Trends in the Periodic Table

 Many physical and chemical properties show distinctive trends across a period or
down a group. These trends are a predictive tool.
 These trends can be explained in terms of atomic structure.

Electrical conductivity – this is related to metallic character of an element; the trend is

not uniform across the Periodic Table ; Ag, Cu, Au, Al have the highest electrical
conductivity.

Trends Electrical Conductivity

Across a period Generally decreases as elements
become less metallic. Non-metals do
not have free mobile electrons in their
crystal structure
Down a group Generally increases as elements
become more metallic(except group
III). Down a group, the valence shell
electrons become further away from
the nucleus and can more easily
escape into a lattice.

Atomic radius – depends on the number of electron shells and the size of the nuclear
charge. Electron shells are attracted inwards as the charge on the nucleus increases.

Trends Atomic Radius

Across a period Decreases as the valence shell moves
closer towards the increasingly
positive nucleus
Down a group Increases as the number of electron
shells increases.

Ionisation energy – valence shell electrons are easily removed if they are further from
the nucleus or the nucleus has a small positive charge. The presence of shielding inner
electron shells reduces the energy required to ionize an atom.

Trends Ionisation energy

Across a period Increases because the atomic radius
decreases across a period so the
valence electrons are closer to the
nucleus
Down a group Decreases because the atomic radius
 increases as there are more electron
shells. The outer shell electrons are
not as strongly attracted to the nucleus
in atoms with more shells.

Melting and Boiling Points – the strength of the bonding in the crystal lattice affects the
melting and boiling points of the element.

Trends Melting and Boiling points

Across a period  Increases in groups I to IV
 Decreases as the lattice changes from
metallic to covalent network and then
covalent molecular.
Down a group  Decreases in groups I to IV
 Increases in groups V to VIII
 Generally increases for transition
metals

Electronegativity – is a measure of the electron –attracting ability of an element. Non-

metals are very electronegative(they attract electrons to complete their valence shell)
while metals are electropositive.

Trends Electronegativity
Across a period Increases as the metallic character
decreases.
Down a group Decreases as the metallic character
increases.

Valency – elements in the same group tend to have the same valency, although some
elements exhibit multiple valencies eg Gp V, Gp VI, Gp VII.

Trends Valency
Across a period Maximum valency increases from groups I
to VII in which group number equals
maximum valency.
Down a group Maximum valency is constant and equal to
the group number (except for Group VIII
with a valency of 0)

Reactivity – noble gases are unreactive ; heavy metals in the lower central region of the
transition metals are the least reactive ; the most reactive elements are found at the
bottom of groups I and II.

Trends Reactivity
Across a period Each period starts with a reactive metal and
 ends with an unreactive noble gas.
Down a group  Increases down group I and II.
 Decreases down a group of transition
metals.
 Decreases down groups III and IV fro
soft metals.
 Generally decreases down groups V to
VII for non-metals
 Increases down the group of noble
gases.

Summary of Periodic Trends

Electrical conductivity ………..decreases……………………………………………….→

.i.
.n. Atomic radius …………….decrease……………………………………………→
.c. .i.
..r .n.
Ionisation energy ……..increases ……………………………………..→
.e .c. .d.
..a .r. .e. Melting and Boiling Point ……increases then decreases…………..→
..s .e. .c. ..
..e ..a ..r .. .. Electronegativity…………….increases…………………→
s s e d
. e a e
. s s c
. . e r
. . s e
. . . a
. . . s
↓ ↓ . e
. s
↓ ↓
 Ionization Energy
Consider the following experiment: Starting with hydrogen and
proceeding through the periodic table, measure how much energy ot
takes to pull an electron away from each atom. The resulting atom
will be a cation and the energy it takes to pull the electron away is
called the ionization energy.

M ----> M+ + e- I.E.

If we plot these ionization energies versus atomic number the

resulting graph below emerges.

