Electron Affinity

This is the energy change occurring when a gaseous non-metal atom accepts one
electron.
The symbol for electron affinity is EA.

The 1st electron affinity, EA₁, is the enthalpy change when 1 mole of electrons is
added to 1 mole of gaseous atoms to form 1 mole of gaseous ions with a single
negative charge under standard conditions.

💡 Note:
The enthalpy change for the 1st electron affinity, EA₁, is generally
exothermic; EA₁ is negative

When an element forms an ion with more than one negative charge, we must use
successive electron affinities.
The 1st, 2nd, and 3rd electron affinities have symbols EA₁, EA₂, and EA₃.

💡 Note:
2nd electron affinities are always endothermic (EA₂ is positive), and so are
3rd electron affinities.
In short, after the 1st electron affinity, all successive electron affinities are
endothermic (EA values are positive).

Trends in EA
Generally, electron affinities for non-metals get more negative (more exothermic)
across a period, with a maximum at Group 17, but the pattern is not always clear.
There is no clear pattern in electron affinities down many groups apart from Groups
16 and 17. In these groups, there is a trend to less negative (less exothermic)
electron affinities as you go down the group, apart from the first member in the
group.

Electron Affinity 1
 Factors influencing EA in Groups 16 & 17
The value of the 1st electron affinity depends on the attraction between the added
electron and the positively charged nucleus. The stronger the attraction, the greater
the amount of energy released. The factors influencing the value of electron affinity
for Groups 16 and 17 are the same as those relating to 1st ionisation energy.

The greater the nuclear charge, the greater the attractive force between the
nucleus and the outer electrons. Cl, which has a greater nuclear charge than S,
will tend to attract electrons more readily, and thus more energy is released
compared to S, when Cl atom gains an electron.

The further away the outer shell electrons are from the positively charged
nucleus (i.e. the greater the atomic radius), the less the attractive force between
the nucleus and the outer shell electrons. Since the number of electron shells
(and atomic radius) increases down Groups 16 and 17, the electron affinity
decreases down these groups.

The greater the number of electron shells, the greater the shielding effect of the
inner shell electrons, thus outer shell electrons experience decreased nuclear
charge. this also causes the electron affinity to decrease down Groups 16 and
17.

Electron Affinity 2
 💡 Note:
Fluorine does not follow this trend. The EA of an F atom is lower than that
of a Cl atom because the atomic radius of the F atom is very small. The
high electron density causes a greater repulsion between the electrons
within the atom. This greatly reduces the attractive force between the
nucleus and the incoming electron.

Expanded
Fluorine has 5 electrons in the 2p-subshell, whereas chlorine has 5
electrons in the 3p-subshell. The 3p-subshell is relatively larger than the
2p-subshell, thus, repulsion among the 5 electrons is greater in fluorine’s
2p-subshell than in chlorine’s 3p-subshell.

Due to the smaller size, and thus greater electron-electron repulsions

within the atom, a fluorine atom less readily accepts an electron compared
to chlorine, and therefore less energy is released, leading to fluorine
having a smaller electron affinity than chlorine.

The same reasoning applies to oxygen and sulfur (except with 4 electrons
in the p-orbitals).

In addition, oxygen has a smaller nuclear charge than fluorine, so its EA is

smaller than its entire group, whereas fluorine’s EA is smaller than chlorine
only.

Electron Affinity 3