
o Catalytic activity
o Paramagnetism (unpaired d-electrons)
Electronic Configuration Chart (1st, 2nd, 3rd series)
Series Elements Atomic No. Electron Config (s + d)
3d Sc to Zn 21-30 Example: Sc – 4s²3d¹, Zn – 4s²3d¹⁰
4d Y to Cd 39-48 Example: Y – 5s²4d¹, Cd – 5s²4d¹⁰
5d La to Hg 57-80 Example: La – 6s²5d¹, Hg – 6s²5d¹⁰
General Trends in Transition Elements Chemistry
A. Metallic Character
• Penultimate (d) shell expands → similar chemical & physical properties.
• Properties: High strength, ductility, malleability, electrical & thermal
conductivity, lustre.
• Structures: ccp/hcp.
• Hard Metals: Cr, Mo, W (due to unpaired electrons, high atomisation enthalpy).
• Metal-metal bonding is more in heavier transition elements (4d, 5d series).
B. Melting & Boiling Points
• Higher than s-block due to strong metallic bonds (unpaired d-electrons).
• Zn, Cd, Hg: Low m.p. & b.p. due to no unpaired electrons.
• 3d-series: m.p. increases till d⁵ (except Mn), then decreases.
• Highest m.p.: W (3400°C), Lowest: Hg (–38°C).
C. Density
• Low atomic volumes + high atomic masses → High densities.
• Trends: Density increases across periods.
• Order within group: 3d < 4d << 5d.
• Max Density: Os, Ir.
D. Ionisation Energies (I.E.)
• Higher than s-block elements.
• Zn, Cd, Hg: Very high 1st I.E. (due to d¹⁰ns² configuration).
E. Variable Oxidation States
• Due to similar energies of ns and (n–1)d orbitals.
• General Rule:
o Min Ox. State = no. of ns electrons.
o Max Ox. State = ns + no. of unpaired (n–1)d electrons.
• Examples:
o Sc (+3), Ti (+2 to +4), V (+2 to +5), Cr (+2 to +6), Mn (+2 to +7).
o Highest Ox. State: +8 (Os, Ru).
o Zero Oxidation State: Metal carbonyls e.g., Ni(CO)₄.
• Trends:
o Across a period, higher oxidation state becomes less stable.
o Down a group, stability of higher oxidation states increases.
F. Electrode Potentials (SRP & SOP)
• Factors: Sublimation enthalpy, Ionisation enthalpy, Hydration enthalpy.
• Cu has positive E° (M²⁺/M) → does not displace H₂ from acids.
• Example:
o Cr²⁺ (reducing agent) → Cr³⁺ (stable half-filled t₂g³).
o Mn³⁺ (oxidising agent) → Mn²⁺ (d⁵ stable).
G. Stability of Higher Oxidation States
• Stabilised in halides (with F) and oxides.
• Fluorides stabilise higher oxidation states due to high lattice/bond enthalpy.
• Oxides stabilise high oxidation states through multiple bonding (π-bonding).
H. Magnetic Properties
• Paramagnetism: Due to unpaired d-electrons.
• Magnetic Moment (μ) = √n(n+2) BM (n = no. of unpaired electrons).
• d¹ to d⁹ → Paramagnetic, d⁰ & d¹⁰ → Diamagnetic.
I. Interstitial Compounds
• Non-metal atoms (H, B, C, N) trapped in metal lattices.
• Properties:
o Non-stoichiometric.
o Hardness (borides ≈ diamond).
o High m.p., retains metallic conductivity, chemically inert.
• Examples: TiC, Fe₃H, TiH₁.₇₀.
J. Catalytic Properties
• Reasons:
o Variable oxidation states.
o Free valencies on surface (adsorption).
o Vacant d-orbitals.
• Examples: Fe in Haber Process, Ni in hydrogenation.
K. Alloy Formation
• Formed by elements with similar atomic radii (within 15% difference).
• Examples:
o Bronze: Cu + Sn.
o Brass: Cu + Zn.
o Stainless Steel: Fe + Cr + Ni.
o Nichrome: Ni + Cr + Fe.
o Amalgam: Metal + Hg (except Fe, Co, Ni).
Coloured Ions
• d-d transitions (electrons jump between d-orbitals).
• Colour observed = complementary to absorbed light.
• Example:
o Ti³⁺ – Purple
o V³⁺ – Green
o Cr³⁺ – Violet
o Mn²⁺ – Pink
o Fe³⁺ – Yellow
o Cu²⁺ – Blue
o Zn²⁺ – Colourless (d¹⁰).
Important Compounds
Potassium Permanganate (KMnO₄)
• Preparation:
o Fusion of MnO₂ with KOH/K₂CO₃ → K₂MnO₄ (green).
o K₂MnO₄ disproportionates to KMnO₄ (purple).
• Properties:
o Purple crystals, oxidising agent in acidic/neutral/alkaline media.
o Example Oxidation Reactions: H₂S → S, SO₂ → SO₄²⁻, Fe²⁺ → Fe³⁺.
o Decomposes to MnO₂, releases O₂ on heating.
Potassium Dichromate (K₂Cr₂O₇)
• Preparation:
o Chromite ore + Na₂CO₃ → Na₂CrO₄.
o Acidify to get Na₂Cr₂O₇ → React with KCl → K₂Cr₂O₇.
• Properties:
o Orange crystals, oxidising agent in acidic medium.
o Reaction: SO₂ → SO₄²⁻, Fe²⁺ → Fe³⁺.
o Chromyl chloride test: NaCl + K₂Cr₂O₇ + H₂SO₄ → CrO₂Cl₂.
o With H₂O₂: forms deep blue CrO₅.
f-Block Elements (Inner Transition Elements)
Lanthanoides (Ce-58 to Lu-71)
• General Config: [Xe] 4f¹–¹⁴ 5d⁰–¹ 6s².
• Properties:
o Reactive, not found free in nature.
o Soft metals, tarnish quickly.
o Decrease in atomic/ionic size across series → Lanthanoid Contraction.
o +3 Oxidation State is common.
o Some show +2 (Eu, Sm) & +4 (Ce, Tb).
o Paramagnetism due to unpaired f-electrons.
o Colour arises from f-f transitions.
• Uses: Misch metal (95% Ce) in lighters, TV phosphors, glass polishing.
Actinoides (Th-90 to Lr-103)
• General Config: [Rn] 5f⁰–¹⁴ 6d⁰–² 7s².
• All are radioactive.
• Oxidation states: +3 common; +4, +5, +6, +7 also seen.
• Show Actinoid Contraction.
• Properties: High densities, high m.p., paramagnetic.
• Examples:
o Thorium: Nuclear reactors.
o Uranium: Nuclear fuel.
o Plutonium: Atomic bombs.
Comparison: Lanthanoids vs Actinoids
Feature Lanthanoids Actinoids
+3 dominant (+2, +4 +3 dominant (+4, +5, +6, +7
Oxidation States
occasionally) common)
Complex
Less tendency Greater tendency
Formation
Except Pm, others non-
Radioactivity All radioactive
radioactive
Basicity of OH⁻ Less basic More basic
