1

FHSC1134
Inorganic Chemistry
Group 14
Chapter 4
Scopes
Group IV elements (C Pb)
Trends & physical properties (atomic
radius, melting point and boiling point,
electrical conductivities and first
ionization energy)
Thermal stability of chlorides with
oxidation number II and IV
Valence electronic configuration
ns
2
np
2
4 e
-
in the outer shell
p-block elements
Similarity between elements between
group less apparent
Change from non-metals through
metalloids to metals as the group
is descended.
General Characteristic of
Group IV Element
This change is due to the increasing atomic
radius and decreasing force of attraction of the
nucleus on the outer electrons.
The atoms, therefore, become more easily to
give up electrons for delocalisation in metallic
bonds.
Some physical & chemical
Properties of Group IV Elements
Elements C Si Ge Sn Pb
First ionization
energy (kJ mol
-1
)
1085 788 760 705 714
Stability of
oxidation states
+4 Stability of +4 oxidation
state
+2
Metallic character
Structure Giant molecular
structure
Metallic structure
Bonding
decrease
Physical Trends When Going
Down Group IV
Size / atomic radius (_______________)
First ionization energy (_____________)
Melting point & boiling point
(_____________)
Electrical conductivity (_____________)
2
Element C Si Ge Sn Pb
Atomic radius/
nm
0.077 0.114 0.122 0.14 0.154
1. Trend in atomic radius
Nuclear charge and screening effect increase.
Increase in screening effect is larger than the
increase in nuclear charge as each atom has one
more shell filled with electrons.
This causes the effective nuclear charge to
decrease.
Attraction (nucleus and e
-
cloud) weaker
Size of atom increases
Element C Si Ge Sn Pb
Atomic radius/
nm
0.077 0.114 0.122 0.14 0.154
2. Trend in 1
st
IE
1
st
IE decreases when going down the group.
Increase in the size of atoms coupled with the
decrease in the effective nuclear charge.
Ineffective nuclear charge causes the weak attraction
between nucleus and e
-
cloud.
e
-
is easier to be removed. Hence, 1
st
IE
IE of Pb is higher than IE Sn ineffective screening by
the 4f electrons in Pb, coupled with the increase in
nuclear charge.
Element C Si Ge Sn Pb
1st ionisation energy/
kJ mol
-1
1090 970 760 710 720
3. Trends in BP & MP
C, Si & Ge have giant covalent structures
(diamond-like).
Each atom is bonded with 4 other atoms
in tetrahedral shape by strong covalent
bonds in 3 dimensional array.
Strength of covalent bonds increases:
________ < ________ < _______ (structure)
Tin (Sn) exist as white tin and grey tin
White tin is metallic at room temperature with strong
metallic bond.
At low temperature, non-metallic grey tin.
Lead (Pb) can only exists as a metallic structure &
has strong metallic bond
Strength of metallic bonds: Sn-Sn > Pb-Pb
Pb (mp) > Sn (mp): exception case
atoms of lead (face centered cubic) are more closely
packed than the atoms of tin (tetragonal) in the solid
lattice.
the close packing increases the strength of the
metallic bond in lead.
Melting of giant covalent structures requires the
complete breaking of all the covalent bonds in
the solid lattice.
Melting of giant metallic structures only involves
the weakening of the metallic bonds.
More energy is required to break giant covalent
structures than giant metallic structures.
C, Si & Ge have higher bp and mp than Sn &
Pb
MP and BP decrease when going down Group IV
Variations in BP & MP
3
C Si Ge Sn Pb
Non-conductor
except for
graphite - poor
conductor
*Diamond not a
conductor
Semiconductor
of electricity
Good
conductors
of heat &
electricity
Non-metal Metalloids Metals
Electrical conductivity increases going down Group IV
4. Trend of Electrical Conductivity
Valence e
-
are located further away from the
nuclear attraction
Electrical Conductivity
when going down Group IV
They become loosely attracted & are easily
delocalised to form an e
-
cloud for the metallic
bond / free e
-
that are able to carry the electrical
charge, good conductor.
Conductivity temperature
Chemical Trends when
going down Group IV
Oxidation states of +2 and +4
Relative stability of the oxidation
states of +2 and +4
Oxidation States of +2 and +4
The +2 oxidation state for C, Si and Ge are
mostly (___________________) whereas for
Sn and Pb are more ionic. This is due to the
in the IE when the atomic size .
