The Periodic Table - Group 4

C
hem
F
actsheet
September 2001 Number 20
To succeed in this topic you need to:
Understand atomic structure (Factsheet 01), bonding (Factsheet
05) and structure of elements and compounds (Factsheet 06)
Understand oxidation numbers (Factsheet 11)
After working through this Factsheet you will:
Know the trends in physical properties of the Group 4 elements
Know the relative stabilities of the +2 and +4 oxidation states
of the Group 4 elements
Know key characteristics of Group 4 oxides and chlorides
Group 4 Elements
The electron configurations of Group 4 are shown below:
Element Electronic Structure
carbon 2.4 [He] 2s
2
2p
2
silicon 2.8.4 [Ne] 3s
2
3p
2
germanium 2.8.18.4 [Ar] 3d
10
4s
2
4p
2
tin 2.8.18.18.4 [Kr] 4d
10
5s
2
5p
2
lead 2.8.18.32.18.4 [Xe] 4f
14
5d
10
6s
2
6p
2
Group 4 elements are part of the p-block.
Trends within the group
As we go down Group 4:
Atomic radius increases - as electrons go into higher energy levels
Density increases - density depends on structure, atomic radius and
atomic mass. Larger atomic masses usually produce higher densities,
since the atomic radius does not increase as fast as the atomic mass.
Melting point decreases - due to the change in structure from giant
molecular to metallic
Ionisation energy generally decreases - since the atomic radius
increases, meaning the outer electrons are further away from the nucleus,
and there is an increased shielding effect due to the greater number of
electrons between outer electrons and the nucleus
Metallic character increases - since an explanation of this requires
knowledge of oxide characteristics, further details are given at the end
of this Factsheet
Structure
Carbon exists as two common allotropes (fig 1):
1
Diamond
Graphite
Fig 1. Allotropes of carbon
Silicon and Germanium have a structure similar to diamond.
Tin has three allotropes, whose stability depends on the temperature. The
allotrope stable at room temperature (white tin) has a metallic structure.
However, the other allotropes, which are stable at other temperatures,
have different structures.
Lead has a metallic structure.
Element Symbol Appearance Melting pt Density Conductivity 1
st
I.E. Bonding Metallic
(
o
C) (gcm
-3
) (kJ mol
-1
) character
carbon (graphite) C shiny black solid 3652 2.26 fairly good 1086 giant molecular non-metal
carbon (diamond) C colourless solid 3730 3.51 non-conductor 1086 giant molecular non-metal
silicon Si shiny grey solid 1410 2.33 semi-conductor 787 giant molecular non-metal
germanium Ge shiny grey solid 937 5.32 semi-conductor 760 giant molecular metalloid
tin Sn silver solid 232 7.3 good 707 giant metallic metal
lead Pb silver solid 327 11.4 good 715 giant metallic metal
Table 1. Elements of Group 4
Giant covalent molecule.
One of the hardest substances known, due to strong covalent bonds.
Insulator.
Giant covalent layer lattice.
Lubricant due to ability of layers to slide across each other.
High melting point due to strong covalent interatomic bonds.
Conductor (in plane of layers) due to presence of delocalised electrons.
Exam Hint: Questions on trends, their explanations and consequences
are common. Candidates need to be able to explain the reasons for the
trends in atomic radius, ionisation energy and metallic character.
Periodic Table - Group 4
Chem Factsheet
2
Oxidation States of Group 4
We might expect group 4 to have a common oxidation state of +4 as it has
4 outer electrons.
However, there are two oxidation states for Group 4: +4 and +2
Going down the group, the stability of the +4 oxidation state falls, and the
stability of the +2 oxidation state rises (fig 2).
reduction
oxidation
>
>
Consequently:
+2 oxidation state of C, Si, Ge, Sn are reducing agents
(ie want to be oxidised and lose 2 electrons). In carbon and silicon, the
+2 state is extremely unstable, so such compounds are rarely met.
+4 oxidation state of Pb is an oxidising agent
(ie wants to be reduced and gain 2 electrons)
Fig 2. Relative stability of +2 and +4 oxidation states in Group 4
Valencies in Group 4 - an explanation
The ground state for the outer electrons of the Group 4 compounds is
as shown below:
Hence, to achieve a valency of four, one s electron must be promoted to
the vacant p orbital:
Promotion of this electron requires energy, but the energy released in
forming the two extra bonds compensates for this.
As we go down the group, the bonding electrons are further from the
nucleus, so the energy gained from forming the extra bonds becomes
less. The s electron therefore becomes less likely to be promoted. This
is known as the inert pair effect.
Since silicon and the elements below it have vacant d-orbitals, they can
show a covalency of up to 6.
p s
p s
So tin(II) will reduce lead(IV) to lead(II):
Sn
2+
(aq) + Pb
4+
(aq) Sn
4+
(aq) + Pb
2+
(aq)
We will see examples of both oxidation states in the Group 4 elements
when we look at their oxides and chlorides.
= silicon = oxygen atom
Fig 3. Structure of silicon dioxide
Oxides of Group 4
Note that lead(IV) oxide is an oxidising agent, and will decompose on
heating to give lead(II) oxide and oxygen.
Acidity of the oxides decreases down the group
Dioxide State Bonding Structure Character
CO
2
gas covalent simple molecular acidic - reacts with aqueous alkalis
CO
2
(g) + 2 OH