Clearly, the most striking feature of this graph is that there is an

inherent periodicity. How can this periodicity be explained? If we
examine the electronic configurations of these elements we find that
all elements with the lowest ionization energies -the alkali metals -
have similar electronic configurations - [NG]ns2. Similarly, all the
elements with the largest ionization energies - the noble gases- have
filled s and p electronic configurations - [NG](nd10)ns2np6. The
elements inbetween these two extremes also have similar electronic
configurations.
 Therefore, the periodicity of the data in the graph is a direct result of
the underlying periodicity in the electronic configuration of the
elements.
Back to index
C101 Class Notes
Prof. N. De Leon

Ionisation energy as evidence for sub-shells

Ionisation energy is a measure of the ease in which atoms lose
electrons and become positive ions.

The first ionisation energy is the energy required to remove one electron from
each atom of a mole of gaseous atoms.

M(g) - e- → M+(g)

Further electrons may be removed giving successive i.e.:

M+(g) - e- → M2+(g)

This energy is usually quoted in units of kilojoules per mole (kJ mol-1).

Energy is required to remove an electron from any atom because there is an

attractive force between the nucleus and the electron being removed which has
to be overcome.

The value of the first ionisation energy depends upon:

1. The effective nuclear charge

2. The distance between the electron and the nucleus
3. The 'shielding' produced by lower energy levels

Shielding involves the repulsion between electrons in inner, filled orbitals and
electron being removed from the outer orbital.
The graphs of atomic number against first ionisation number show that across

each period there is an increase in ionisation energy

Beryllium (Group II) has an extra electron and proton compared with
lithium. The extra electron goes into the same 2s orbital. The increase in
ionisation energy (I.E.) can be attributed to the increased nuclear charge.

The ionisation energy of Boron is less than that of Beryllium because in Boron
there is a complete 2s orbital. The increased shielding of the 2s orbital reduces
the ionisation energy.

Similarly, the I.E. of Oxygen is less than that of Nitrogen because the extra
electron is shielded by the half-filled 2p orbital.

The break in the graph between N-O can be explained by the increased repulsion
produced when two electrons are in the same orbital. The latter seems to be
preferred by examiners!

Within a group the first I.E. decreases down the group as the outer electron
becomes progressively further from the nucleus. Also there is more shielding
because of the extra filled orbitals.

The graph below shows the successive I.E. for sodium:

 The electronic structure for sodium is 1s2 2s2 2p6 3s1. The energy required to
remove the first electron is relatively low. This corresponds to the loss of one 3s
electron.

To remove the second electron needs a much greater energy because this
electron is closer to the nucleus in a 2p orbital.

There is a steady increase in energy required as electrons are removed from 2p

and then 2s orbitals.

The removal of the tenth and eleventh electrons requires much greater amounts
of energy, because these electrons are closer to the nucleus in the 1s orbital.

Finally an alternative way of expressing electron configuration as s, p,d, and f is

to use box notation as shown below for silicon:

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This page explains what second, third, (etc) ionisation

energy means, and then looks at patterns in
successive ionisation energies for selected elements.
It assumes that you understand about first ionisation
energy.

Important! If you have come straight to this page via a

search engine, you should read the page on first ionisation
energy before you go any further.

Defining second ionisation energy

Second ionisation energy is defined by the equation:

It is the energy needed to remove a second electron

from each ion in 1 mole of gaseous 1+ ions to give
gaseous 2+ ions.

More ionisation energies

You can then have as many successive ionisation

energies as there are electrons in the original atom.

The first four ionisation energies of aluminium, for example, are given by

1st I.E. = 577 kJ

mol-1
2nd I.E. = 1820 kJ
mol-1
3rd I.E. = 2740 kJ
mol-1
4th I.E. = 11600 kJ
mol-1

In order to form an Al3+(g) ion from Al(g) you would have

to supply:

577 + 1820 + 2740 = 5137 kJ mol-1

That's a lot of energy. Why, then, does aluminium form

Al3+ ions?

It can only form them if it can get that energy back

from somewhere, and whether that's feasible depends
on what it is reacting with.

For example, if aluminium reacts with fluorine or

oxygen, it can recover that energy in various changes
involving the fluorine or oxygen - and so aluminium
fluoride or aluminium oxide contain Al3+ ions.

If it reacts with chlorine, it can't recover sufficient

energy, and so solid anhydrous aluminium chloride
isn't actually ionic - instead, it forms covalent bonds.

