Group IV Elements

• The group IV elements are in the p block of

the periodic table
• They all have four electrons in their outer
principal quantum shell
• They are all solids at room temperature
Element Structure Melting point Electrical
conductivity
Carbon (diamond) Non-metal 3550 Non conductor
Silicon Si Metalloid 1410 Semi-conductor
Germanium Ge Metalloid 937 Semi-conductor
Tin,Sn Metal 232 conductor
Lead Pb Metal 327 conductor
 Structures of the elements
• The trend from non-metal to metal as you go
down the Group is clearly seen in the
structures of the elements themselves.
• Carbon at the top of the Group has giant
covalent structures in its two most familiar
allotropes - diamond and graphite.
Structures of the elements Cont’d
• Diamond has a three-dimensional structure of
carbon atoms each joined covalently to 4
other atoms.
Structures of the elements Cont’d
• Exactly this same structure is found in silicon
and germanium and in one of the allotropes
of tin - "grey tin" or "alpha-tin".
Structures of the elements Cont’d
• The common allotrope of tin ("white tin" or
"beta-tin") is metallic and has its atoms held
together by metallic bonds
• The structure is a distorted close-packed
arrangement
• In close-packing, each atom is surrounded by
12 near-neighbours.
Structures of the elements Cont’d
• For lead, the atoms are arranged in a
straightforward 12-co-ordinated metallic
structure
 Physical properties of the elements
Melting points and boiling points
• If you look at the trends in melting and boiling
points as you go down Group 4
• The trends reflect the increasing weakness of
the covalent or metallic bonds as the atoms
get bigger and the bonds get longer
• The low value for tin's melting point
compared with lead is presumably due to tin
forming a distorted 12-co-ordinated structure
rather than a pure one.
• The tin values in the chart refer to metallic
white tin.
• Si and Ge have giant covalent structures
similar to that of C (diamond)
• They all have very high melting points due to
the fact that a lot of energy is needed to break
the many covalent bonds in the structure
• The decrease in melting points from C to Ge is
a result of decreasing energy needed to break
the bonds
• Sn and Pb have relatively low melting points
compared to most other metals
• The strength of the metallic bonding
decreases as the size of the ions increases
• Brittleness
• There is a much clearer non-metal / metal
difference shown if you look at the brittleness
of the elements.
• Carbon as diamond is, of course, very hard -
reflecting the strength of the covalent bonds.
• However, if you hit it with a hammer, it
shatters
• Once you apply enough energy to break the
existing carbon-carbon bonds
• Silicon, germanium and grey tin (all with the
same structure as diamond) are also brittle
solids.
• However, white tin and lead have metallic
structures
• The atoms can roll over each other without
any permanent disruption of the metallic
bonds - leading to typical metallic properties
like being malleable and ductile
• Lead in particular is a fairly soft metal.
 Electrical conductivity
• Carbon as diamond doesn't conduct electricity
• In diamond the electrons are all tightly bound
and not free to move

