What are the periodic trends for atomic radii, ionization

energy, and electron affinity?

Chemistry  The Periodic Table  Periodic Trends in Ionization Energy

2 Answers

SCooke
Nov 13, 2016

They will all increase (generally) with increasing atomic number.

Explanation:

Generally, the atomic radius increases with element size (atomic number). Ionization energy and electron
affinity also increase with increasing atomic number, but primarily along the same row (left to right)
of elements in the Periodic Table.

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Truong-Son N.
Nov 13, 2016

Of these, atomic radius is the most predictable, and ionization energy and electron affinity trends follow (at
least in part) from such trends.

ATOMIC RADII
 In general, the atomic radius (except for many transition metals) has a pattern where it decreases from the
bottom-left to the top-right of the periodic table.

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This is because:

Effective nuclear charge increases from left to right.

As we go across the periodic table from left to right, protons are more massive than electrons, so adding one
proton and one electron to obtain a new atom means that Zeff↑. Higher Zeff means smaller radius.

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A new quantum level corresponds to the valence shell on a new row (below).
This new quantum level is farther out, and therefore, the radius increases as we go downwards on the
periodic table.

Note that it means you cannot, say, compare N and S fairly, since they have conflicting periodic trends.

IONIZATION ENERGIES
As I said, the ionization energies follow somewhat from atomic radius. The smaller the atomic radius,
the more closely the electrons are held by the nucleus, and thus the higher the ionization energy.

So, in general, ionization energy increases from the bottom-left to the upper-right of the periodic table.

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There are, however, some exceptions to this general rule, as you can see in the diagram below:
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Elements on a new row have their final electron start on a new quantum level, so naturally its ionization
energy drops a bunch.

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Elements in the same row that start to fill a new subshell (a new l) have a drop in ionization energy
downwards.
The new subshell is higher in energy (less core-like). Therefore, the first ionization energy (IE1) for, say, B, is
lower than for Be, because the 2p orbitals are higher in energy than the 2s, and so, B can be more easily
ionized than Be.

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For elements with electrons in a subshell of l≥1, once electron pairing starts occurring, the paired electron
is easier to remove than an unpaired electron.
Electron pairing causes electron repulsion between like-charges which means that the ionization energy
required to remove the first electron (IE1) is smaller. For instance, it is smaller for O than for N, since the
fourth 2p electron on O is paired but the 2p electrons on N are not.

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ELECTRON AFFINITY

Electron affinity is not particularly patterned or necessarily predictable. In general, smaller atomic

radius *usually* corresponds to a higher electron affinity, since a higher Zeff can accommodate more
electrons more easily than a lower Zeff.

So, in general, electron affinity increases from the bottom-left to the top-right of the periodic table.

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