Rev.

10/2013

APC NOTES
Unit 5: Periodic Trends
Periodic Trends are predictable patterns of physical and chemical properties of atoms based on
their location on the periodic table. Often, these properties change in a predictable way as we
move across a period or down a group of the periodic table.
We will cover 6 periodic trends in this unit:
1. Atom Size
2. Ion Size
3. Ionization Energy
4. Electron Affinity
5. Metallic Character
6. Electronegativity

Atom Size

It is difficult to determine the size of an atom because the "edge" is not sharply defined but
rather part of the electron cloud (which is only a probable location of electrons).

Unless otherwise noted, the size of an atom always

refers to its bonding atomic radius which means half
the distance between the nuclei of atoms bonded
together.
o Because of the attractive forces present
between two bonded atoms, bonded atoms
tend to get closer to each other and the
bonding atomic radius is therefore slightly
smaller than the nonbonding atomic radius as
shown in the diagram at right.
o

Atomic radii are usually measured with the unit,

Angstrom (). 1 = 10-10 meters

Atomic Radii have a predictable trend on the periodic table as shown in the picture below:

Atomic Radius decreases as you move

up and to the right on the periodic table.

One way to explain this trend is to look at the effective nuclear charge of atoms

Effective Nuclear Charge

The force of attraction between two charged particles is defined by Coulombs Law which
states the force of attraction depends on the magnitude of the charges (Q) and the distance
(d) between them:

F = Q1Q2
d2
o
o

As the magnitude of the charges increase, the force of attraction between them
increases
As the distance between the charges increases, the force of attraction between
them decreases
The size of an atom is determined by the force of attraction felt between the
protons in the nucleus and the outer electrons

In multi-electron atoms, the electrons are attracted to the nucleus but also repelled by
other electrons. In addition, the attractive force of the nucleus is shielded or blocked
from outer electrons by the inner electrons. The amount of positive charge from the
nucleus that actually acts on an electron is called the effective nuclear charge (Zeff).
Effective Nuclear Charge = (Actual Nuclear Charge) (Shielding Effect)

An outer electron might be "shielded" from

the attractive force of protons if there are
other electrons between it and the proton.

To Calculate the Effective Nuclear Charge (Zeff) :

Zeff

Z - S

# of protons

# of core
electrons

*As Zeff increases, there is more attraction between the nucleus and an outer electron, so the
atomic radius will decrease.
Core electrons are all the
"inner" electrons (doesn't
include the valence electrons)

Example: Compare Zeff for Silicon and Phosphorus

Si
Zeff = 14 - 10 = 4

P
Zeff = 15 - 10 = 5

Since Zeff is larger for P, P will have a smaller radius (there is more attractive force
between the protons and outer electrons in phosphorus than there is in silicon)

Example: Compare Zeff for Fe, Co, Ni (all transition metals)

Fe
Co
Ni
*It's hard to see what the core electrons are for transition metals, so it might help to do
electron configurations. Remember: core electrons are all the electrons EXCEPT the
valence ones.
Fe
1s22s22p63s23p64s23d6
Zeff=26-24=2

Co
1s22s22p63s23p64s23d7
Zeff=27-25=2

Ni
1s22s22p63s23p64s23d8
Zeff=28-26=2

*Zeff doesn't change within a period for the transition metals so we don't see them get
very much smaller as you move RIGHT within a period.

Know how to answer these 2 questions!!!

WHY do atoms get LARGER as you move DOWN within the same group on the periodic table?
o

As you move down a group, electrons are added to higher energy levels that are
consequently farther from the nucleus. In addition, the electrons in higher energy levels
are more shielded by the inner electrons thus greatly reducing the attractive force
between the nucleus and outer electrons and allowing the outer electrons to move
farther from the nucleus thus resulting in a larger atom.

WHY do atoms get SMALLER as you move RIGHT within the same period on the periodic table?
o

As you move right within a period, each atom has additional protons and electrons, but
the additional electrons are not being added to higher principal energy levels so the
amount of shielding by the inner electrons does not increase. Therefore, the additional
protons in the nucleus are able to pull more strongly on the outer electrons and thus
pull them in closer to the nucleus making the atom smaller.

Problems: Arrange each group of atoms from smallest to largest:

a. Mg, S, Si
S, Si, Mg
b. As, N, P
N, P, As
c. As, Sb, Se
Se, As, Sb

Ion Size
o

This trend doesn't have much of a pattern on the periodic table, but it is definitely
predictable.

CATIONS ARE SMALLER than the atom from which they form
o To form a cation, an atom must lose it's outer electrons thus getting rid of an entire
principal energy level

You can prove that cations are smaller based

on Zeff also:
Mg
1s 2s22p63s2
Zeff = 12 - 10 = 2
2

Mg2+
1s 2s22p6
Zeff = 12 - 2 = 10
2

Zeff is much larger for the Mg2+ ion so that

means the protons have more attraction for
the outer electrons and thus make the ion
smaller.

