Periodic Table 1

The Periodic Table

The elements in the periodic table
are arranged in order of atomic Hydrogen is sometimes shown,
number, starting with hydrogen, as here, in Group 1. It may also
which has atomic number 1. be placed in the middle of the
The groups are the vertical Periodic Table and not in any
column in the periodic table and group.
the periods are the horizontal
rows.
Periodic Table 2

Variation of properties down a group and across a period

Electronegativity
In a covalent bond between two different atoms the atoms do not attract the electron pair in the
bond equally. How strongly the electrons are attracted depends on the size of the individual
atoms and their nuclear charge.

ELECTRONEGATIVITY is a measure of the attraction of an atom in a molecule for the

electron pair in the covalent bond of which it is a part.

Electronegativity decreases down a group - the reason for this is

Electronegativity increases across a period - the reason for this is

Periodic Table 3

First Ionisation Energy

The first ionisation energy for an element is the energy required to remove the outermost
electron from a gaseous atom, that is the energy for the The full definition is: the energy required
process: to remove one electron from each atom
in one mole of gaseous atoms under
standard conditions.

Variation of Ionisation Energy Down a Group

Down any group in the

Ionisation Energy for Group 1
Periodic Table the ionisation
550
energy decreases.
Li
500
Na
Ionisation Energy / kJ mol -1

This can be seen in the graph.

450
This is because
K
Rb
400

350 Cs

300
0 1 2 3 1
Group 4 5 6

Variation of Ionisation Energy across a Period

If the data for Period 3, from Na 1600

to Ar in the Periodic Table is 1400 Ar

-1
First ionisation energy / kJ mol

considered:
1200
Cl
1000
The general trend is P S
that the Ionisation 800
energy increases from Mg
Si
600
left to right across a
Al
period. 400 Na

200

0
0 1 2 3 Period
4 35 6 7 8 9
Periodic Table 4

Metallic properties

The metallic and non-metallic properties of elements can be related to ionisation energies.

A metallic structure consists of a regular lattice of positive ions in a sea of delocalised

electrons. To form a metallic structure, an element must be able to lose electrons fairly readily
to form positive ions. Going across a period the ionisation energy increases and so elements
lose electrons less easily. So, metallic structures are formed by elements on the left-hand side
of the periodic table, which have lower ionisation energies.

Going down a group in the periodic table, ionisation energy decreases, therefore elements are
much more likely to exhibit metallic behaviour lower down a group. This can be seen
especially well in group 14 going from non-metallic carbon at the top, through the metalloids
(Si and Ge) to the metals tin and lead at the bottom.

In general, metallic elements tend to have large atomic radii, low ionisation energies, less
exothermic electron affinity values and low electronegativity.
Periodic Table 5

Atomic Radius
The atomic radius is basically used to describe the size of an atom. The larger the atomic
radius, the larger the atom.

The atomic radius is usually taken as half the internuclear

distance in the element. For example in a diatomic molecule
such as chlorine, where two identical atoms are joined together,
the atomic radius would be defined as shown in the diagram.

Atomic radius increases down a group.

Atomic radius decreases across a period.

200
The graph shows the
180
Na variation of the atomic
160 radius across Period 3 in
Mg
the Periodic Table.
Atomic radius / pm

140
Al
120

100
Si No atomic radius is shown
P
S
Cl for argon as
80

60

40
20
0
0 1 2 3 Period
4 35 6 7 8 9
Periodic Table 6

Ionic radius
The ionic radius is a measure of the size of an ion. In general, the radii of positive ions are
smaller than their atomic radii and the radii of negative ions are greater than their atomic
radii.

300
Cs
Rb
250 K

200 Na
Radius / pm

Li
Cs+
150
Rb+
K+
100
+
Na
+
50 Li

0
Group 1

250
-
- I
Br
200 -
Cl
Radius / pm

150
- Br
F
I
100
Cl
F
50

0
Group 7
Periodic Table 7

Li Na K Na+ Na

Cl Cl- Na Cl

Cl- Ar K+ Na+ Mg2+ Al3+

Periodic Table 8

Electron affinity
The first electron affinity involves the energy change when one electron is added to a gaseous
atom:

Variation of electron affinity down a

group:

Variation of electron affinity across a period

Periodic Table 9

Group 1 elements
The reactions of an element are
The elements in group 1 are known as the alkali metals. They determined by the number of
are all highly reactive, soft, low melting point metals . They electrons in the outer shell (highest
are placed together in group 1 for two reasons – they all have main energy level) of their atoms.
one electron in their outer shell and they react in very similar Because elements in the same
ways (similar chemical properties). group in the periodic table have the
same number of electrons in their
outer shell, they react
The bonding in all these elements is metallic. The solid is in basically the same way.
held together by electrostatic attraction between the positive
ions in the lattice and the delocalised electrons.