(aq) CO
3
2
(aq) + H
2
O(l)
SiO
2
solid covalent macromolecular (Fig 3) v. weakly acid - reacts with hot concentrated alkalis
SiO
2
(s) + 2OH

(l) SiO
3
(aq) + H
2
O(l)
GeO
2
amphoteric - react with both acids and alkalis
SnO
2
solid some ionic character giant structure With alkali: SnO
2
(s) + 2OH

(aq) + 2H
2
O(l) Sn(OH)
6
2
(aq)
PbO
2
With acid: SnO
2
(s) + 4H
+
(aq) Sn
4+
(aq) + 2H
2
O(l)
Monoxide Reducing agent? Bonding Character
CO Yes - important industrially covalent neutral
SiO Yes covalent amphoteric - react with both acids and alkalis
SnO Yes some covalent character With alkali: PbO(s) + 2OH

(aq) + H
2
O (l) Pb(OH)
4
2
(aq)
PbO No ionic With acid: PbO(s) + 2H
+
(aq) Pb
2+
(aq) + H
2
O(l)
Dioxides (+4 oxidation state)
Monoxides (+2 oxidation state)
C Si Ge Sn Pb
+4 state
+2 state
r
e
l
a
t
i
v
e

s
t
a
b
i
l
i
t
y

f
a
l
l
s
relative stability rises
Only lead has a more stable +2 state than +4 state
Exam Hint: Candidates must be able to recall suitable equations
to demonstrate the amphoteric character of oxides.
Chem Factsheet
3
Periodic Table - Group 4
Chlorides of Group 4
Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum Press, Unit 305B,
The Big Peg, 120 Vyse Street, Birmingham, B18 6NF ChemistryFactsheets may be copied free of charge by
teaching staff or students, provided that their school is a registered subscriber. No part of these Factsheets may
be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without
the prior permission of the publisher. ISSN 1351-5136
Note: the dichlorides become increasingly ionic down the group as the
"inert pair effect" (page 2) becomes more pronounced.
Element dichlorides (+2 oxidation state) tetrachloride (+4 oxidation state)
bonding stability & hydrolysis bonding stability & hydrolysis
carbon covalent extremely unstable unreactive
silicon covalent extremely unstable hydrolyses
germanium covalent hydrolyses with oxidation reversible hydrolysis
GeCl
2
(s) + 2H
2
O(l) GeO
2
(s) + 4HCl(aq)
tin partially ionic reversible hydrolysis reversible hydrolysis
SnCl
2
(s) + H
2
O(l) SnClOH(s) + HCl(aq)
lead ionic stable, insoluble unstable, rapidly hydrolysed
Unlike the other tetrachlorides, CCl
4
will not hydrolyse in water. The
reason for this can be seen by examining the mechanism for hydrolysis of
SiCl
4
.

