📘 COMPREHENSIVE NOTES: THE D- AND F-BLOCK ELEMENTS

(Based entirely on NCERT – made NEET-ready)

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📘 ADDITION: HOTSPOT SECTION IN NOTES

🔹 INTRODUCTION
• d-block = Groups 3 to 12; lling of (n−1)d orbitals.

• f-block = Lanthanoids (4f) and Actinoids (5f); placed separately.

• Transition elements = Incomplete d-subshell in atoms or common oxidation states.

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 • Zn, Cd, Hg = Not transition metals (have d¹⁰ con guration in all states).

🔹 GENERAL PROPERTIES OF D-BLOCK ELEMENTS

1. Electronic Con guration

• General: (n−1)d¹–¹⁰ns¹–²

• Exceptions:

◦ Cr: [Ar] 3d⁵4s¹ (more stable half- lled d)

◦ Cu: [Ar] 3d¹⁰4s¹ (more stable full- lled d)

2. Atomic & Ionic Sizes

• Gradual decrease in size across period (poor shielding by d-electrons).

• 4d and 5d series have similar sizes due to lanthanoid contraction.

3. Melting & Boiling Points

• High due to strong metallic bonding (involving d-electrons).

• Peaks at middle elements (Cr, Mn, Fe).

4. Density

• Increases with atomic number due to increase in atomic mass and smaller size.

5. Ionisation Enthalpies

• Increase gradually across a period.

• 1st I.E. trend is irregular due to electronic con guration.

• Mn and Zn have abnormal trends (d⁵ and d¹⁰ stability).

🔹 OXIDATION STATES
• Variable due to involvement of (n−1)d and ns electrons.

• Common states:

◦ Sc (+3), Ti (+3, +4), V (+2 to +5), Cr (+2 to +6), Mn (+2 to +7), Fe/Co/Ni (+2, +3),
Cu (+1, +2)

• Stability:
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 ◦ High states common in early series.

◦ Mn has maximum oxidation states (+2 to +7).

• Cu(I) is unstable in aqueous solution (disproportionates to Cu and Cu²⁺).

🔹 COLOURED IONS
• Colour arises due to d–d transitions.

• Requires:

◦ Partially lled d-orbitals

◦ Presence of ligands causing crystal eld splitting

• Colourless ions: Sc³⁺, Zn²⁺ (d⁰/d¹⁰)

🔹 MAGNETIC PROPERTIES
• Due to unpaired electrons.

• Magnetic moment (μ) = √[n(n+2)] BM, where n = no. of unpaired electrons

• Sc³⁺, Zn²⁺ = diamagnetic; others are paramagnetic.

🔹 COMPLEX FORMATION
• High tendency due to:

◦ Small size

◦ High charge density

◦ Availability of vacant d-orbitals

🔹 CATALYTIC PROPERTIES
• Due to:

◦ Variable oxidation states (redox behavior)

◦ Surface adsorption (provides active sites)

• Examples:
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 ◦ Fe: Haber process

◦ V₂O₅: Contact process

◦ Ni: Hydrogenation

🔹 INTERSTITIAL COMPOUNDS
• Small atoms like H, B, C occupy spaces in metal lattice.

• Properties:

◦ Harder

◦ Retain metallic conductivity

◦ Chemically inert

🔹 PREPARATION & PROPERTIES OF COMPOUNDS

A. Potassium Dichromate (K₂Cr₂O₇)

• Orange crystals; prepared from chromite ore.

• Strong oxidising agent in acidic medium.

• Changes:
Cr₂O₇²⁻ (orange) → Cr³⁺ (green)
e.g., oxidises Fe²⁺ to Fe³⁺

B. Potassium Permanganate (KMnO₄)

• Deep purple; prepared from pyrolusite (MnO₂).