Reactions of the elements in Group 1

The elements in Group 1 are all reactive metals that react readily with, among other things,
oxygen, water and halogens. The atoms all have 1 electron in their outer shell and reactions
virtually all involve the loss of this outer shell electron to form the positive ion M+. The
reactions become more vigorous as the group is descended because

Reaction with oxygen: the alkali metals react vigorously with oxygen and all tarnish rapidly
in air. The general equation for the reaction is:
M2O is a basic oxide, which will dissolve in water to
4M(s) + 2O2(g) → M2O(s) form an alkaline solution, containing M+ and OH- ions.

Reaction with water: the alkali metals react rapidly with water. The general equation for
the reaction is:
2M(s) + 2H2O(l) → 2MOH(aq) + H2(g) Li, Na and K are all less dense than water.

An alkaline solution is formed. The alkali metal hydroxides are strong bases and ionise
completely in aqueous solution.
The reaction with water becomes more vigorous as the group is descended, thus sodium melts
into a ball, fizzes rapidly and moves around on the surface of the water, but, as well as this,
potassium bursts into flames (lilac) and caesium explodes as soon as it comes into contact
with water.
Periodic Table 10

Group 17
The elements in group 17 are known as the
halogens. They are all non-metals consisting of
diatomic molecules (X2).

Melting point increases down Group 17

The atoms of the elements in Group 17 all have 7 electrons in their outer shell and react, either
by gaining an electron to form the X- ion or by forming covalent compounds. The reactivity
decreases down the group and fluorine is the most reactive element known, reacting directly
with virtually every other element in the Periodic Table.
The halogens all react with the alkali metals to form salts. How vigorous the reaction is depends
The general equation is: on the particular halogen and alkali
2M(s) + X2(g) → 2MX(s) metal used; the most vigorous reaction
occurs between fluorine and caesium
The salts formed are all white/colourless fairly typical and the least vigorous reaction
ionic compounds. They contain M+ and X- ions. All alkali between lithium and iodine.
metal chlorides, bromides and iodides are soluble in
water and form colourless, neutral solutions.

Displacement reactions of halogens

These are reactions between a solution of the halogen and a solution containing halide ions.
A small amount of solution of a halogen is added to a small amount of a solution containing a
halide ion and any colour changes are observed.
Potassium chloride, bromide and iodide solutions are all colourless.

The more reactive halogen displaces the halide ion of the less reactive halogen from solution.
Thus chlorine displaces bromide ions and iodide ions from solution and bromine displaces
iodide ions from solution.
 Periodic Table 11
Oxides of Period 3 Elements

Sodium Magnesium Aluminium Silicon Phosphorus Sulphur Chlorine

Phosphorus(III)
Sulphur(IV) oxide Chlorine(I) oxide
Name of Sodium Magnesium Aluminium Silicon(IV) oxide
Oxide Oxide oxide oxide oxide Phosphorus(V)
Sulphur(VI) oxide Chlorine(VII) oxide
oxide
Formula of
oxide
Physical LIQUID GAS GAS
State at 25 oC SOLID SOLID LIQUID LIQUID
Bonding in
oxide IONIC COVALENT
Structure
Species
present in
liquid state
Electrical
conductivity
when molten
 Periodic Table 12

Reactions of Period 3 oxides with water

Sodium Magnesium Aluminium Silicon Phosphorus Sulphur Chlorine
P4O6 SO2 Cl2O
Formula of oxide Na2O MgO Al2O3 SiO2
P4O10 SO3 Cl2O7
Nature of element Metal Non-metal
GIANT
Bonding in oxide IONIC COVALENT MOLECULAR
COVALENT
Nature of oxide BASIC AMPHOTERIC ACIDIC
Reaction with Soluble Sparingly soluble,
Insoluble Soluble and react
water and reacts some reaction
Solution formed Alkaline Slightly alkaline - Acidic

