GROUP 14

DR ZAITUN GHAZALI
LEARNING OUTCOMES:
Student can analyse:
1. Physical properties: melting points, electrical
conductivity, atomic radius, first ionization energy
of Group 14 elements: C, Si, Ge, Sn, Pb.

2. Chemical properties : oxidation states of +2 and

+4; relative stability of the +2 and +4 oxidation
state.

3. Tetrachlorides of group 14: physical properties;

thermal stability; hydrolysis of the tetrachlorides
INERT PAIR EFFECT
5

• The inert pair effect is the reluctance of 's' electrons for participating in
bonding.

• The Electrons present in the intervening d-(and f-) orbitals do not

effectively shield the s-electrons of the violence shell down the group.

• As a result, the inert pair of s electrons remains more tightly held by the
nucleus and hence participates less in bond formation.

• As a result the s electron are less readily availablr for chemical reaction.
 6

Note: The consequences of the inert pair effect are:

1. Stability of the electrons and compounds changes due to
inert pair effect.
2. Inert pair effects cause the variable valency of the
elements.
3. It influences the oxidizing and reducing properties of the
compounds.
4. It also affects the melting and boiling point of the
elements.
•The lower oxidation states of the elements of this 7
group are formed due to the inert pair effect.

•Example: For Sn, there are two oxidation

states +2 and +4. Out of these, Sn2+ is formed due to the
inert pair effect, where the valence shell s− electrons
remain paired instead of participating in bond
formation.
sp3 hybridization 8

the s and p orbitals of the

excited state carbon are
hybridized to form four
identical in size, shape,
and energy orbitals.
 Presentation title 9

tetrahedral geometry
 10

The sp2 hybridization occurs when the s orbital is mixed with

only two p orbitals as opposed to the three p orbitals in the sp3
hybridization. So, three orbitals are mixed, and the outcome is
three hybrid orbitals which are called sp2 hybrid orbitals.
Presentation title 11
 DISCUSSION
1. Trend in physical properties: melting points, electrical conductivity , atomic radius, first
ionization energy of Group 14 elements: C, Si, Ge, Sn, Pb
- Increasing screening effect
and nuclear charge.
- The screening effect cancel
out the nuclear charge.
- Effective nuclear charge
almost constant.
- Attraction between nucleus
and electron weaker.
- -Atomic radius increases
- Giant covalent to giant
metallic
- Giant covalent: cannot not
conduct electricity( Carbon)
- Giant metallic : conductor
- Increases in atomic radius,
more electron delocalized,
hence conductivity increases
- Giant covalent to giant
metallic
- Giant covalent (C): large
energy required to overcome
the covalent bond
- Si and Ge: Going down the
group the increases in atomic
radius, the strength of covalent
bond decreases
- Sn &Pb: weak metallic bond
- -Attraction between nucleus
and electron valance
weaker.
- Energy decreases
- However Sn < Pb: ineffective
screening of 4f electrons in
Pb atom. Increases in
effective nuclear charge in
Pb atom.
CHEMICAL PROPERTY Presentation title 13

oxidation states of +2 and +4 relative stability of the +2 and +4 oxidation number

Going down the group:

+2 oxidation state of element increases
+4 oxidation state of element decreases

C Si Ge Sn Pb
+4 +2

C2+ Si2+ Ge2+ Sn2+ Pb2+

Covalent Covalent with ionic Ionic

C4+ Si4+ Ge4+ Sn4+ Pb4+

Covalent
Standard Electrod Potential 14

The stability of the +2 and +4 oxidation state can be illustrated using SEP of M4+/ M2+ system
Standard electrode potentials
(redox potentials) are one way
of measuring how easily a
substance loses electrons.
The more negative the E° value,
the further the position of
equilibrium lies to the left
EXAMPLES: 15

Relative stability of the +2 and +4 oxidation number

Chemical equation

C CO is not stable. Oxidised readily to

CO2
Si SiO not stable react with O2

Ge GeO not stable react with O2

Pb PbO2 not stable, oxidises

concentrated hydrochloric acid on
heating
PbO2 decomposes to form PbO
PbCl4 thermally unstable.
Decompose when warmed to form
PbCl2
TETRACHLORIDES OF GROUP 14 ELEMENTS
CCl4 > SiCl4 > GeCl4 > SnCl4 > PbCl4
Cl2 + CS2 → CCl4 + S2Cl2
Si, Ge, Sn: Si + Cl2 → SiCl4
PbO + 4HCl → PbCl4 + 2H2O
16
Simple covalent molecules
Covalent bond
Held by van der Walls forces
Tetrahedral shape
Undergoes sp3 hybdridisation
PHYSICAL PROPERTIES Melting Point 17
 Thermal Stability

C Si Ge Sn Pb
Stable to heat Decompose on Partially decompose at
strong heat room temperature
Hydrolysis
All Group 14 tetrachloride undergoes hydrolysis except
CCl4
General equation:
Tetrachloride + 2water → oxide + 4HCl
Example: 3s 3p 3d

| | | |

CCl4 does not undergoes hydrolysis

→ SiO2 + 4HCl 2s 2p

| | | |

The mechanism: C does not have empty d-orbital in its

SiCl4 + 2H2O → SiCl4(H2O)2 valence shell to form coordinate bond
SiCl4(H2O)2 → SiO2 + 4HCl
TUTORIAL
1. Describe and explain the thermal stability of tin(IV)chloride ang
lead(II)chloride.
2. Pure silicon dioxide (silica) can be obtained by reacting silicon
tetrachloride with water.
(i) write an equation for the hydrolysis of silicon tetrachlorides
(ii) state two uses of silica

3. Explain the thermal stability of tetrachlorides of the Group 14

elements from carbon to lead. Write the equations for the reaction
involved.

