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Ionization Enthalpy Anomaly

Hardchemistry

Why is the first ionization enthalpy of oxygen slightly lower than that of nitrogen, contrary to the general increase across a period?

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About This Question

Subject
chemistry
Chapter
classification of elements and periodicity in properties
Topic
ionization enthalpy anomaly
Difficulty
Hard
Year
2025
Tags
ionization enthalpy anomalyhalf-filled stabilitynitrogen oxygenexchange energyelectron pairing

Solution

Correct Answer:

Nitrogen has an extra-stable half-filled 2p subshell

First ionization enthalpy generally rises across a period, but exceptions occur where electronic configuration confers special stability. Nitrogen has the configuration 1s^2 2s^2 2p^3, with an exactly half-filled 2p subshell that is unusually stable due to symmetrical electron distribution and favourable exchange energy. Removing an electron from this stable arrangement requires extra energy. Oxygen has the configuration 1s^2 2s^2 2p^4, where the fourth 2p electron must pair up in an already occupied orbital, introducing electron-electron repulsion that makes it easier to remove. Consequently oxygen's first ionization enthalpy is slightly lower than nitrogen's. The option of smaller nuclear charge for oxygen is false, since oxygen has more protons. The option of more shells is wrong, as both are in period two. The option that nitrogen is a metal is incorrect. This half-filled stability anomaly is a key JEE Advanced periodicity point. Understanding ionization enthalpy anomaly in this way ties directly into the wider study of classification of elements and periodicity in properties, where the same reasoning recurs across many problems. Plausibility check: the analogous dip occurs between phosphorus and sulphur, confirming that half-filled stability causes the reversal.

This hard difficulty chemistry question is from the chapter classification of elements and periodicity in properties, covering the topic of ionization enthalpy anomaly. It appeared in the 2025 exam.

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