ANIONS ARE LARGER than the atom from which they form
o To form an anion, an atom will gain electrons
o The additional electrons cause electron/electron repulsion which tends to "push"
the electrons away from each other (they spread out more) thus making the ion
larger
This effect is not due to changes in Zeff since the
additional electrons are added to the same
principal energy level.
F
1s 2s22p5
Zeff = 9 - 2 = 7
2

F1s 2s22p6
Zeff = 9 - 2 = 7
2

Zeff is the same for both atom and anion, so the

change in size must be due to increased electron
repulsions from the gained electrons.

Isoelectronic Species
o

These are particles (atoms and ions) that have the same number of electrons
Example: Which is smallest?
Ne
1s22s22p6
10e
Zeff=10-2=8

Na+
1s22s22p6
1s22s22p6
10e
Zeff=11-2=9
Zeff=12-2=10

Mg2+
10e

*Mg2+ is the smallest because it has the largest Zeff

*For isoelectronic species, the one with the most protons is always going to be the
smallest!!!

Problems: Arrange from smallest to largest:

Fe3+, K+, S2-, Se2Calculate Zeff for all
K+, S2-, Se2-, Fe

Ionization Energy
o

The minimum amount of energy required to remove an electron from a gaseous atom in its
ground state
o 1st ionization energy = energy required to remove 1st electron
o 2nd ionization energy = energy required to remove 2nd electron
o 3rd ionization energy = energy required to remove 3rd electron

Example: Na atom
1st I.E. = 496 kJ/mol
(results in Na+)
2nd I.E. = 4,560 kJ/mol (results in Na2+)
*We never see an Na2+ ion because the energy requirement to make it is too high!!!

Example: Mg atom
1st I.E. = 738 kJ/mol
(Mg+)
2nd I.E. = 1450 kJ/mol (Mg2+)
3rd I.E. = 7730 kJ/mol (Mg3+)
*Note how big the 3rd I.E. is...that's why you never see an Mg3+ ion.

The general trend for Ionization Energy is shown below:

Ionization energy increases as you move

up and to the right on the periodic table.

*You can see that smaller atoms have higher ionization energies because the outer electrons are
more strongly attracted to the nucleus.

There are several exceptions to the ionization energy periodic trend:

o You can see that ionization energy drops going from "s" orbitals to "p" orbitals in the
same period
This is because electrons in "p" orbitals are higher energy and are thus
easier to remove from the atom
o

There is another dip in energy when you go from group 15 to group 16 in the same
period
This is due to the pairing of electrons in the "p" orbitals
Group 15

Group 16

2 electrons in the same

orbital causes slightly more
repulsion so it makes the
electron easier to remove

Electron Affinity
o

The energy change associated with adding an electron to an atom

o It is easy to add an electron to an atom that has a high electron affinity
o It is difficult to add an electron to an atom that has a low electron affinity
o

Some textbooks show electron affinity values as negative energy values because
electrons must release energy to get closer and closer to the nucleus and eventually
become part of the atom (energy releases are negative, right?)
In these books, chlorine has the most negative electron affinity value and
thus has the highest electron affinity of any atom (it is the easiest atom to
add an electron to)

There is a more recent trend in textbooks to show electron affinity values as

positive energy values which makes them a little easier to work with
In these books, chlorine has the most positive electron affinity value, yet it
still has the highest electron affinity of any atom (it is still the easiest atom
to add an electron to)

Just know that atoms with large electron affinity values (whether they are positive
or negative number) will generally accept electrons.
o

*Noble gases are not involved in this trend

(because they do NOT want another electron
to be added to them)

Electron Affinity increases as you move up

and to the right on the periodic table.

Metallic Character
o
o

The easier it is to remove an electron, the more "metallic" an atom is.

Therefore, larger atoms have the most metallic character
o Because their outer electrons are so far from the nucleus, they are not strongly
attracted to the nucleus

Metallic character increases as you

move down and left on the periodic
table.

Electronegativity
o

The attraction an atom has for electrons in a bond

Example: The HF molecule

H and F share electrons to form a bond
between them. However, Fluorine has a
stronger attraction for the shared
electrons and thus pulls the electrons
closer to it. This creates a region of higher
electron density around the fluorine
nucleus and makes the "fluorine end" of
this compound more negatively charged.
We call this a polar molecule when there is
an uneven sharing of electrons in a bond.

Fluorine is the most electronegative element.

Each element is assigned an electronegativity
number from 0 to 4 (4 being the most
electronegative)

Electronegativity increases as you move

up and to the right on the periodic table.
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