Why doesn't aluminium form an Al4+ ion? The fourth

ionisation energy is huge compared with the first
three, and there is nothing that aluminium can react
with which would enable it to recover that amount of
extra energy.

Why do successive ionisation energies get larger?

Once you have removed the first electron you are left
with a positive ion. Trying to remove a negative
electron from a positive ion is going to be more
difficult than removing it from an atom. Removing an
electron from a 2+ or 3+ (etc) ion is going to be
progressively more difficult.

Why is the fourth ionisation energy of aluminium so

large?

The electronic structure of aluminium is

1s22s22p63s23px1. The first three electrons to be
removed are the three electrons in the 3p and 3s
orbitals. Once they've gone, the fourth electron is
removed from the 2p level - much closer to the
nucleus, and only screened by the 1s2 (and to some
extent the 2s2) electrons.

Using ionisation energies to work out which group an

element is in

This big jump between two successive ionisation

energies is typical of suddenly breaking in to an inner
level. You can use this to work out which group of the
Periodic Table an element is in from its successive
ionisation energies.

Magnesium (1s22s22p63s2) is in group 2 of the Periodic

Table and has successive ionisation energies:

Here the big jump occurs after the second ionisation

energy. It means that there are 2 electrons which are
relatively easy to remove (the 3s2 electrons), while
the third one is much more difficult (because it comes
from an inner level - closer to the nucleus and with
less screening).

Silicon (1s22s22p63s23px13py1) is in group 4 of the

Periodic Table and has successive ionisation
energies:

Here the big jump comes after the fourth electron has
been removed. The first 4 electrons are coming from
the 3-level orbitals; the fifth from the 2-level.

The lesson from all this:

Count the easy electrons - those up to (but not

including) the big jump. That is the same as the group
number.
Another example:

Decide which group an atom is in if it has successive

ionisation energies:

The ionisation energies are going up one or two

thousand at a time for the first five. Then there is a
huge jump of about 15000. There are 5 relatively easy
electrons - so the element is in group 5.

Exploring the patterns in more detail

If you plot graphs of successive ionisation energies

for a particular element, you can see the fluctuations
in it caused by the different electrons being removed.

Not only can you see the big jumps in ionisation

energy when an electron comes from an inner level,
but you can also see the minor fluctuations within a
level depending on whether the electron is coming
from an s or a p orbital, and even whether it is paired
or unpaired in that orbital.

Chlorine has the electronic structure

1s22s22p63s23px23py23pz1.

This graph plots the first eight ionisation energies of

chlorine. The green labels show which electron is
being removed for each of the ionisation energies.
If you put a ruler on the first and second points to
establish the trend, you'll find that the third, fourth
and fifth points lie above the value you would expect.
That is because the first two electrons are coming
from pairs in the 3p levels and are therefore rather
easier to remove than if they were unpaired.

Again, if you put a ruler on the 3rd, 4th and 5th points
to establish their trend, you'll find that the 6th and 7th
points lie well above the values you would expect
from a continuation of the trend. That is because the
6th and 7th electrons are coming from the 3s level -
slightly closer to the nucleus and slightly less well
screened.

The massive jump as you break into the inner level at

the 8th electron is fairly obvious!

Warning! People sometimes get confused with these

graphs because they forget that they are removing
electrons from the atom. For example, the first point refers
to the first electron being lost - from a 3p orbital. Basically,
you start from the outside of the atom and work in towards
the middle. If you start from the 1s orbital and work
outwards, you are doomed to failure!

To plot any more ionisation energies for chlorine

needs a change of vertical scale. The seventeenth
ionisation energy of chlorine is nearly 400,000 kJ mol-
1
, and the vertical scale has to be squashed to
accommodate this.

This is now a "log graph" - plotted by finding the

logarithm of each ionisation energy (press the "log"
button on your calculator). This doesn't simply squash
the vertical scale. It distorts it as well, to such an
extent that the only useful thing the graph now shows
is the major jumps where the next electron to be
removed comes from an inner level. The distortion is
so great in the first 8 ionisation energies, for example,
that the patterns shown by the previous graph are
completely (and misleadingly) destroyed.

Where would you like to go now?

To the atomic properties menu . . .

To the atomic structure and bonding menu . . .

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© Jim Clark 2000