13.

1 - Periodic trends Na

Ar (the third period)

Periodic trends are often shown graphically and questions ask you to explain
the trend illustrated. e.g.:

See the Period Table Trends shockwave software program to illustrate many
more examples of periodicity

Characteristic

Trend (left to right)

Reason

Atomic radius

decreases in size from

left to right

increased attractive force (acting

on the same energy shell) from
the nucleus as the number of
protons (and hence the nuclear
charge) increases

Ionic radius

decreases across the

period until formation
of the negative ions
then there is a sudden
increase followed by a
steady decrease to the
end

In general as above. The sudden

increase on formation of negative
ions is due to the new (larger)
outer shell

Electronegativity Increases

More electron attracting power of

the larger nuclear charge as we
move to the right

Metallic
character

Decreases - Na, Mg, Al Metallic character is a measure of

metals; Si metalloid;
the ease of loss of electrons from
P, S, Cl, Ar non-metals the outer shell. This decreases
with increasing nuclear charge.

Oxides

Na, Mg - alkaline
Al - amphoteric
Si, P, S, Cl -acidic

What is an amphoteric oxide?

Chloride
character

NaCl - ionic
MgCl2 - some covalent
character
AlCl3 - covalent
The remainder
covalent

Increasing charge density of the

positive ion polarises the chloride
ion as we move to the right hand
side

Melting point

Na
Al steady
increase

Increasing availability of electrons

in the metallic bonding associated
with greater charge density of the
metal ion
Si giant macromolecular structure
P4 molecules
S8 molecules
Cl2 molecules and Ar atoms

Si massive increase
P large decrease
S small increase
Cl
Ar decrease

The 3rd Period is often studied to show periodic trends

Chemical periodicity of period 3 oxides

Na2O

MgO

Al2O3

SiO2

P4O10

SO3

(or
P4O6)

(or
SO2)

Cl2O7
Cl2O

P4O10 + SO3 + Cl2O7 +

6H2O -> H2O -> H2O ->
4H3PO4 H2SO4 2HClO4

Add H2O

Na2O + MgO +
H2O -> H2O -> Insoluble
2NaOH Mg(OH)2

Insoluble

Add HCl

Na2O +
H+ ->
2Na+ +
H2O

No
No
No
No
reaction reaction reaction reaction

Add NaOH

MgO +
2H+ ->
Mg2+ +
H2O

Al2O3 +
6H+ ->
2Al3+ +
3H2O

Al2O3 +
No
No
2OH- +
reaction reaction 3H2O ->
2Al(OH)4

Basic
Oxide
Conductivity Good
Melting
1275
Point
Nature

P4O6+ SO2 + Cl2O +

6H2O -> H2O -> H2O ->
4H3PO3 H2SO3 2HOCl

H3PO4 +
OH- -> SO2 +
H2PO4- OH- ->
SiO2 +
2OH- -> + H2O HSO4
SiO32- + H PO + SO +
3
3
2
H2O
OH- -> OH- ->

Basic
Oxide
Good

Amphoteric Acidic
Oxide
Oxide
Good
None

H2PO3+ H2O
Acidic
Oxide
None

2852

2027

24

1610

HCl2O7 +
OH- ->
Cl2O72- +
H2O

HSO3Acidic
Oxide
None

HOCl +
OH- ->
OCl- +
H2O
Acidic
Oxide
None

17

-92

Chemical periodicity of period 3 chlorides

NaCl
Add H2O

MgCl2

Al2Cl6

Dissolves Dissolves Hydrolysis

to give
to give
to give

SiCl4

PCl3

PCl5

Cl2

Reacts Reacts Reacts Dissociates

to
to
to
to give HOCl

free ions

ionic
Nature
Conductivity Good
Melting
801
Point

free ions

[Al(H2O)6]3+ produce produce produce and HCl

and Cl- ions HCl and H3PO3
H3PO4
Si(OH)4 and HCl and HCl

ionic

covalent

covalent covalent covalent covalent

Good

None

None

None

714

178

-70

-112

None

None
-101

Questions
Ionisation Energy IE:

M(g)

M2+(g) +

e- (kJ/mol-1)

Why does IE decrease as you move down a metallic group?

Why does IE increase across the period?

Electronegativity
When an atom is covalently bonded its electronegativity is its ability to
attract a bonded pair of electrons to itself. (This is on an arbitrary scale: the
Pauling scale)

How does electronegativity change across the periodic table/

How does it change as atomic number increases down a group?

Atomic Radius: the distance between the nuclei of bonded atoms.

What are the main trends in atomic radius?

Explain the trend across the period.

Explain the trend down group 1

Ionic Radius: the distance between the nuclei of bonded ions.

For positive (+) Cations:

d/2

How do cations compare in size with the atoms they came from? Explain your
answer.

Explain the trend in size of the iso electronic ions Na +, Mg2+ and Al3+

For negative (-) Anions

How do anions in group VII compare in size with the atoms they come from?
Explain your answer.

