CHAPTER 18

[Group 14: C, Si, Ge, Sn,

Pb]

Prepared by: Chong Tze

Hui
Grace Wong
Chai Jui Jun
Group 14:
Element Carbon Silicon Germaniu Tin(Sn) Lead
Proton (C)
6 (Si)
14 m(Ge)
32 50 (Pb)
82
number
Electronic 2.4 2.8.4 2.8.18.4 2.8.18.18. 2.8.18.32.
configurat 4 18.4
ion

­They are known as the p­block elements.

carbon,C [He]2s22p2

silicon,Si [Ne]3s23p2
 germanium,Ge [Ar]3d10 4s2 4p2

tin,Sn [Kr]4d10 5s2 5p2

 lead,P b
[Xe]4f14 5d10 6s2 6p2
Physical Prop
erties
Atomic Radius

 C The nuclear charge and screening effect

increases.
 Si Screening effect increases faster than
nuclear charge.
 Ge This causes the effective nuclear
charge to
 decrease and the size of the atoms to
 Sn increases.

Sn Pb
Si Ge
C
 Pb


 Increases
First Ionisation Energy
1
 First ionisation energy/kJ mol‾


-First ionisation energy when
 CX descending the group,because

the in the effective nuclear charge,
 The valence electrons are easy to

remove.


Si -Pb is slightly higher than Sn,this is due

X
to the ineffective screening by the f


 electrons in the Pb.In fact,there is a slight


decrease in the screening effect from Sn


to Pb.

GeX


Sn



X Pb X


Proton number
 Melting Point
Element C Si Ge Sn Pb

Melting 3730 1410 937 232 327

Point/ºc
Structure Giant covalent molecule giant metallic

- Because the atomic saiz of Ge > Si > C, the

strength of the covalent bond in the lattice in
the order C > Si > Ge. Therefore, the melting
point from C to Ge.
 Lead are arranged according The atoms follow a tetragonal
to face-centred cubic structured arrangement which is
structure(Closely-packed) . more open.

This c ause s the  me lting po int o f le ad to  be  highe r than tin.
 Electric Conductivity
C Non-conductor(except for graphite)
Si & Ge Semi-conductor
Sn & Pb Conductors

C Si Ge Sn Pb         

INCREASE

This corresponds with the properties of the elements which changes

from non-metals to metal.
Oxidation States of +2 & +4
The stable oxidation number is in hold.
Elements Oxidation number
C +2, +4
Si +4
Ge +4
Sn +2, +4
Pb +2, +4

The elements of Group 14 from two oxidation states: +2 & +4.

Relative Stability of the +2 &+4
Oxidation State
 The +4 oxidation state involves the
promotion of an s electron to an empty p
orbital.
Energy


Energy
absorbed

+2 State +4 State
 Pb with big proton number is less likely to use two
electrons from the s orbital to be shared. This is
called the inert pair effect.
 The in the atomic size when going down the group
causes the covalent bonds to become
weaker.Therefore, the energy released when the
two covalent bonds are formed is not enough to
“excite” the s electrons to promote it to the f
orbitals in the case of lead.
 Relative stability

--------------------------

 +2



+4

 proton number
 C Si Ge Sn Pb
 4+ 2+
ø
a.Ge (aq) +2e Ge (aq) E = -1.60V
4+ 2+
ø
b.Sn (aq) + 2e Sn (aq) E = +0.15V
4+ 2+ ø
c.Pb (aq) + 2e Pb (aq) E = +1.80V
d.
As the E
Ø
values become increasingly positive going
down 4+
the group,the
2+ tendency for the M state to get
converted
to the M state increases.



 Example:
 Carbon monoxide is a reducing agent
because the +4 oxidation state is more
stable. In industries , carbon monoxide is
used in the extraction of iron from its ore.


 Fe2O3(s)+ 3CO(g) →2Fe(s) + 3CO2(g)



 Carbon monoxide is oxidised to carbon

dioxide.