The +4 oxidation state is normally covalent
as the IE required to remove 4 e
-
is very
high.
Moreover, X
4+
(high charge density) can
distort the e
-
cloud surrounding the anion
covalent character in the bonding.
Oxidation
state of +4
Before the
formation of bond
Promotion of 1
of the s e
-
to the
empty p orbital
4 unpaired e
-
can
form 4 covalent
bonds
Relative stability of
+2 and +4 oxidation states
(Proton number)
Relative
stability
+4 oxidation state
+2 oxidation state
4
+4 Oxidation State becomes Less Stable
down Group IV
Group IV elements: the valence electronic
configuration of ns
2
np
2
The oxidation state of +4 is where all these
outer electrons are directly involved in the
bonding.
Lead tend to form +2 oxidation state instead
of +4 oxidation state.
This is due to the stronger inert pair effect in
lead.
(_____________________)
= As going down the the group, there is an
increasing tendency for the s
2
pair e
-
not to be
used in the bonding.
WHY?
The increase in the atomic size when going
down the group causes the covalent bond to
become weaker.
Thus, energy released when two covalent
bonds are formed is not enough to excite the
s e
-
to promote it to p orbitals.
Easy reduction of lead from +4 to +2
PbCl
4(l)
PbCl
2(s)
+ Cl
2(g)
Yellow liquid white solid
Thus Pb
2+
is much more stable than Pb
4+
Diamond Structure Graphite Structure
Allotropes of carbon
Properties Diamond Graphite
Bonding C atoms are bonded by strong
covalent bonds in a giant
arrangement tetrahedral
structure.
C atoms are bonded by strong
covalent bonds in a
hexagonal structure.
Layers of these hexagon
structures are held by weak
Van der Waals forces
Conductivity Does not conduct electricity
due to the absence of free
moving valence electrons
Conducts electricity due to
the presence of free moving
valence electrons
Hardness Hard because of D network of
strong covalent bonds.
Soft because the layers can
easily slide over one another
due to weak Van Der Waals
forces.
Uses Glass cutter Pencil leads, ribbons for
typewriters.
All the Group IV elements can form
tetrachlorides, MCl
4
(tetrahedral shape)
M = C, Si, Ge, Sn, Pb
MCl
4
simple molecules that are held together
by weak van der Waals forces
M-Cl bond
(______________________)
Group IV Tetrachlorides
5
M
Cl
Cl
Cl
Cl
Tetrahedral shape
All bonds in
ideal 109.5
Group IV Tetrachlorides
All elements in Group IV forms tetrachloride,
which is tetrahedral in shape.
It has a simple molecular structure, held
together by weak van der Waals forces
Low MP and BP due to weak van der Waals
forces makes tetrachlorides volatile liquids at
room temperature.
MP and BP increase down the group because
of van der Waals forces as molecular size .
Thermal stability of tetrachloride
(____________________) when going down
Group IV.
CCl
4
, SiCl
4
& GeCl
4
are stable tetrachloride.
However, SnCl
4
and PbCl
4
decompose upon
heating.
(________________________________)
(on strong heating)
(________________________________)
(on slightly warming)
Oxidation
states of
Sn & Pb
from +4
+2
Thermal Stability of MCl
4
Decrease Down Group IV
Going down a group, size of atom
Size of bonded atom , bond length
M-Cl bond becomes longer & attraction
becomes weaker due to the smaller
overlapping of the orbitals
Bond energy as weaker covalent bond
Carbon Diamond
Graphite
-High speeding drilling material
-Lubricants, electrodes and
moderator in nuclear reactors
- component in the composite
material of bullet-proof vests/ in
the bodies of aircraft
Silicon Silicon
Silicone
-Micro-electronic devices
- making of silicone
- lubricants, oils, hydraulic fluids,
car polishes, electro-insulators,
elastomers, paints, greases and
water proof fabric
Tin - Plating of iron/ steel in food
containers (tin can)
- Making alloys (pewter, solder and
bronze)
Uses of Group IV elements
Summary
Physical properties of Group 4 element
Electrical conductivity,
Thermal stability of MCl
4
Inert pair effect