• Unlike diamond (which doesn't conduct

electricity), silicon, germanium and grey tin
are semiconductors
• Some of the electrons can move out of
position by “Jumping” to different places in
the lattice
• Their conductivity increases with temperature
• White tin and lead are normal metallic
conductors of electricity.
• There is therefore a clear trend from the
typically non-metallic conductivity behaviour
of carbon as diamond, and the typically
metallic behaviour of white tin and lead.
 Trends in oxidation states
The overall trend
• The typical oxidation state shown by elements
in Group 4 is +4, found in compounds like CCl4,
SiCl4 and SnO2.
• However, as you go down the Group, there
are more and more examples where the
oxidation state is +2, such as SnCl2, PbO, and
Pb2+.
• With tin, the +4 state is still more stable than
the +2, but by the time you get to lead, the +2
state is the more stable - and dominates the
chemistry of lead.
• The only common example of the +2 oxidation
state in carbon chemistry occurs in carbon
monoxide, CO
• Carbon monoxide is a strong reducing agent
because it is easily oxidised to carbon dioxide -
where the oxidation state is the more
thermodynamically stable +4.
• For example, carbon monoxide reduces many
hot metal oxides to the metal - a reaction
which is used, for example, in the extraction
of iron in a blast furnace.
• For tin, the +2 state has become increasingly
common, and there is a good range of both tin(II)
and tin(IV) compounds
• However, tin(IV) is still the more stable oxidation
state of tin.
• That means that it will be fairly easy to convert
tin(II) compounds into tin(IV) compounds.
• This is best shown in the fact that Sn2+ ions in
solution are good reducing agents.
• For example, a solution containing tin(II) ions
(for example, tin(II) chloride solution) will
reduce a solution of iodine to iodide ions. In
the process, the tin(II) ions are oxidised to
tin(IV) ions
• Tin(II) ions also reduce iron(III) ions to iron(II)
ions. For example, tin(II) chloride solution will
reduce iron(III) chloride solution to iron(II)
chloride solution. In the process, the tin(II)
ions are oxidised to the more stable tin(IV)
ions.
• Tin(II) ions will also, of course, be easily
oxidised by powerful oxidising agents like
acidified potassium manganate(VII) solution
(potassium permanganate solution).
• This reaction could be used as a titration to
find the concentration of tin(II) ions in a
solution
• With lead, the situation is reversed
• This time, the lead(II) oxidation state is the
more stable, and there is a strong tendency
for lead(IV) compounds to react to give
lead(II) compounds.
• Lead(IV) chloride, for example, decomposes at
room temperature to give lead(II) chloride and
chlorine gas:
• lead(IV) oxide decomposes on heating to give
lead(II) oxide and oxygen
• Lead(IV) oxide also reacts with concentrated
hydrochloric acid, oxidising some of the
chloride ions in the acid to chlorine gas
• Once again, the lead is reduced from the +4
to the more stable +2 state
 Trends in oxidation states
• the normal Group oxidation state is +4
• All of the elements in the group have the
outer electronic structure ns2npx1npy1, where n
varies from 2 (for carbon) to 6 (for lead)
• The oxidation state of +4 is where all these
outer electrons are directly involved in the
bonding
• As you get closer to the bottom of the Group,
there is an increasing tendency for the s2 pair
not to be used in the bonding
THE CHLORIDES OF CARBON, SILICON AND LEAD
 Carbon, silicon and lead tetrachlorides
•These all have the formula XCl4.
•They are all simple covalent molecules with
a typical tetrahedral shape
• All of them are liquids at room temperature.
• At room temperature, lead(IV) chloride will tend to
decompose to give lead(II) chloride and chlorine gas
• Lead(II) chloride, PbCl2
 is a white solid, melting at 501°C
 It is very slightly soluble in cold water, but more
soluble in hot water
 lead(II) chloride is mainly ionic in character.
 Stability
•At the top of Group 4, the most stable
oxidation state shown by the elements is +4.
•This is the oxidation state shown by carbon
and silicon in CCl4 and SiCl4
•These therefore have no tendency to split
up to give dichlorides.
• The relative stability of the +4 oxidation
state falls as you go down the Group
• The +2 oxidation state becomes the most
stable by the time you get to lead.
• Lead(IV) chloride decomposes at room
temperature to give the more stable
lead(II) chloride and chlorine gas
 Reaction with water
(hydrolysis)
• Carbon tetrachloride
(tetrachloromethane)
• Carbon tetrachloride has no reaction with
water
• If you add it to water, it simply forms a
separate layer underneath the layer of
water.
• Suppose a water molecule is going to
react with the carbon tetrachloride
• The reaction would have to start by the
water molecule's oxygen attaching itself to
the carbon atom via the oxygen's lone pair
• A chlorine atom would get pushed off the
carbon in the process.
• The chlorines are so bulky and the carbon
atom so small, that the oxygen can't easily
get at the carbon atom.
• if it did, there will be a stage where there is
considerable cluttering around that carbon
atom before the chlorine atom breaks away
completely
• There is going to be a lot of repulsion
between the various lone pairs on all the
atoms surrounding the carbon.
• That cluttering is going to make this half-
way stage (properly called a "transition
state") very unstable
• A very unstable transition state means a
very high activation energy for the
reaction.
• The other problem is that there isn't a
convenient empty orbital on the carbon
that the oxygen lone pair can attach to.
• If it could attach before the chlorine starts
to break away, that would be an
advantage..
• Forming a bond releases energy, and that
energy would therefore be readily
available for breaking a carbon-chlorine
bond
• But in the case of a carbon atom, that isn't
possible
 Silicon tetrachloride
•The situation is different with silicon
tetrachloride.
•The silicon atom is bigger, and so there is
more room around it for the water molecule
to attack, and the transition state will be less
cluttered.
• Also silicon has the additional advantage
that there are empty 3d orbitals available
to accept a lone pair from the water
molecule
• Carbon doesn't have 2d orbitals because
there are no such things
• There are no empty 2-level orbitals
available in the carbon case
• This means that the oxygen can bond to
the silicon before the need to break a
silicon-chlorine bond
• This makes the whole process
energetically easier.
• Therefore silicon tetrachloride reacts
violently with water to give white solid
silicon dioxide and steamy fumes of HCl.
• Liquid SiCl4 fumes in moist air for this reason
- it is reacting with water vapour in the air.
 Lead tetrachloride (lead(IV) chloride)
•The reaction of lead(IV) chloride with water
is just like the silicon tetrachloride one
• You will get lead(IV) oxide produced as a
brown solid and fumes of hydrogen chloride
given off
• Lead(II) chloride
• Unlike the tetrachlorides, lead(II) chloride can be
thought of as ionic
• It is sparingly soluble in cold water, but more soluble
in hot water
• Looked at simply, solubility in water involves the
break-up of the ionic lattice and the hydration of the
lead(II) and chloride ions to give Pb2+(aq) and Cl-(aq).
 Group IV oxides: Structure &
stability
The oxides of the Group IV elements exist in the +2 & +4 oxidation states.

