IB ChemistryStructure 33.13.1.6

Ionisation Energy Anomalies

Why Be→B and N→O break the periodic trend. Subshell energy and spin-pairing.

Structure 3.1 HL Extension ⏱️ ~5 min revision

While first IE generally increases across Period 2, there are two anomalous dips that examiners love to test:

1st Ionisation Energy across Period 2

Ionisation Energy Period 2 0 500 1000 1500 2000 2500 Li Be B C N O F Ne Element (Period 2) 1st Ionisation Energy (kJ mol⁻¹) Be → B Dip N → O Dip

Anomaly 1: Be → B (Group 2 → 13)

Subshell Dip

Beryllium to Boron (Be → B): 2s vs 2p Subshell

Be (\(1\text{s}^2\,2\text{s}^2\)): Electron removed from the \(2\text{s}\) subshell.
B (\(1\text{s}^2\,2\text{s}^2\,2\text{p}^1\)): Electron removed from the \(2\text{p}\) subshell.

The \(2\text{p}\) subshell is higher in energy and less penetrating than \(2\text{s}\) (shielded by \(2\text{s}^2\)). Therefore, the single \(2\text{p}\) electron in Boron requires less energy to remove despite higher nuclear charge.

Anomaly 2: N → O (Group 15 → 16)

Spin-Pairing Dip

Nitrogen to Oxygen (N → O): Spin-Pairing Repulsion

N (\(2\text{p}^3\)): Three unpaired electrons in separate p-orbitals (\(\uparrow\, \uparrow\, \uparrow\)) with zero pairing repulsion.
O (\(2\text{p}^4\)): One doubly occupied p-orbital (\(\uparrow\!\downarrow\, \uparrow\, \uparrow\)).

The paired electron in Oxygen experiences inter-electron spin-pairing repulsion within the same orbital. This raises its potential energy and makes it easier to remove, resulting in a lower \(\text{IE}_1\) than Nitrogen.

Examiner Trap

Period 2 Anomalies Mirror Period 3

The exact same two anomalies repeat across Period 3: \(\text{Mg} \rightarrow \text{Al}\) (3s vs 3p subshell) and \(\text{P} \rightarrow \text{S}\) (3p spin-pairing repulsion). You must be prepared to write electron configurations and orbital box diagrams for both periods.

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