Explain the trend in size of the iso electronic ions P 3-, S2- and Cl-

How do cations and anions change in radius down all groups? Explain your
answer?

Melting Point
M.P. depends on
1. The strength of the bond between the particles
2. The type of structure. (eg Metallic, Giant covalent or Simple Molecular)
Groups I & VII have simple trends. Other groups eg group IV change from
non-metallic to metallic down the group so the trend in MP may not be simple.

Describe & explain how MP changes as you go down group I

Describe & explain how MP changes as you go down group VII

Why is the MP of carbon so high? How does it compare to the MPs of the
other group IV elements?

13.2 - d-block elements (first row: Sc

Zn)

Characterised by the following properties:

Variable oxidation states
Complex ions
Magnetic properties

Coordinated ligands
Coloured compounds
Catalytic properties

Variable oxidation state

The multiple oxidation states of the d-block (transition metal) elements are
due to the proximity of the 4s and 3d sub shells (in terms of energy). All
transition metals exhibit a 2+ oxidation state (both electrons being lost from
the 4s and all have other oxidation states (common in red).
Sc Ti

V Cr Mn Fe Co Ni Cu Zn
+1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3
+4 +4
+4
+5
+6 +6 +6
+7
Write the names & formulas of some transition metal compounds that you
have already met.
Coordinated ligands
Ligands are the molecules (or ions) which donate an electron pair to form a
dative covalent bond with the central transition metal atom (forming a
complex molecule or ion).
List some molecules that have lone pairs which could be important ligands.

Coordination (See separate PowerPoint)

Complexes
These are species which are formed around a central atom, with other
atoms, ions or molecules donating an electron pair to form a covalent bond
to this central atom. The result is a "complex" usually an ion but may also be
a molecule.

Complex
[Fe(H2O)6]3+
[Fe(CN)6]3[CuCl4]3[Cu(NH3)4]2+
[Ag(NH3)2]+
Ni(CO)4

shape

ligands

coordination
name
number
octahedral water
6
hexa-aqua iron III ion
hexacyano ferrate III
octahedral cyanide CN6
ion
tetrahedral chloride Cl4
tetrachloro cuprate I ion
square
tetra-ammine copper II
ammonia
4
planar
ion
linear
ammonia
2
diammine silver I ion
carbon
tetracarbonyl Nickel 0
tetrahedral
4
monoxide
molecule

Draw an example of an octahedral, a planar and a linear complex ion.

Coloured compounds
The colour in the transition metals (d-block) is often due to the splitting of
the d shell orbitals into slightly different energy levels. As a result, certain
wavelengths of energy can be absorbed by the d-block elements (with
electrons jumping between these slightly different energy levels), resulting
in the complementary colour being visible. Colour is affected by both the
oxidation state of the transition metal and the type of ligand.
Draw a simple diagram explaining this phenomenon.
Complex ion

Oxidation state of metal colour

ligand

[Fe(H2O)6]3+
[Fe(H2O)6]2+
[Cu(H2O)6]2+

III
II
II

Red/brown
Yellow/green
blue

water
water
water

[Cu(NH3)4]2+

II

deep blue

Ammonia

[CuCl4]2-

II

green

chloride
ion

OPTIONAL EXTRA INFO Crystal field theory: (See separate PowerPoint)

Magnetism

Transition metals and their ions often have unpaired 'd' electrons which
produce an asymmetric magnetic field that can be detected. This is called
paramagnetism. Examples:
Complex ion electronic configuration no of unpaired electrons magnetism
[Fe(H2O)6]3+
[Ar]4s0 3d5
5
paramagnetic
3+
[Cr(H2O)6]
[Ar]4s0 3d3
3
paramagnetic
2+
[Cu(H2O)6]
[Ar]4s0 3d9
1
paramagnetic
2+
[Ni(NH3)6]
[Ar]4s0 3d8
2
paramagnetic
2[CoCl4]
[Ar]4s0 3d7
3
paramagnetic
Catalytic activity
'd' block elements make good catalysts due to their multiple oxidation states
(hence their ability to react with different species and produce a path of
lower activation energy, and so allow the reaction to proceed at a faster
rate). Another possible reason for their catalytic activity is their available 'd'
orbitals which allow reacting molecules to co-ordinate to the surface of the
transition metal which in turn weakens the bonding within the molecule
allowing it to react.
Examples...

MnO2 in decomposition of hydrogen peroxide

V2O5 or Pt in the Contact process

Fe in Haber process

Ni in conversion of alkenes to alkanes, (hydrogenation)

Platinum or rhodium, as used in a car catalytic converter

Write out the equations, showing state symbols, of each of the

reactions used as examples above.
Draw diagrams illustrating what happens on the surface of nickel
when it catalyses the hydrogenation of an alkene.
What is meant by homogenous catalyst? Give an example.