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Exercises · 4.29

Q.Considering the x-axis as the internuclear axis which out of the following will not form a sigma bond and why?

(a) 1s and 1s
(b) 1s and 2px2p_x
(c) 2py2p_y and 2py2p_y
(d) 1s and 2s.
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A sigma bond requires end‑on (head‑on) overlap along the internuclear axis. The 2py2p_y orbitals are perpendicular to the x‑axis, so they can only overlap sideways to form a pi bond — not a sigma bond. Hence, option (c) does not form a sigma bond.


The Core Idea: Orbital Hybridisation and Bonding Geometry

When two atoms come close, their atomic orbitals overlap to form molecular orbitals. The type of bond formed — sigma (σ\sigma) or pi (π\pi) — depends entirely on how the orbitals overlap relative to the internuclear axis.

  • A sigma bond is formed by end‑on (head‑on) overlap along the line joining the two nuclei (the internuclear axis). This overlap is strong and cylindrically symmetric about the axis.
  • A pi bond is formed by sideways (lateral) overlap above and below the internuclear axis. This overlap is weaker and has a nodal plane containing the axis.

The question gives the x‑axis as the internuclear axis. So any orbital that can point directly along the x‑axis, or has a lobe centred on the x‑axis, can form a sigma bond. Orbitals that lie perpendicular to the x‑axis cannot — they will only form pi bonds.


Step‑by‑Step Analysis

1. Option (a): 1s and 1s

Both 1s orbitals are spherically symmetric. They can overlap head‑on along the x‑axis without any directional restriction. This is the classic sigma bond in H2\text{H}_2.

1s + 1s→σ(1s) bond\text{1s + 1s} \rightarrow \sigma(1s) \text{ bond}

Conclusion: Forms a sigma bond.


2. Option (b): 1s and 2px2p_x

The 2px2p_x orbital has its two lobes aligned exactly along the x‑axis. The 1s orbital can approach along the same axis and overlap end‑on with one lobe of the 2px2p_x. This is a sigma bond — for example, in HF, the 1s of H overlaps with the 2px2p_x of F.

Tip

The pxp_x orbital is the only p‑orbital that points along the x‑axis. pyp_y and pzp_z point along y and z respectively.

Conclusion: Forms a sigma bond.


3. Option (c): 2py2p_y and 2py2p_y …

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