d-Block and f-Block Elements - Key Points

d-Block (Transition Metals):

 Position: Groups 3-12 in the periodic table, where d orbitals are progressively filled.
 Electronic Configuration: General form is (n-1)d¹–¹⁰ns¹–². Examples: Sc (3d¹ 4s²), Cr (3d⁵ 4s¹).
 Not Transition Metals: Zn, Cd, Hg have full d¹⁰ configurations and are not considered transition metals.
 Properties:
o Incomplete d orbitals lead to various oxidation states, colored ions, and complex formation.
o Catalytic Activity and Paramagnetism are common.

f-Block (Inner Transition Metals):

 Position: Located at the bottom of the periodic table. Includes lanthanoids (4f) and actinoids (5f).
 Electronic Configuration: Involves 4f and 5f orbitals.

General Characteristics:

 Transition vs Non-Transition: Transition metals have incompletely filled d orbitals, whereas non-transition
metals do not.

Examples:

 Scandium (Z = 21): Transition element due to 3d¹ configuration.

 Zinc (Z = 30): Not a transition element because of its completely filled 3d¹⁰ configuration.

Trends:

 Horizontal Trends: Properties change gradually across periods.

 Group Trends: Some similarities are observed among groups.

 Physical Properties: Transition metals are hard, ductile, and conduct electricity well. They have high
melting/boiling points due to strong metallic bonding involving both (n-1)d and ns electrons.

Lattice Structures:

 Transition metals can have different lattice structures (e.g., bcc, ccp, hcp) depending on the element.

Trends in Atomic and Ionic Sizes:

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  Atomic radii decrease across a series due to increasing nuclear charge and incomplete shielding by d-electrons.
 Lanthanoid contraction causes the atomic radii of the 4d and 5d series to be similar despite different atomic
numbers.
 As atomic radii decrease, density increases across the transition series.

Ionisation Enthalpies:

 Ionisation enthalpies show a gradual increase across each series due to increased nuclear charge.
 However, the increase is less steep than in non-transition elements, with exceptions at specific points due to stable
electron configurations (e.g., d⁵ or d¹⁰).
 The second and third ionisation enthalpies rise sharply, especially for elements with stable d configurations.

Oxidation States:

 Transition metals exhibit a wide range of oxidation states, typically varying by one unit, owing to the incomplete
filling of d orbitals.
 Manganese shows all oxidation states from +2 to +7, while elements at the extremes (Sc, Zn) show fewer
oxidation states (mainly +2).
 The highest oxidation states are most stable near the middle of the transition series and decrease toward the
extremes. For example, Mo(VI) and W(VI) are more stable than Cr(VI).

Trends: The variability of oxidation states arises from incomplete filling of d orbitals, and p-acceptor ligands can stabilize
lower oxidation states (e.g., Ni in Ni(CO)₄).

 Electrode Potentials and Oxidation States:

o Copper's positive E° value (+0.34V) is due to its high ΔH° of atomization (DaH) and low hydration
enthalpy.
o Transition metals show varying E° values for the M²⁺/M couple, reflecting differences in ionization
enthalpies and hydration energies.
o The stability of Mn²⁺ (d⁵) and Zn²⁺ (d¹⁰) contributes to their relatively stable electrode potentials.

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 Stable Halides of 3d Metals:

 Highest oxidation states are seen in compounds like TiX₄, VF₅, and CrF₆.
 Fluorine stabilizes high oxidation states due to its high lattice energy and bond enthalpy (e.g., VF₅, CrF₆).
 Mn does not form simple halides in the +7 oxidation state but forms MnO₃F.
 Lower oxidation state fluorides (e.g., VX₂) are generally unstable.

 Oxides and Highest Oxidation States:

 Oxides exhibit higher oxidation states compared to halides, e.g., Mn₂O₇ (Mn in +7) vs. MnF₄.
 The ability of oxygen to form multiple bonds stabilizes these states (e.g., tetrahedral [MO₄]ⁿ⁻ ions like MnVII).

 Oxidizing and Reducing Trends:

 Stability of oxidation states decreases across the series.

 Mn³⁺/Mn²⁺ is more positive than Cr³⁺/Cr²⁺ due to the high third ionization energy of Mn.
 Oxidizing power increases in the series VO₂⁺ < Cr₂O₇²⁻ < MnO₄⁻, as the reduced forms become increasingly
stable.

 Magnetic Properties:

 Transition metals show paramagnetism due to unpaired electrons, with magnetic moments calculated using the
formula μ = √(n(n+2)) (where n = unpaired electrons).
 Example: Mn²⁺ (d⁵) has a magnetic moment of 5.92 BM.