+2 Oxidation states +4 Oxidation states

CO Simple CO2 Molecular
molecular
SiO Simple SiO2 Giant covalent
molecular
GeO Ionic with GeO2 Giant covalent
some covalent
character
SnO Giant ionic SnO2 Giant covalent
With ionic character
PbO Giant ionic PbO2 Giant covalent
With ionic character
 Group IV oxides: Structure &
stability
• Down each series of oxides the structures get
more ionic as the metallic character of Group
IV elements increase.
• SnO2 and PbO2 have some degree of covalent
character in their ionic structure.
• All the oxides, apart from CO and CO2 are
solids with giant structures and high mpts.
 Group IV oxides: Structure &
stability
• CO and CO2 are gases at room temperature
because they have simple molecular
structures with only weak forces between
their molecules in the solid and liquid states.
 Group IV oxides: Structure &
stability
• CO has a strong triple bond and does not
decompose on heating.
 Group IV oxides: Structure &
stability
• Germanium (II) oxide disproportionates on
heating:
• 2GeO (s)  GeO2 (s) + Ge (s)
+2 +4 0 (Oxidation numbers )
 Group IV oxides: Structure &
stability
• Tin (II) oxide and lead (II) oxide do not
decompose on heating in the absence of air.
They are readily oxidised to higher oxides in
the presence of oxygen.
• Carbon dioxide has strong double bonds and
do not decompose on heating
 Group IV oxides: Structure &
stability
• The oxides in the +4 oxidation state tend to
decrease in stability down the group.
• Only lead (IV) oxide (PbO2), however,
undergoes significant thermal decomposition:
PbO2 (s)  PbO (s) + O2 (g)
Lead (IV) oxide Lead (II) oxide
 Acid-base properties of the oxides
+2 Oxidation states +4 Oxidation states
CO Very weakly acidic CO2 Acidic
SiO - SiO2 Very weakly acidic
GeO Amphoteric GeO2 Amphoteric
SnO Amphoteric SnO2 Amphoteric

PbO Amphoteric PbO2 Amphoteric

Acid-base properties of the oxides
• The oxides in the +2 oxidation states are less
acidic (more basic) than the corresponding
oxides in the +4 oxidation states.
• Eg: CO only reacts with hot concentrated
NaOH, but CO2 forms an acidic solution in
water.
• CO2 (g) + H2O(l) ⇋ HCO3-(aq) + H+ (aq)
 Acid-base properties of the oxides
• CO2 (g) also reacts with dilute alkalis :
• CO2 (g) + 2NaOH (aq)  Na2CO3(aq) + H2O (l)

• The oxides in both oxidation states become more basic down

the group as the metallic character of group IV atoms increases.
For example:
• CO2 reacts with aqueous alkalis ( OH+ ions) but Silicon dioxide
only reacts with conc. Alkalis:
• SiO2 (s) + 2NaOH (aq)  Na2SiO3 (aq) + H2O (l)
sodium silicate
Reactions of amphoteric oxides of
Group IV
Oxidation state +2
•GeO, SnO and PbO are all amphoteric, but have
increasingly basic character in the order GeO<
SnO< PbO
•They all react with acids to form a salt with
oxidation state +2
•Eg: SnO (s) + 2HCl (aq)  SnCl2 (aq) + H2O (l)
 Reactions of amphoteric oxides of
Group IV
• They all react with alkalis to form oxo ions with
oxidation state +2
• Eg: GeO (s) + 2OH-(aq)  GeO22-(aq) +H2O (l)
Germanate (II) ion

• SnO (s) + 2OH-(aq)  SnO22-(aq) +H2O (l)

Stannate (II) ion

• PbO (s) + 2OH-(aq)  PbO22-(aq) +H2O (l)

• Plumbate (II) ion
Reactions of amphoteric oxides of
Group IV
Oxidation state +4
•GeO2, SnO2 & Pbo2 are all amphoteric
•They all react with acids to form a salt with
oxidation state +4
Eg: SnO2(s) + 4HCl (aq)  SnCl4(aq) + 2H2O (l)
SnO2(s) reacts with dilute acid but PbO2 will only
react with conc. Acid, oxidising it to chlorine.
Reactions of amphoteric oxides of
Group IV
• GeO2, SnO2 & Pbo2 all react with alkalis to
form oxo ions with oxidation states +4
• Eg: GeO2 (s) + 2OH-(aq)  GeO32-(aq) +H2O (l)
• Germanate (IV) ion

• SnO2 (s) + 2OH-(aq)  SnO32-(aq) +H2O (l)

• Stannate (IV) ion

• PbO2 (s) + 2OH-(aq)  PbO32-(aq) +H2O (l)

• Plumbate (IV) ion