When atoms gain electrons they become negative ions or anions
Electron affinity (EA) can be thought of as the opposite process of ionisation energy and is defined as
The amount of energy released when one mole of electrons is gained by one mole of atoms of an element in the gaseous state to form one mole of gaseous ions
Electron affinities are measured under standard conditions which are 298 K and 100 kPa
The units of EA are kilojoules per mole (kJ mol-1)
The first electron affinity is always exothermic
E.g. the first electron affinity of chlorine is:
Cl (g) + e- → Cl- (g) ∆H = - 349 kJ mol-1
However, the second electron affinity can be an endothermic process
O- (g) + e- → O2- (g) ∆H = + 753 kJ mol-1
This is due to the fact that you are overcoming repulsion between the electron and a negative ion, so energy is required making the process endothermic overall
Trends in electron affinity
Electron affinities across a period
Electron affinities show periodicity
The pattern is very similar to ionisation energies, except that it is inverted and the minimum points are displaced one element to the right
As might be expected, the most exothermic electron affinities are for group 17 elements which also have the highest electronegativities
The strongest pull on electrons correlates with the greater amount of energy released when negative ions are formed
Noble gases do not form negative ions, so they don't appear in this chart
The electron affinities reach a peak for group 2 and group 5 elements
Electron affinities down a group
Electron affinities generally decrease down a group
As the atoms become larger the attraction for an additional electron is less, since the effective nuclear charge is reduced due to increased shielding
Electron affinity become less exothermic going down the group
An exception to this is fluorine whose electron affinity is smaller than expected
This is because fluorine is such a small atom and an additional electron in the 2p subshell experiences considerable repulsion with the other valence electrons