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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).
Atomic Radii have a predictable trend on the periodic table as shown in the picture below:
One way to explain this trend is to look at the effective nuclear charge of atoms
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)
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)
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)
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.
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.
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
Mg2+
1s 2s22p6
Zeff = 12 - 2 = 10
2
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
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
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.
*You can see that smaller atoms have higher ionization energies because the outer electrons are
more strongly attracted to the nucleus.
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
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)
Just know that atoms with large electron affinity values (whether they are positive
or negative number) will generally accept electrons.
o
Metallic Character
o
o
Electronegativity
o