Chemical Bonding: Common Mistakes and Fixes (3)

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Question

Predict the shape, hybridisation, and bond angle of XeF4\text{XeF}_4 using VSEPR theory. Then explain why it differs from CF4\text{CF}_4 even though both have four fluorine atoms attached.

Solution — Step by Step

Xe has 8 valence electrons. Four are used in bonds with F atoms (one each). The remaining 4 electrons form two lone pairs.

Total electron pairs around Xe: 4 bonding + 2 lone = 6 pairs.

Six electron pairs \to sp3d2sp^3 d^2 hybridisation.

With 6 electron pairs and 2 lone pairs, the lone pairs occupy positions opposite to each other (axial of the octahedron) to minimise repulsion. The four bonding pairs lie in the equatorial plane.

Shape: square planar. Bond angle: 90°90°.

Carbon has 4 valence electrons, all used in bonding with F. No lone pairs. So CF4\text{CF}_4 is sp3sp^3 hybridised, tetrahedral, bond angle 109.5°109.5°.

Xenon (period 5) has empty 5d5d orbitals available for hybridisation, allowing it to expand its octet to 12 electrons. Carbon (period 2) has no dd orbitals in its valence shell, so it cannot exceed 8 electrons. The lone pairs on Xe force the geometry to flatten into a square plane.

XeF4\text{XeF}_4: sp3d2sp^3 d^2, square planar, 90°90°. CF4\text{CF}_4: sp3sp^3, tetrahedral, 109.5°109.5°.

Why This Works

VSEPR theory says electron pairs (bonding and lone) repel each other and arrange to minimise this repulsion. The basic geometry is set by the total number of pairs; lone pairs distort the shape by pushing harder than bonding pairs.

Period 3+ elements can use dd orbitals to host extra electrons. This is why SF6\text{SF}_6, XeF4\text{XeF}_4, PF5\text{PF}_5 exist while their period-2 counterparts (e.g. OF6\text{OF}_6) do not.

Alternative Method

Use the steric number formula: SN=(lone pairs)+(bonded atoms)SN = (\text{lone pairs}) + (\text{bonded atoms}). For XeF4\text{XeF}_4: SN=2+4=6sp3d2SN = 2 + 4 = 6 \to sp^3 d^2. For CF4\text{CF}_4: SN=0+4=4sp3SN = 0 + 4 = 4 \to sp^3. Skips the electron-pair counting. Faster for MCQs.

Common Mistake

Predicting tetrahedral geometry for XeF4\text{XeF}_4 because it has 4 F atoms. The bonded atoms count alone does not determine geometry — lone pairs count too. Always include lone pairs when computing the steric number.

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