• Strong oxidising agent in acidic, neutral, basic media:

◦ Acidic: MnO₄⁻ → Mn²⁺

◦ Basic: MnO₄⁻ → MnO₂

🔹 F-BLOCK ELEMENTS: LANTHANOIDS &

ACTINOIDS
1. Electronic Con guration
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 • Lanthanoids: [Xe] 4f¹–¹⁴ 5d⁰–¹ 6s²

• Actinoids: [Rn] 5f¹–¹⁴ 6d⁰–¹ 7s²

2. Oxidation States

• Lanthanoids: Mostly +3 (some +2, +4 in Sm²⁺, Eu²⁺, Ce⁴⁺)

• Actinoids: Variable from +3 to +6 (Uranium shows +6)

3. Lanthanoid Contraction

• Steady decrease in size across the series.

• Caused by poor shielding of 4f electrons.

• Consequence:

◦ Similar radii of 4d and 5d transition elements (Zr ≈ Hf)

4. Magnetic & Coloured Ions

• Many are paramagnetic.

• Colour arises due to f–f transitions (sharp, not easily split).

5. Actinoids

• All radioactive.

• Show more variable oxidation states than lanthanoids.

• Early actinoids = more reactive due to poor shielding in 5f orbitals.

🔹 TRENDS IN E° VALUES (STANDARD ELECTRODE

POTENTIAL)
Meta E° (M²⁺/
Special Notes
l M)
Noble metal, doesn’t liberate
Cu +0.34 V
H₂
Zn -0.76 V Reactive
Fe -0.44 V Moderate

• Mn²⁺ (d⁵) and Zn²⁺ (d¹⁰) are extra stable

• Cr²⁺ is a strong reducing agent, Mn³⁺ is a strong oxidising agent

🔹 PYQ HOTSPOTS (Based on 2012–2024)
• Mn oxidation states, KMnO₄/K₂Cr₂O₇ redox reactions

• Colour & magnetic behavior of ions

• Lanthanoid contraction effects

• Stability of oxidation states from E° data

• Complexes with unusual oxidation states

• Disproportionation reactions (e.g., Cu⁺)

🔥 PYQ HOTSPOTS (2012–2024) – MUST DO FOR FULL

SCORE
1. Most Stable Oxidation States:

◦ Mn²⁺ (d⁵): highly stable

◦ Zn²⁺ (d¹⁰): stable and colourless

◦ Cu⁺: disproportionates in water → Cu + Cu²⁺

◦ Cr²⁺ → Cr³⁺: strong reducing agent

◦ Mn³⁺ → Mn²⁺: strong oxidising agent

2. Most Asked Compounds:

◦ KMnO₄ & K₂Cr₂O₇: oxidising agents, reactions in acidic, basic, neutral medium

◦ MnO₄⁻ (purple) → Mn²⁺ (colourless) = popular concept

◦ Cr₂O₇²⁻ (orange) → Cr³⁺ (green) in acid

3. Coloured & Colourless Ions:

◦ Coloured: Cr³⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺

◦ Colourless: Sc³⁺ (d⁰), Zn²⁺ (d¹⁰), Cu⁺ (sometimes)

◦ Reason: d–d transitions → requires partially lled d-orbitals

4. Magnetic Moment & Paramagnetism:

◦ Use: √n(n+2) to calculate μ (Bohr Magneton)

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 ◦ Mn²⁺ = 5 unpaired = 5.92 BM

◦ Zn²⁺, Sc³⁺ = diamagnetic

5. Lanthanoid Contraction:

◦ Decrease in size from Ce to Lu due to poor 4f shielding

◦ Results in similar size of Zr and Hf

◦ Asked with 4d–5d chemistry comparison

6. Standard Electrode Potentials (E°):

◦ Cu: +0.34 V → no H₂ evolution with acids

◦ Zn: –0.76 V → highly reactive

◦ Fe: –0.44 V → moderate

◦ Use E° trends to predict redox behavior

7. Disproportionation Reactions:

◦ Cu⁺ in aqueous: 2Cu⁺ → Cu + Cu²⁺

◦ Mn³⁺ is unstable → reduces to Mn²⁺

8. Trick Questions:

◦ Sc³⁺ = transition or not?

◦ Zn²⁺ = not a transition metal

◦ Order of magnetic moment, oxidation states, ionisation enthalpy