In general, metallic oxides are basic and non-metallic oxides are acidic.
A basic oxide is one which will react with an acid to form a salt and, if soluble in water, will produce an Na2O(s) + H2O(l) → 2NaOH(aq)
alkaline solution.
Magnesium oxide, because of the high charges on the ions, is not very soluble in water but it does react MgO(s) + H2O(l) → Mg(OH)2(aq)
to a small extent to form a solution of magnesium hydroxide, which is alkaline:
Aluminium, is right on the dividing line between metals and non-metals and forms an amphoteric oxide (some of the properties of a basic
oxide and of an acidic oxide). Aluminium is here exhibiting properties which are between that of a metal and a non-metal.
The remaining oxides in the table are all acidic oxides. An acidic oxide is one which reacts with bases/alkalis to form a salt and, if
soluble in water will produce an acidic solution.
Non-metal oxides such as SO2 are produced in
P4O10(s) + 6H2O(l) → 4H3PO4(aq) SO3(g) + H2O(l) → H2SO4 various industrial processes, when coal is burnt
Phosphoric(V) acid sulphuric (VI) acid and when petrol is burnt in an internal
combustion reaction. These can be responsible
Nitrogen oxides
for acid rain which can, amongst other things,
There are many oxides of nitrogen, ranging in formula from N2O to N2O5. Two of the most environmentally
important are nitrogen(II) oxide [NO] and nitrogen(IV) oxide [NO2].
kill fish in lakes and trees in forests.
Nitrogen reacts with oxygen at very high temperatures to form NO [nitrogen monoxide, nitric oxide or
nitrogen(II) oxide]: N2(g) + O2(g) → 2NO(g) Nitrogen oxides (NOx) may be formed in internal
This reaction occurs in the internal combustion engine. NO is virtually insoluble in water and is classified as combustion engines and these are involved in
a neutral oxide. NO can be oxidised in the atmosphere to NO2, which can react with water to produce the formation of photochemical smog in cities.
nitric(V) acid [HNO3], which is one of the acids responsible for acid deposition. NO2 can be classified as an
acidic oxide: 2NO2(g) + H2O(l) → HNO2(aq) + HNO3(aq)
Periodic Table 13

The Transition Elements (d-block)

The first row d-block elements are:
There are also two other
rows of d-block elements.
They are called d block elements because the sub-shell being filled across this series is the 3d
subshell. The electronic configuration range from [Ar] 4s2 3d1 for scandium to [Ar] 4s2 3d10 for
zinc.

The transition elements can be defined A transition element is an element which forms at
as different from the d-block elements least one stable oxidation state (other than 0) with a
and the definition we will use here is: partially-filled d subshell
According to this definition zinc will not be counted as a transition element as the only ion formed
by Zn is the 2+ ion, with electronic configuration 1s2 2s2 2p6 3s2 3p6 3d10.

The inclusion/exclusion of scandium as a transition element according to this definition is much

more controversial. In virtually every compound scandium has oxidation state +3 (no d
electrons) however, it also forms a couple of compounds (ScH2 and CsScCl3) with formal
oxidation state +2, but the bonding in these compounds is more complicated and they do not
necessarily contain the 2+ ion.
Periodic Table 14

Properties of the transition elements

1600
Ar It can be seen that the
1400
-1

variation of ionisation
First ionisation energy / kJ mol

Cl
1200 energy and atomic radius
P across the series of the
1000
S transition elements is
Si
800 Mg
Cu much smaller than across
Cr Fe Co Ni
600
Ti Mn Period 3.
V
Al
400 Na

200

0
0 1 2 3 4 5 6 7 8 9

200
Na
180
Mg
160
Ti Al
Atomic radius / pm

140
Cr Mn Fe Co Ni Cu
V
120
Si
100 P Cl
S
80

60

40
20

0
0 1 2 3 4 5 6 7 8 9

Characteristics of Transition Metals

They are all typical metals, i.e. they have high melting points and
densities.
They can exhibit more than one oxidation state in
compounds/complexes.
They form complex ions.
They usually form coloured compounds/complexes.
The elements and their compounds/complexes can act as catalysts in
many reactions.
Periodic Table 15

Ionisation of transition metals The 4s electrons are always removed before the 3d electrons
Element Electronic configuration Ion Electronic configuration
Thus the 2+
Cr
electronic Cr
configurations of Cr3+
some transition Mn Mn2+
metal ions are:
Fe2+
Fe
Fe3+
Co Co2+
Cu+
Cu
Cu2+

Variable Oxidation States

The positive oxidation states exhibited by the transition elements are shown in the table:

Mn Not all oxidation states

Cr 7 Fe are common.
V 6 6 6
Ti 5 5 5 5 Co Ni Cu The greatest number
4 4 4 4 4 4 4 4 of different oxidation
3 3 3 3 3 3 3 3 states and the highest
oxidation states are
2 2 2 2 2 2 2 2 found in the middle of
1 1 1 1 1 1 1 the series.
0 0 0 0 0 0 0 0

In most cases this is because

ALL TRANSITION METALS SHOW OXIDATION STATE +2 they have 2 electrons in the 4s
sub-shell and removal of these generates an oxidation state of +2.