4. Explain the reactivity of carbon tetrachlorides and silicon

tetrachloride with water. Write the equation for the reaction involved.
OXIDES OF GROUP 14 21

C CO, CO2

Si SiO, SiO2

Ge GeO, GeO2

Sn SnO, SnO2

Pb PbO, PbO2
 MONOXIDES OF GROUP 14, +2 OXIDATION STATE

Thermal stability
C CO 2CO + O2 → 2CO2
Easily
Simple oxidised to
Si SiO covalent dioxides 2SiO(g) → Si + SiO2

Ge GeO 2GeO + O2 → 2GeO2

Sn SnO Ionic with 2SnO + O2 → 2SnO2

covalent
characteristic
Pb PbO Stable 6PbO + O2 2Pb2O3
 MONOXIDES OF GROUP 14, +2 OXIDATION STATE

Acid-Base Property
With hot dilute acid With hot concentrated alkali
C CO
Neutral
Si SiO
Ge GeO GeO + 2H+ → Ge2+ + H2O GeO + 2OH- + H2O→ Ge(OH)42-

Sn SnO
Amphoteric

Pb PbO
 MONOXIDES OF GROUP 14, +4 OXIDATION STATE

Thermal stability
C CO2 CO2 Simple non polar covalent molecules, sp2

SiO2 stable giant molecules, sp3

Covalent
Si SiO2

Stable
Ge GeO2 GeO2 Intermidiate structure between simple
SnO2 and giant

Sn SnO2
Ionic

Pb PbO2 Unstable 300 °C

2PbO2 → 2Pbo + O2
 MONOXIDES OF GROUP 14, +4 OXIDATION STATE

Acid-Base Property
Water
C CO Slightly soluble- H2CO3
Disolves
CO2 + OH- → CO32- + H2O

Si SiO Acidic Disolves

Insoluble SiO2 + OH- → SiO32- + H2O

With hot concentrated HCl With hot concentrated alkali

Ge GeO GeO + 4H+ → Ge4+ + 2H2O GeO2 + 2NaOH + H2O→ Na2Ge(OH)6

sodium germanate(IV)
SnO2 + 2NaOH + H2O→ Na2Sn(OH)6
Sn SnO COLD
Amphoteric PbO2 + 2NaOH + H2O→ Na2Pb(OH)6
PbO + 4H+ → Pb4+ + 2H2O
Pb PbO HOT
PbO + 4H+ → Pb2+ + Cl2 +2H2O
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ZEOLITE
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REFERENCES:
https://testbook.com/learn/chemistry-p-block-group-14-elements/

https://www.slideshare.net/Thivyaapriya/inorganic-chemistry-group-14-and-
coumpounds
TUTORIAL
1. Describe and explain the thermal stability of tin(IV)chloride and
lead(II)chloride.

-Both decompose according to the equation:

SnCl4 → SnCl2 + Cl2
PbCl4 → PbCl2 + Cl2

- The ease of decomposition depend to the length of element-chlorine

bond.
- Lead atom is larger than tin atom.
- Pb-Cl bond is longer than Sn-Cl bond
- PbCl4 thermally less stable compare to SnCl4.
TUTORIAL
2.Pure silicon dioxide (silica) can be obtained by reacting silicon
tetrachloride with water.
(i) write an equation for the hydrolysis of silicon tetrachlorides
(ii) state two uses of silica

a)SnCl4 + 2 H2O → SiO2 + 4HCl

b)
TUTORIAL
3. Explain the thermal stability of tetrachlorides of the Group 14
elements from carbon to lead. Write the equations for the reaction
involved.

thermal stability decreases down the group

atomic size increases
X-Cl bond length longer and weaker
CCl4, SiCl4, GeCl4 stable to heat
SnCl4 and PbCl4 are not stable. Decompose when heated to form
dichlorides and chlorine gas

PbCl4 → PbCl2 + Cl2

TUTORIAL
4. Explain the reactivity of carbon tetrachlorides and silicon
tetrachloride with water. Write the equation for the reaction involved.

CCl4 does not react with water.

Carbon atom cannot expends its octet because it does not have d
orbitals

SiCl4 undergoes hydrolysis in water

Liberates white fumes hydrogen chlorides
Silicon atom has empty 3d orbitals to form temporary bonds with water
SiCl4 + 2H2O → SiO2 + 4H2O