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Q.Define electron affinity. Why electron affinity of Cl is more than F although electron affinity decreases down the group?

Assam AhsecAHSEC Higher Secondary (HS) 1st Year Examination 2020Subjective· 2mImportance★★★★★
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Electron affinity is the energy released on adding an electron to a neutral gaseous atom. Despite the general trend (EA decreases down a group), Cl > F because fluorine's tiny 2p orbital suffers strong electron-electron repulsion when a new electron is added.

Electron gain enthalpy (electron affinity), ΔegH\Delta_{eg}H, is defined as the enthalpy change when an electron is added to a neutral, isolated gaseous atom to form a gaseous anion: X(g)+e−→X−(g)X(g) + e^- \rightarrow X^-(g).

As a general periodic trend, electron affinity becomes less negative (weaker attraction for the extra electron) on descending a group, because atomic size increases and the added electron is farther from the nucleus, feeling a weaker effective nuclear charge.

Fluorine is a striking exception to this trend, however: its atomic radius is unusually small and its 2p subshell (only n=2) is very compact. When an extra electron is forced into this small, already electron-dense 2p subshell, the strong inter-electronic repulsion between the incoming electron and the existing electrons releases significantly less net energy than expected — this repulsion partly cancels the energy gained from the favourable nuclear attraction.

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