Why transition metals have variable oxidation state

Periodic Table 16

Magnetic properties of transition metal compounds

Paramagnetism is caused by unpaired electrons – paramagnetic substances are

attracted by a magnetic field.

Diamagnetism is caused by paired electrons – diamagnetic substances are

repelled slightly by a magnetic field.

All substances have some paired electrons and so all substances exhibit diamagnetism.
However, the diamagnetic effect is much smaller than the paramagnetic effect and so, if there
are any unpaired electrons present, the paramagnetic effect will dominate and the substance
will be paramagnetic overall and attracted by a magnetic field. The more unpaired electrons,
the greater the paramagnetism (magnetic moment).

e.g. FeCl3

Classify each of the following ions as diamagnetic or paramagnetic:

ION Diamagnetic Paramagnetic

Ti2+
Cu+
Co3+
Mg2+
Zn2+
Cr3+
Ni2+
Periodic Table 17

Complex Ions
A complex ion consists of a central transition metal ion surrounded by LIGANDS.
The structure of [Fe(H2O)6]2+ is :

LIGANDS are negative ions A ligand must

or neutral molecules which possess a lone pair
use lone pairs of electrons of electrons.
to bond to a transition metal
ion to form a complex ion.
Co-ordinate covalent A ligand is a
bonds are formed between Lewis base.
the ligand and the transition
metal ion.

H2O is the ligand in this complex ion.

The shape of this complex ion is octahedral and it is called the hexaaquairon(II) ion.

The oxidation state of a transition metal in a complex ion

The oxidation number of a transition metal in a complex Neutral Ligands 1- ligands
ion is worked out from the charges on the ligands. H2O Cl-
Ligands may be either neutral of negatively charged. NH3 CN-
Examples of each type of ligand are:
Consider:
Oxidation state of transition metal
[Fe(H2O)6]2+
[Ni(CN)4]2-
[Co(NH3)2Cl4]-

Work out the total charge on each of the following ions

Oxidation state of transition metal Overall charge
[Cu(NH3)4(H2O)2] +2
[Mn(H2O)5OH] +3
[Co(NH3)3Cl3] +3
Periodic Table 18

Shapes of Complex Ions

Transition metal complexes do NOT obey VSEPR rules so that, although 6 co-ordinate
complexes are virtually ALWAYS OCTAHEDRAL, 4 co-ordinate complexes may be tetrahedral or
square planar.
The shapes of some complex ions are shown in the table:

Formula [Fe(H2O)6]3+ [Fe(CN)6]3-

Shape
Oxidation number of metal

Formula [CuCl4]2- [Ni(CN)4]2-

Shape tetrahedral square planar
Oxidation number of metal

Formula [Ag(NH3)2]+
Shape linear
Oxidation number of metal
Periodic Table 19

Formation of Complex Ions

Complex ions may undergo substitution reactions where H2O ligands are replaced by other
ligands.
As the HCl is added the
Addition of concentrated hydrochloric acid to copper sulphate solution solution goes through
[Cu(H2O)6]2+(aq) + 4Cl-(aq)  [CuCl4]2-(aq) + 6H2O(l) green (mixture of blue
pale blue yellow and yellow) to yellow