The reaction between silicon tetrachloride and water is:
SiCl
4
(l) + 2H
2
O (l) SiO
2
(s) + 4HCl (aq)
This reaction can occur because a lone pair of electrons on the oxygen in
water is allowed to approach the central silicon atom in SiCl
4
and form a
dative bond, starting this reaction.
Tetrachloromethane, CCl
4
, does not hydrolyse in water, as carbon is
smaller than silicon, causing:
C - Cl bonds to be shorter than Si - Cl bonds
C - Cl bonds to be stronger than Si - Cl bonds
Cl atoms to be more closely packed around central C atom, not
allowing water molecule to approach it.
Carbon, unlike silicon, has no available d - subshell to accept electrons
and form a new active bond.
CCl
4
and SiCl
4
have
tetrahedral structures
(Fig 4)
All tetrachlorides
covalent liquids with
simple molecular
structures
Cl
Cl
C
Cl
Cl
Fig 4. Structure of carbon and silicon tetrachlorides
Cl
Cl
Si
Cl
Cl
Metallic Character in Group 4 - Summary and Explanation
"Metallic character" is judged from a set of properties:
Metals Good conductors of electricity.
Form ionic compounds by losing electrons to produce
positive ions
Form basic oxides.
Non-Metals Non-conductors of electricity (insulators) except graphite
Form ionic compounds by gaining electrons to produce
negative ions, or form covalent compounds
Form acidic oxides.
So metallic character in Group 4 is measured by:
Electrical conductivity - this depends on the structure of the element.
With the exception of graphite, conducting solids (as opposed to
semiconductors) have a metallic giant structure, with free electrons. Tin
and lead are the only group 4 elements with such a structure.
Covalent or ionic nature of compounds. Since +4 compounds are covalent
(with the exception of a small number of lead(IV) compounds), the change
in metallic character is best shown by examining:
the relative stability of +2 and +4 compounds
This depends on the "inert pair effect" as described on page 2.
the ionic or covalent nature of +2 compounds
This depends on ionisation energy, which decreases down the group.
Nature of oxides. Although no Group 4 oxides are basic, a change in
character can be seen from acidic to amphoteric - i.e. becoming more basic
in character. This is due to the increasingly ionic bonding in the oxides.
Questions
1. Explain the trend in first ionization energies down Group 4.
2. State the two oxidation states exhibited by Group 4 elements in their
compounds, and indicate which is the most common.
3. Describe the trend in acidity of the Group 4 oxides.
4. Give examples to show that lead(II) oxide is amphoteric.
5. Use the electronic structure of carbon and silicon to explain why
carbon tetrachloride does not hydrolyse.
Answers
1. First ionisation energies decrease going down Group 4. This is due to:
increase in atomic radius; less attraction between outer electrons and
nucleus; increased shielding effect as more electrons exist between outer
electrons and nucleus. Consequently outer electrons are easier to remove
from larger atoms such as lead.
2. Oxidation states of group 4 are +2 and +4. +4 is more common.
3. Acidity of the oxides decreases down the group.
4. PbO(s) + 2OH

(aq) + H
2
O(l) Pb(OH)
4
2
(aq)
PbO(s) + 2H
+
(aq) Pb
2+
(aq) + H
2
O(l)
5. Hydrolysis of SiCl
4
can occur because a lone pair on an oxygen atom in
water forms a dative bond to the Si atom. This is possible because Si has
the 3d subshell which can accept electrons. The outer electrons of carbon
are in the second energy level, which has no d subshell, so the dative
bond cannot be formed.
Exam Hint: Candidates must describe the inert pair effect in full;
just saying "because of the inert pair effect" will not gain full marks.
Exam Hint: Explaining the stability of carbon tetrachloride is a
common examination question.