 For Tin, the +4 oxidation state is slightly
more stable than the +2 oxidation
state.Aqueous tin(II)ions are weak
reducing agent.
 Example: it can reduce iron(III) salt solution
to iron (II).
3+ 2+
vSn2+ (aq)+ 2Fe (aq) → 2Fe (aq) +4+Sn (aq)


 Lead(IV)oxide is a strong oxidising

agent.
 PbO2(s)+4HCl(aq)→PbCl2(s)+ Cl2(g)+ 2H2O(l)



Tetrachlorides of group 14
 All elements in Group 14 forms Tetrachloride
compounds.(XCl4)


 The X-Cl bond is a covalent bond and the

intermolecular forces of attraction between
the tetrachloride molecules is the weak
van der waals forces.
Cl


 109.5°

X

Cl
 Cl
Cl
 Exist as simple MCl₄ molecule with a tetrahedral
shape.
 Prepared by passing dry chlorine gas into liquid carbon
disulphide and boiling under reflux ,iodine as
cataylst.
 Germanium tetrachlorides-Ge(s)+2Cl₂ (l)→GeCl₄ (l)


 Silicon tetrachlorides-Si(s)+ 2Cl₂(l)→SiCl ₄(l)




 Tin tetrachlorides-Sn(s)+2Cl →SnCl (l)


 Lead tetrachlorides
- prepare with cool lead+concentrated HCl to prevent

the decomposition
- Pb(s)+4HCl(aq)→PbCl ₄ (l)+2H₂ (g)


 Physical properties of the
tetrachlorides
Tetrachlor
ides *CCl₄ SiCl₄ GeCl₄ SnCl₄ PbCl₄
Melting
point/ºC -23 -70 -50 -33 -15
Boiling decompos
point/ºC 77 59 86 114 e

ht of the van der Waals forces increasing,melting point and boiling point increasing
Thermal stability of tetrachlorides
 X-Cl bond weak.
 Thermal stability decrease.

decreasing
Ø
Ø
Ø CCl₄ SiCl₄ ,and GeCl₄ are stable at high temp.
Ø SnCl₄decompose on heating
 SnCl₄ (l)→SnCl ₂ +Cl₂ (g)
 tin(П)chloride
Ø PbCl₄decompose on slight warming
 PbCl₄(l)→PbCl₂+Cl₂(g)
 lead (П) chloride

Hyrolysis of the tetrachlorides

 XCl₄(l)+2H₂O(l) →XO₂(s)+4HCl(aq)


 All tetrachlorides (except CCl₄) are hyrolysed

by water.
 Si,Ge,Sn and Pb’s empty d orbitals respective
to Cl to form coordinate (dative) bond with
water molecule.



Mechanism for the hydrolysis of SiCl₄

O
 Oxides of group 14:
Elemnt C Si Ge Sn Pb
Monoxide CO SiO GeO SnO PbO
Dioxide CO₂ SiO2 GeO₂ SnO₂ PbO₂

All oxides formed by Group 14 elements are of two

types:
(a) Monoxides , XO with an oxidation state of +2 for
its element.
(b)Dioxides , XO 2 with an oxidation state of +4 for
its element.
 Monoxides:


 For the Group 14 elements at the top of the

group, the oxidation state of +2 is unstable
compared to the oxidation state of +4.
Hence, the monoxides of C, Si, Ge, & Sn
are easily oxidised upon heating.



Monoxide CO SiO GeO SnO PbO

Structure Simple molecule Primary ionic
Physical
state
Thermal Gas Gas* Solid
stability
Acid/Base Convert to dioxide Stable
nature Natural Amphoteric

( *SiO) exists as a gas only at temp. above 2000ºC

(a)Thermal stabilityof the monoxides
 CO
-is a gsa under room conditions,

-burns with blue flame in air form CO₂

-slowly get oxidised to dioxide when exposed

to air
 2CO(g) +O₂(g)→2CO₂(g)
 SiO
-only exists in gas phase at temp. above

2000ºC
-it changes spontaneously to dioxide when

cooled 2SiO (g) → SiO₂(s)+ Si (s)


 GeO,SnO
-readily oxidised to dioxide when left

composed to air
 (a) 2GeO(s) +O₂ (g) → 2GeO₂ (s)
 (b) 2Sn (s) + O₂(g) → 2SnO₂ (s)
 PbO

 - stable on heat

 -heating at temp. above 400ºC,it get

converted to Triplumbum tetraoxide,Pb₃O₄
 400°c
6PbO(s) + O₂(g) 2Pb₃O₄(s)
yellow 470°c orange/brown

(b) The acid/base nature of the
monoxides
 CO and SiO are neutral
- sodium methanoate is formed when CO is

bubbled through concentrated sodium

hyroxide at 200ºC.
 CO(g) +NaOH (aq) → HCOONa (aq)
 GeO,SnO and PbO are amphoteric.
(a)They react with dilute acids to form salts.