When iron(III) salts are dissolved in water very little of the pale purple [Fe(H2O)6]3+(aq) ion is
present. The [Fe(H2O)6]3+(aq) ion is unstable in aqueous solution as the 3+ charge on the metal
ion causes the water molecules to be strongly polarised so that the ion dissociates:
[Fe(H2O)6]3+(aq)  [Fe(H2O)5(OH)]2+(aq) + H+ Le Chatelier’ Principle – a strongly
acidic solution means that the
The [Fe(H2O)6]3+ ion can then only be prepared in strongly
concentration of H+ ions is high and
acidic solution.
the position of equilibrium is shifted to
the left hand side.
If a high concentration of cyanide (!) ions is added to a
solution containing the Fe3+(aq) ion, the [Fe(CN)6]3- ion can be formed. We can represent the
reaction as:
[Fe(H2O)6]3+(aq) + 6CN-  [Fe(CN)6]3-(aq) + 6H2O
red/orange
If ammonia solution is added to a solution of silver nitrate the colourless [Ag(NH3)2]+ ion is
formed:
[Ag(H2O)2]+ + 2NH3(aq)  [Ag(NH3)2]+(aq) + 2H2O(l)
Periodic Table 20

Formation of Coloured Complexes

[Cu(H2O)6]2+ blue
The colours of some complex ions are: [Cu(NH3)4(H2O)2]2+ deep blue/violet
[Fe(SCN)(H2O)5]2+ blood red
[Ni(H2O)6]2+ green
In a gaseous transition metal ion all the 3d
orbitals have the same energy, that is, they are
degenerate. However, when this ion is
surrounded by ligands in a complex ion, these d
orbitals are split into two groups. In an
octahedral complex ion there are two orbitals in
the upper group and three orbitals in the lower
group.

The splitting is due to the repulsion between the

electrons in the metal ion d orbitals and the
lone pairs on the ligands. Two of the metal d
orbitals point directly at the ligands and are so
raised in energy whereas the other three d
orbitals point between the ligands and are
lowered in energy.

Energy in the form of visible light can be absorbed to promote an electron from
the lower set of orbitals to the higher set.

These are called

d-d transitions.
Colours arise when
light is absorbed in
the visible region of
the spectrum
The complex appears the
complementary colour to the light
absorbed. Complementary
colours are given by a colour
wheel.

White light is a mixture of all

the colours of the spectrum
Consider copper sulphate solution:
Periodic Table 21

When white light travels through this solution orange

light is absorbed to cause an electron to be promoted
from the lower set of d orbitals to the higher set. This
means that the light coming out contains all the
colours of the spectrum except orange and so will
appear blue.
Blue is the complementary colour to orange.

For a substance to appear coloured light in the

visible region of the spectrum must be absorbed.

Formation of coloured complex ions/compounds requires the presence of a partially-filled d subshell.

Explain why the following ions are colourless

ION REASON FOR BEING COLOURLESS

Ti4+

Zn2+

Sc3+

Predict the colour of the following transition metal complex

Factors which affect the colour of transition metal complexes

Periodic Table 22

1 IDENTITY OF THE METAL

DIFFERENT METALS IN THE SAME Mn2+(aq) (3d5) is pale pink

OXIDATION STATE WILL HAVE Fe2+(aq) (3d6) is pale green
DIFFERENT COLOURS.

Different metals will have different electronic configurations and since colours are due to
electronic transitions, different arrangements of electrons will give rise to different colours. The
colour is also influenced by the number of protons in the nucleus – different numbers of
protons means that the ligands will be pulled in to different extents and the d orbitals will be
split by a different amount.

2 OXIDATION NUMBER

THE SAME METAL IN DIFFERENT OXIDATION [Fe(H2O)6]2+(aq) is pale green

STATES WILL HAVE DIFFERENT COLOURS. [Fe(H2O)6]3+(aq) is pale violet

NOTE: most aqueous solutions of Fe3+

This is due to two reasons are actually yellow but they do not
• the electronic configurations of the two ions are different contain [Fe(H2O)6]3+(aq)
• the greater charge on the Fe ion causes the ligands to be
3+

pulled in more closely so that the splitting of the d orbitals increases.

3 NATURE OF THE LIGAND

THE SAME METAL ION CAN EXHIBIT [Cu(H2O)6]2+(aq) is pale blue
DIFFERENT COLOURS WITH DIFFERENT [Cu(NH3)4(H2O)2]2+(aq) is dark blue/violet
LIGANDS.
This is mainly due to the different splitting of the d orbitals caused by the different ligands.

Ligands can be arranged into a SPECTROCHEMICAL SERIES according to how much they
cause the d orbitals to split:

I− < Br− < Cl− < F– < OH− < H2O < NH3 < CO ≈ CN−
e.g. NH3 causes greater splitting of the d orbitals than H2O

[Cu(H2O)6]2+(aq) [Cu(NH3)4(H2O)2]2+(aq)

• greater splitting of d orbitals

• higher frequency of light absorbed