 Color and Complex Formation:

 Colors of ions arise from d-d transitions, influenced by the ligand field (e.g., Ti³⁺ is purple, V²⁺ is violet).
 Complex formation stabilizes various oxidation states and gives rise to diverse chemical behavior.

Complex Compounds

 Definition: Compounds in which metal ions bind with anions or neutral molecules to form complex species.
 Examples: [Fe(CN)₆]³⁻, [Fe(CN)₆]⁴⁻, [Cu(NH₃)₄]²⁺, [PtCl₄]²⁻.
 Properties: Transition metals form numerous complexes due to small ionic sizes, high charges, and available d-
orbitals.

Catalytic Activity

 Reason for Activity:

1. Ability to adopt multiple oxidation states.
2. Tendency to form complexes.
 Examples:
o Vanadium (V) oxide in the Contact Process.
o Finely divided iron in the Haber’s Process.
o Nickel in catalytic hydrogenation.

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  Mechanism: Transition metals lower activation energy by forming bonds with reactants, concentrating them on
the surface and weakening their bonds.

Interstitial Compounds

 Definition: Formed when small atoms like H, C, or N occupy interstitial spaces in the metal lattice.
 Examples: TiC, Mn₄N, Fe₃H, VH₀.₅₆, TiH₁.₇.
 Characteristics:
1. High melting points.
2. Extreme hardness (some borides approach diamond hardness).
3. Retain metallic conductivity.
4. Chemically inert.

Alloys

 Definition: Mixtures of metals forming solid solutions or compounds.

 Formation: Alloys are formed when metallic radii differ by ≤15%.
 Examples:
o Ferrous alloys (e.g., stainless steel).
o Brass (copper-zinc) and bronze (copper-tin).
 Properties: Hard, high melting points, and industrially important.

Oxides and Oxoanions of Metals

 Oxides Formation: Metals react with oxygen at high temperatures forming oxides (e.g., MO for Sc to Mn).
 Oxidation Number Trend: Highest oxidation number matches group number (e.g., Mn in Mn₂O₇). Oxides
beyond Fe₂O₃ are unknown.
 Acidic Nature: Higher oxides (e.g., Mn₂O₇, CrO₃) are acidic; they form acids like HMnO₄ and H₂CrO₄.

Key Equations:

1. Mn₂O₇ → HMnO₄
2. CrO₃ → H₂CrO₄

Potassium Dichromate (K₂Cr₂O₇)

 Preparation:
o Fusion of chromite (FeCr₂O₄) with Na₂CO₃ and air forms Na₂CrO₄.
o Acidifying Na₂CrO₄ with H₂SO₄ gives Na₂Cr₂O₇, converted to K₂Cr₂O₇ using KCl.
2Na2CrO4+2H+→Na2Cr2O7+H2O2Na₂CrO₄ + 2H⁺ → Na₂Cr₂O₇ + H₂O 2Na2CrO4+2H+→Na2Cr2O7
+H2O Na2Cr2O7+2KCl→K2Cr2O7+2NaClNa₂Cr₂O₇ + 2KCl → K₂Cr₂O₇ + 2NaCl Na2Cr2O7
+2KCl→K2Cr2O7+2NaCl
 Oxidising Agent:
o Acidic dichromate oxidises Fe²⁺ to Fe³⁺ and I⁻ to I₂.
Cr2O72−+14H++6Fe2+→2Cr3++6Fe3++7H2OCr₂O₇^{2⁻} + 14H⁺ + 6Fe²⁺ → 2Cr³⁺ + 6Fe³⁺ + 7H₂O
Cr2O72−+14H++6Fe2+→2Cr3++6Fe3++7H2O

Potassium Permanganate (KMnO₄)

 Preparation:
o Fusion of MnO₂ with KOH and oxidants forms K₂MnO₄, disproportionates to KMnO₄ in acidic solution.
3MnO42−+4H+→2MnO4−+MnO2+2H2O3MnO₄^{2⁻} + 4H⁺ → 2MnO₄⁻ + MnO₂ + 2H₂O 3MnO42−
+4H+→2MnO4−+MnO2+2H2O
 Oxidising Reactions:
1. In Acidic Medium:

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 Oxalates oxidised to CO₂: 5C2O42−+2MnO4−+16H+→2Mn2++10CO2+8H2O5C₂O₄^{2⁻} +
2MnO₄⁻ + 16H⁺ → 2Mn²⁺ + 10CO₂ + 8H₂O 5C2O42−+2MnO4−+16H+→2Mn2++10CO2
+8H2O
 Fe²⁺ to Fe³⁺: 5Fe2++MnO4−+8H+→5Fe3++Mn2++4H2O5Fe²⁺ + MnO₄⁻ + 8H⁺ → 5Fe³⁺ +
Mn²⁺ + 4H₂O 5Fe2++MnO4−+8H+→5Fe3++Mn2++4H2O
2. In Neutral/Alkaline Medium:
 I⁻ to IO₃⁻: 2MnO4−+H2O+I−→2MnO2+2OH−+IO3−2MnO₄⁻ + H₂O + I⁻ → 2MnO₂ + 2OH⁻ +
IO₃⁻ 2MnO4−+H2O+I−→2MnO2+2OH−+IO3−
 Mn²⁺ to MnO₂: 2MnO4−+3Mn2++2H2O→5MnO2+4H+2MnO₄⁻ + 3Mn²⁺ + 2H₂O → 5MnO₂
+ 4H⁺ 2MnO4−+3Mn2++2H2O→5MnO2+4H+
 Limitation: KMnO₄ reacts with HCl, liberating Cl₂ gas, making it unsuitable for titrations in acidic medium.

The f-block elements are divided into lanthanoids (atomic numbers 57–71) and actinoids (atomic numbers 89–103). These
elements are characterized by the progressive filling of 4f and 5f orbitals, respectively.

Lanthanoids

 Electronic Configuration: All lanthanoids have the general configuration [Xe]6s²4fⁿ (n = 1 to 14).
 Lanthanoid Contraction: A steady decrease in atomic and ionic radii across the series due to poor shielding by 4f
electrons. This affects the properties of other elements, e.g., the similar radii of Zr and Hf.


 Oxidation States: The most stable oxidation state is +3. Some elements (e.g., Ce⁴⁺, Eu²⁺, Yb²⁺) exhibit +2 and +4
due to stable empty, half-filled, or fully-filled f subshells.


 Physical Properties: Silvery-white, soft metals that tarnish in air; good conductors of heat and electricity. Density,
hardness, and melting points vary across the series.


 Chemical Properties: React with water, acids, halogens, and other elements to form hydroxides, halides, and
oxides. Basic hydroxides resemble alkaline earth metals.
 Applications:
o Alloys: Mischmetall, used in steel production and lighter flints.
o Catalysts: For petroleum cracking.
o Phosphors: In TV screens and other fluorescing surfaces.

Actinoids

 Electronic Configuration: Variable configurations due to 5f orbital filling; [Rn]6d¹⁻²7s² for early actinoids.
 Oxidation States: Wider range (+3 to +6), contributing to complex chemistry.

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 
 Radioactivity: Most actinoids are radioactive, complicating their study and applications.
 Applications: Nuclear energy (e.g., uranium and thorium).

Key Trends and Features

 Lanthanoid Contraction: Leads to chemical similarity among third-row transition metals.

 Paramagnetism: Due to unpaired f-electrons; exceptions are La³⁺ and Lu³⁺.
 Reactivity: Decreases across the lanthanoid series, resembling aluminum in later elements.

Lanthanoids and actinoids are crucial for advancements in metallurgy, catalysis, and technology, despite their challenging
extraction and handling.

Iron and Steel

 Importance: Iron and steel are key construction materials used in various industries.
 Production: Involves:
o Reduction of iron oxides.
o Removal of impurities.
o Addition of alloying elements like Cr, Mn, Ni, and C for desired properties.

Special Compounds

 TiO: Used in the pigment industry.

 MnO₂: Essential for dry battery cells.

Battery Metals

 Zn: Widely used in batteries.

 Ni/Cd: Employed in rechargeable battery systems.

Group 11 Elements

 Coinage Metals: Cu, Ag, and Au.

o Modern coins often use Cu-coated steel or Cu/Ni alloys instead of pure metals.

Catalysts in Industry

 V₂O₅: Oxidizes SO₂ in sulfuric acid production.

 TiCl₄ with Al(CH₃)₃: Ziegler catalysts for polyethylene manufacturing.
 Iron: Catalyst for ammonia synthesis in the Haber process.
 Nickel:
o Hydrogenates fats.
o Useful in the polymerization of alkynes and aromatic compounds.
 PdCl₂: Catalyst in the Wacker process for ethanal production.

Photographic Industry

 AgBr: Used for its light-sensitive properties in film photography.

These metals and compounds are vital for diverse industrial applications, including construction, energy, and chemical
synthesis.