 MO(s) +2H⁺ (aq) → M²⁺ (aq) +H₂O (l)

(b) They react with hot and dilute alkali to form

salts.
 MO(s) +2OH⁻(aq)+HO (l)→M(OH)₄²⁻

Dioxide of the group 14 element

Dioxide CO₂ SiO₂ GeO₂ SnO₂ PbO₂

Structure Simple molecule Primary ionic

Physical
State Gas Solid
Thermal Decompose
Stability Stable to PbO
Acid/Base
Nature Acidic Amphoteric
(a) Thermal stability
 CO₂ , SiO₂ , GeO₂ and SnO₂ stable to heat.
 Lead (IV)oxide decompose on heating to form
lead (II) oxide.
 2PbO₂(s) →2PbO(s) + O₂(g)

(b)Acid/Base Nature Of The Dioxides
 CO₂ and SiO₂ are acidic.
vCarbon dioxide react with dilute sodiun
hydroxide form carbonate.
 CO₂(g) +2NaOH(aq)→ Na₂CO₃(aq) +
H₂O(l)
vSilicon dioxide dissolves in hot and
concentrated sodium hydroxide form silicate.
 SiO₂(s) + 2NaOH (aq) → Na₂CO₃(aq) +
H₂O (l)
vSilicon dioxide is also soluble in concentrated
hydrofluoric acid,HF.
 SiO₂(s) + 6HF (aq) →[SiF₆]²⁻+2H⁺(aq)
+2H₂O(l)
 GeO₂,SnO₂ and PbO₂ are amphoteric
a.)Reaction with acid(react with hot and

concentrated hyrochloric acid to form salts)

 GeO₂ (s)+4HCl(aq) → GeCl₄(l) +
2H₂O(l)
 SnO₂(s) + 4HCl (aq)→ SnCl₄(l) + 2H₂O(l)
 -lead dioxide react with hot and
concentrated hyrochloric acid →lead (II)
chloride and chlorine gas
 PbO₂(s)+4HCl(aq) → PbCl₂(s)+Cl₂(g)+
2H₂O(l)
 - lead dioxide react with cold <20ºC and
concentrated hyrochloric acid →lead (IV)
chloride
 PbO₂(s)+4HCl(aq) → PbCl₄(s) + 2H₂O(l)
 -lead (IV) chlorided decompose slowly at
room temp.to lead (II) chloride

b.)Reaction with alkali
 -GeO₂ , SnO₂ ,and PbO₂ react with hot
and concentrated sodiun hydroxide→
Ø germanate(IV) GeO₂(s)+2NaOH(aq)
+2H₂O(l)→Na₂Ge(OH)₆(aq)
Ø stanate(IV)
 SnO₂(s) +2NaOH(aq)
+2H₂O(l)→Na₂Sn(OH)₆(aq)
Ø plumbate(IV)
 PbO₂(s) +2NaOH(aq)
+2H₂O(l)→Na₂Pb(OH)₆(aq)

Catenation
 Ability of an element to form bonds between
atoms of the same element
 —C—C—C—C—C—

M-M
bond C—C Si—Si Ge—Ge Sn—Sn C=C CΞC
Bond
energy/k 348 176 188 150 610 840
Jmol⁻¹
vCarbon has strongest M­M  bonds,strong double and triped bonds
vOnly Carbon can cantention to form a series of compound(organic 
compounds)
Use of Carbon
qCommon Uses of Carbon
vUsed as a decorative tool in jewelry items.
vUsed as a base for the ink that is used in
inkjet printers.
vUsed in the rims of automobiles as a black
fume pigment.
vVegetal carbon, is sometimes used as a
bleaching agent or a gas absorbent.
vCarbon (in the form of carbon dioxide) is also
used in carbonated and fizzy drinks, fire
extinguishers, and also as dry ice when
they are in a solid state.

vIn metallurgy, carbon monoxide is also
utilized as a reduction agent in order to
derive many other elements and
compounds.
vCarbon in the form of 'Freon' is also used in
cooling devices and systems.
vMany metal cutters and heat resistant tools
and devices are also manufactured with
carbon.

Some allotropes of carbon: a) diamond; b)
graphite; c) lonsdaleite; d–f) fullerenes
(C60, C540, C70); g) amorphous carbon;
h) carbon nanotube.
Uses of Carbon Element - Graphite

 one of the allotropes of carbon that

 out of all the materials that are found in
nature, graphite is one of the softest
substances.
 primary uses of graphite:

1.Used as a lubricant.
2.Used as lead in pencils.
3.In the form of coke, used in the production
process of steel.

Product oF carbon-Graphite
Uses of Carbon Element -
Diamond
 Making of high speed drilling materials and
precious stone.
-Diamond bearing are used in instruments for

laboratoties.
-Diamond cutting tools cut much faster and

accurately than other tools. Metals can be

sliced thinner than human hair by the
diamond blade.

