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Exercises · 4.25

Q.Describe the change in hybridisation (if any) of the Al atom in the following reaction: AlCl3+Cl−→AlCl4−AlCl_3 + Cl^- \rightarrow AlCl_4^-.

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In this reaction, the aluminium atom changes from sp2sp^2 hybridisation in AlCl3AlCl_3 to sp3sp^3 hybridisation in AlCl4−AlCl_4^-, because the electron-deficient AlCl3AlCl_3 accepts a lone pair from Cl−Cl^-, increasing its coordination number from 3 to 4.

The key to understanding this change lies in Orbital Hybridisation Theory — the idea that atomic orbitals mix to form new, equivalent hybrid orbitals that match the geometry of the molecule. The hybridisation of an atom is determined by the number of sigma bonds and lone pairs around it (its steric number). You don’t need to memorise every case; just count the regions of electron density.

Let’s walk through the reaction step by step.

  1. Start with AlCl3AlCl_3.

    Aluminium has 3 valence electrons (3s23p13s^2 3p^1). In AlCl3AlCl_3, it forms three sigma bonds with three chlorine atoms. There are no lone pairs on Al.

    Steric number = 3 (three bond pairs, zero lone pairs).

    This corresponds to trigonal planar geometry, which requires sp2sp^2 hybridisation — one ss orbital mixes with two pp orbitals to give three equivalent sp2sp^2 hybrids.

  2. Now consider Cl−Cl^-.

    The chloride ion has a complete octet and carries a negative charge. It has three lone pairs and one empty orbital that can donate a lone pair to an electron-deficient centre. Aluminium in AlCl3AlCl_3 is electron-deficient — it has only 6 electrons in its valence shell, so it readily accepts a lone pair.

  3. The reaction occurs: AlCl3+Cl−→AlCl4−AlCl_3 + Cl^- \rightarrow AlCl_4^-.

    The Cl−Cl^- donates its lone pair to the Al atom, forming a new coordinate (dative) bond. Now Al is bonded to four chlorine atoms.

    Count the electron density regions around Al: four sigma bonds, zero lone pairs.

    Steric number = 4.

    This gives tetrahedral geometry, which requires sp3sp^3 hybridisation — one ss orbital mixes with three pp orbitals. …

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