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Chapter 24: Problem 11

Discuss the factors affecting the magnitude of crystal field splitting.

Short Answer

Expert verified
The magnitude of crystal field splitting is affected by three main factors - the nature of the ligand, the oxidation state and geometry of the metal ion, and the type of orbital overlap.

Step by step solution

01

Factor 1: Nature of Ligand

The nature of the ligand affects crystal field splitting by influencing the energy of the d-orbitals. Some ligands, like ions or molecules with lone pairs of electrons, can polarize the electrons in the d-orbitals, consequently changing the energy. In the spectrochemical series, ligands have been ranked based on the difference they create in the energy of d-orbitals. Higher the place in the series, stronger is the ligand and greater is the crystal field splitting.
02

Factor 2: Oxidation State and Geometry of the Metal Ion

The oxidation state of the metal ion affects the magnitude of crystal field splitting. Metal ions with higher oxidation states have smaller ionic radii leading to stronger ligand-field interactions and thereby, a higher splitting of d orbitals. The geometry of the complex also matters. For instance, octahedral complexes have larger crystal field splitting than tetrahedral complexes due to differences in the spatial arrangement of the ligands.
03

Factor 3: Type of Orbital Overlap

The type of orbital overlap between metal ion and ligands also matters. Greater the orbital overlap between the metal ion and ligand, greater is the crystal field splitting. In sigma bonding (head-on overlap), the orbital overlap is significant leading to higher splitting. While in pi bonding (sideways overlap), the splitting is less due to less significant overlap.

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Most popular questions from this chapter

Discuss the molecular orbital diagram of a tetrahedral complex with the help of a suitable example.

Discuss in brief the crystal field theory and represent the splitting of ' \(d\) ' orbitals in octahedral and tetrahedral fields.

What are the limitations of valence bond theory?

Explain the following: (a) \(\left[\mathrm{Fe}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{3+}\) is paramagnetic and coloured. (b) \(\left(\mathrm{Ni}(\mathrm{CN})_{4}\right)^{2-}\) is square planar, but \(\left[\mathrm{Ni}(\mathrm{Cl})_{4}\right]^{2-}\) is tetrahedral. (c) \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{6}\right]^{3+}\) is more stable than \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{6}\right]^{2+}\), while \(\left[\mathrm{Co}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{2+}\) is more stable than \(\left[\mathrm{Co}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{3+}\) (d) Octahedral complexes are less stable than the square planar complexes. (e) \(\left[\mathrm{Co}(\mathrm{CN})_{6}\right]^{3-}\) is a low-spin complex, but \(\left[\mathrm{CoF}_{6}\right]^{3-}\) is high-spin complex.

Discuss Sidgwick's concept of effective atomic number with the help of suitable example.
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