Products of diamonds
 Uses of Tin
1.Tin is extracted from the cassiterite ore (SnO₂ ) .
2.SnO₂  is reduced to tin by carbon at 1200­1300°C in an electrical furnace.

3.used in solder,tin plating, tin chemicals,



brass and bronze, and other.

 Solder

vTin-Antimony
1.High temperature and food industry
applications
2.Non-toxic.
3.Good high temperature properties.
4.Better electrical conductivity and strength
than tin-lead solders.
5.Good wetting.
Product of Tin

Pewter plate
Inside of a tin platted can
vTin-Antimony-Lead
1.Suitable fo joining copper/other alloy metals
2.Improved mechanical properties over Tin-
Lead solders.
3.Can not be used with zinc due to brittle zinc-
antimony inter-metallic compounds
vTin-lead
1.General purpose, and the most widely used
solders.
2.Good process characteristics and the best
understood solders.

vTin-Silver
1.Used for soldering medical or high precision
instruments.
2.High temperature applications
3.Non-toxic but expensive. Good high
temperature properties.

Uses Of Silicon
 essentially a semi-metal (has some metallic
properties such as metallic conductivity)
that allows it to be used in semi-conductor
devices (i.e., silicon is a semiconductor).
 Making silicane(an organosilicon
polymer)used as lubricants,hydraulic
fluids ,car polish,electric insulator,water-
proof fabric, elastomers, resin, grease,and
resinous materials.
Strucuture of Silicone


Strucuture of Silicone



 silicone

Polyester Resin for Hybrid Powder Coating

 A mobile phone case made from silicone

A silicone rubber hose

Silicon(IV)Oxide Or Slilica
Sructure Of Silica

Repeating unit in silicon(IV)oxides is the tetrahedral “SiO₄”

 Chemical Properties
 Of

 Silicon (IV) Oxide

 Silicon(IV) oxide is chermically inert.
 Only attacked by:
1. hydrofluoric acid →hexafluoric acid

 SiO₂(s)+6HF(aq) → 2H⁺(aq)+[SiF₆]²⁻(aq)
+2H₂O(l)
2. concentrated alkalis→silicate

 SiO₂(s) +2NaOH(aq) →Na₂SiO₃(aq)

+H₂O(l)
Used Of Silica , Silicon(IV) Oxide
 Quart or sand
―glass and lenses for optical

instrument.
―important component in electronic

such as radar.
 Silica
--(sand) is used extensively in making

cement, concrete and ceramics.


Extraction of Phosphorous
 Used in the anhhydrite process to eliminate
sulphur dioxide.
 SiO₂(s) +3C(s) ―→ SiC(s) +2CO(g)
 silicon carbide


 There are three naturally occuring crystalline

forms of silicon(IV) oxide.
 The most stable form of silicon(IV) oxide at
room condition is quartz. Sand is powdered
quartz contaiminated with iron(III) oxide.

 Quartz

870ºC

Tridymite

1470ºC

cristobalite
 Glass

Quartz glass

-When silica is heated at around 1710°C,silicate glass (or quartz

glass) is formed.

-Quartz glass are transparent to infrared and ultraviolet

radiations.
Soda-lime Glass



Potash Glass



Borosilicate glass



Aluminosilicate Glass

 Silicate

Silicates
When silicon(IV)oxide(silica) reacts with a
molten base, silicates are formed.
The basic building block of all silicates is
the SiO⁴¯₄.
qSilicates with discrete SiO₄⁴⁺ ions.
- simple silicates such as Mg₂SiO ₄, ZrSiO ₄
contain SiO₄⁴⁺ ions.
-
-

 Aluminosilicate


 When Si⁴⁺ ions are replaced by Al³⁺ions,

aluminosilicates are formed.
 To maintain electrical neutrality, another cation, e.g.;
Na⁺, K⁺ or Ca²⁺, must be incorporated.



History
Carbon


 Carbon was known in prehistory in the form

of soot; while charcoal was made in Roman
times (by heating wood while exclude air)
and diamonds were known as early as 2500
BC in China. In 1772, Antoine Lavoisier
showed that diamonds were a form of
carbon, when he burned samples of carbon
and diamond and showed that both formed
the same amount of carbon dioxide per
gram of material. Carl Scheele showed that
graphite was a form of carbon rather a form
of lead.

