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d- and f-Block Elements Notes

Questions

5–8 MCQs per paper

Difficulty

Medium

Importance

High yield for JEE Main and NEET

Overview

The d- and f-block elements represent the transition and inner transition metals, characterized by the progressive filling of d- and f-orbitals. Mastering this topic is crucial for entrance exams as it integrates electronic configurations, oxidation states, and coordination chemistry, forming the basis for high-weightage inorganic chemistry questions.

General Properties of Transition Metals

Transition elements exhibit metallic character, high melting points, and variable oxidation states due to the participation of (n-1)d electrons. Their atomic radii decrease across a series but remain relatively constant after the middle due to the shielding effect of d-electrons.

  • High atomization enthalpy due to strong interatomic metallic bonding
  • Variable oxidation states arise from small energy gap between ns and (n-1)d orbitals
  • Paramagnetism increases up to group 7 and then decreases
  • Ionic radii decrease across a series (Lanthanoid contraction impacts d-series)

Oxidation States and Stability

Transition metals show a wide range of oxidation states, with the most stable states often linked to half-filled or fully-filled d-orbitals. Understanding the relative stability of ions in aqueous solutions requires looking at electrode potentials (E°) rather than just sublimation or ionization energy.

  • Mn exhibits highest oxidation state of +7 in KMnO4
  • Stability of +2 state increases across the series for M2+/M
  • E°(M2+/M) values are negative except for Cu (+0.34V)
  • Cr2+ is a strong reducing agent (d4 to d3 configuration)

Coloured Compounds and Magnetic Moments

The color of transition metal ions arises from d-d transitions, which occur when electrons absorb energy to move between split d-orbitals. Magnetic behavior is typically calculated using the 'spin-only' formula, which is a standard quantitative question type in JEE/NEET.

  • Color is observed when d-orbitals are partially filled
  • Spin-only magnetic moment formula: μ = sqrt(n(n+2)) BM
  • d0 and d10 systems are colorless (e.g., Sc3+, Zn2+)
  • Magnetic moment increases with the number of unpaired electrons (n)

Lanthanides and Actinides

Lanthanoids exhibit a steady decrease in atomic/ionic size known as lanthanoid contraction, which influences the properties of subsequent 4d and 5d series elements. Actinides show a greater range of oxidation states compared to lanthanoids due to comparable energies of 5f, 6d, and 7s orbitals.

  • Lanthanoid contraction causes similarity in size between Zr and Hf
  • Common oxidation state for lanthanoids is +3
  • Actinides exhibit +3, +4, +5, +6, and +7 oxidation states
  • 4f electrons have poorer shielding than d-electrons

Formula Sheet

Magnetic moment μ = sqrt(n(n+2)) BM

Effective Nuclear Charge Zeff = Z - σ

E°cell = E°cathode - E°anode

Exam Tip

Always check the electronic configuration of Cr and Cu exceptions first before calculating oxidation states or magnetic moments.

Common Mistakes

  • Confusing paramagnetic character with the presence of any d-electron rather than counting unpaired electrons specifically.
  • Neglecting the effect of Lanthanoid contraction when comparing atomic sizes of 4d and 5d transition series.
  • Assuming all colored compounds are due to d-d transitions, while ignoring charge transfer spectra in compounds like KMnO4.

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