 Figure 2: German-Swedish
pharmaceutical chemist Carl Wilhelm
Scheele (1742 - 1786). Author Isaac
Asimov has called him "hard-luck Scheele"
because he made a number of chemical
discoveries before others who are
generally given the credit
Figure 1: French chemist and biologist
Antoine-Laurent de Lavoisier (1743 –
1794).
 A new allotrope of carbon, fullerene, was
discovered in 1985 by Robert Curl, Harry
Kroto, and Richard Smalley who
subsequently shared the Nobel Prize in
Chemistry in 1996. Fullerenes have been
reveled to include nanostructured forms
such as buckyballs and nanotubes. The
renewed interest in new forms lead to the
discovery of further exotic allotropes,
including glassy carbon, and the realization
that amorphous carbon is not amorphous.

Silicon
 Silicon was first identified by Antoine
Lavoisier in 1787 as a component of flints,
and was later mistaken by Humphry Davy
for a compound rather than an element. In
1824, Berzelius prepared amorphous silicon
by the reaction of potassium with silicon
tetrafluoride.



Figure 4: British chemist and inventor Sir
Humphry Davy FRS (1778 - 1829).

Figure 5: Swedish chemist Jöns Jacob

Berzelius (1779 – 1848).
 Germanium is one of three elements the
existence of which was predicted in 1871
by the Russian chemist Dmitri Mendeleev
when he first devised his periodic table.
Not until 1886, however, was germanium
identified as one of the elements in a
newly found mineral.
 Dmitri Mendeleev
 The origins of tin seem to be lost in history. It
appears that bronzes, which are alloys of
copper and tin, were used by prehistoric
man some time before the pure metal was
isolated.
 Lead is mentioned often in early Biblical
accounts. The Babylonians used the metal
as plates on which to record inscriptions.
The Romans used it for tablets, water pipes,
coins, and even cooking utensils; indeed, as
a result of the last use, lead poisoning was
recognized in the time of Augustus Caesar.
The compound known as white lead was
apparently prepared as a decorative
pigment at least as early as 200 BCE.
Modern developments date to the
exploitation in the late 1700s of deposits in
End
QUESTION:
 [Q2 Paper(2A)STPM 2000]
 1.a)The tetrachlorides of Group 14 elements,
i.e. CCl₄, SiCl₄, GeCl₄, SnCl₄ and PbCl₄ are
liquids at room temperature. All the
tetrachlorides, with the exception of CCl₄,
are hydrolysed i n aqueous solution to form
acidic solutions.
 i) State the molecular shape of all the Group
14 tetrachlorides.
 ii) Write a balanced eq. for the hydrolysis of
SiCl₄.
 iii) Explain why CCl₄ does not undergo
hydrolysis. [4]
b) The standard electrode potentials,at 298K, for some half-cells are
given below.
Half-cell E° / V

Ge⁴⁺(aq)+2e Ge⁴⁺(aq) -1.60

Sn⁴⁺(aq) +2e Sn²⁺(aq) +0.15

Pb⁴⁺(aq) +2e Pb²⁺(aq) +1.80

i)Arrange the Ge⁴⁺ ion, Sn⁴⁺ ion and Pb⁴⁺ ion in the order of
decreasing stability in aqueous solution.
ii)Which ion has the most powerful reducing property?
iii)Which is more stable in aqueous solution, Pb²⁺ or Pb⁴⁺?
Explain your answer.
[4]
 STPM 2005/P2/Q7
 A scheme of reaction is shown below.
 X(l) Y(s)+Cl₂(g)


 HCl(aq)


 
 Tetrachloroplumbate(ll)(aq) ion


 Identify compound X and discuss its chemical

properties.
 Compound X is an oily liquid while compound
Y is a white solid. Explain the different
physical states of the two compounds.

 Answers: [Q2 Paper(2A)STPM 2000]
1.a)i) Tetrahedron

ii) SiCl₄(l)+2H₂O(l)→SiO₂(s)+ 4HCl(aq)

iii)C is an element in period 2 of the periodic

table. It does not empty orbitals in its

valence shell (n=2 )to form co-ordinate
bonds with water molecules.
b)i) Stability: Ge⁴⁺> Sn⁴⁺> Pb⁴⁺

ii)Ge²⁺

iii)Pb²⁺


STPM 2005/P2/Q7
1.a)X is PbCl₄, lead(IV)chloride.

 X is thermally unstable and will

decompose on heating.
 Pb⁴⁺has strong oxidizing power.
b)X is a covalent compound with weak van der

waals forces of attraction.

 Y (PbCl₂)is an ionic compound with strong
ionic bonds between Pb²⁺ion and Cl‾ ions.
