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PRE-UNIVERSITY

PRESEMESTER 1
CHAPTER 3
CHEMICAL
BONDING

Chemical Bonding can be generally divide to 5 main group








Electrovalent bonding (ionic)


Covalent bonding
Metallic bonding
Hydrogen bonding
Van der Waals bonding

To represent the types of bonding, a Lewis diagram (dot(dot-and


and-cross) is used. Each dot or cross represent one electron in
valence shell and its a more convenient way in showing
electrovalent.
For both ionic & covalent bonding, octet rule must be fulfill
where tendency of atoms to achieve noble gas configuration.
Table 6.2 show some cation/anion with difference number of
valence electron.

Electrovalent bond (ionic bond)


 Formed by transfering 1 or more ee- from outer orbital to
another. The atom donate electron is name as cation and the
atom who receive electron is name as anion. The bond form
when electrostatic attraction occur between 2 opposite charge
ions.
 Formation of ionic compound involving a metal with low IE and
a nonnon-metal with high EA. Example for lithium fluoride (LiF).
The electronic structure of the lithium and fluorine are :
Lithium (Li) = 1s2 2s1
Fluorine (F) = 1s2 2s2 2p5

Practice : Draw the Lewis dot and cross diagram for these ionic
compound
Sodium chloride

Magnesium fluoride

2+

+
Na

Mg

Cl

_
F
2

Na

Cl

Mg

2+

Aluminium oxide

3+

2O

Al

Al

3+
2

23

Covalent Bonding : Sharing of Electron


 Covalent bond is bond that formed in between atoms by
sharing electron from its atoms in order to achieve a stable
electronic configuration of ns2 np6 for atoms involve. (hydrogen
achieve 1s2)
 Some nonnon-metallic elements exist naturally as diatomic
molecules like hydrogen, and halogens groups.
groups.
Hydrogen molecule

Chlorine molecule

Oxygen molecule

Nitrogen molecule

From example above, we can see that in covalent bond,


molecules may form single bond, double bond or triple bond in
order to achieve stable valence electrons. Though, there are
some molecules with the exceptions of achieving stable
valence electrons.

Electron deficient compounds compounds which the molecule


(especially the center atom) does not achieve octet electron
arrangement. Examples of these molecules are BeCl2 ; BF3 and
AlCl3.
Beryllium dichloride

Cl

Be

Cl

Boron trifluoride

Aluminium trichloride

Electron rich compounds compounds which have more than 8


electrons at center atom of molecules, such as PCl5, SF6 and ICl5.

Phosphorous pentachloride

Sulphur hexachloride

Iodine pentachloride

However, not all compounds can have more or less than 8 electrons
in the center of the atom. There are certain limitation towards the
application of the expansion of center atom

For example, nitrogen (N) and phosphorous (P) are both from

15
Group @@@
but phosphorous can exist as PCl3 and PCl5 while
nitrogen can only have NCl3 but not NCl5. This is because
nitrogen
which only have
2 shell, do not have empty dd-orbital
@@@@.....................@@@@@@@@@@@@@@@@@@@@
@@@@.....................
@@@@@@@@@@@@@@@@@@@@
available,
but phosphorous contain dd-orbital to fill in more electron
@@@@@@@@@@@@@@@@@@@@..................................


Same things occur when it come to hydrolysis of CCl4 and SiCl4.


SiCl4 can undergoes hydrolysis with water according to the equation

SiCl

+ 2 H O  SiO + 4 HCl

4
2
2
@@@@@@@@@@@@@@@@@@@@@@@@@@.

while CCl4 cannot. Despite the factors that they are from the same

14
group (Group @@@),
CCl4 cannot undergoes hydrolysis as
carbon which only have 2 shell, do not have empty dd-orbital
@@@@@@@@@@@@@@@@@@@@...@@@@@@@@@
available, so water cannot form coordinative with carbon hence
@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@
cannot undergoes hydrolysis.

Examples : Draw the Lewis structure for the following molecules.


CO2

HCN

CH3COOH

C2H2

NH3

CO32-

SO42-

C3H6




6.2.1
Dative bond
Now, try drawing the Lewis structure for these molecules : SO2,
SO3, NO3- or CO.
SO2

SO3

NO3-

CO

Dative bond is formed when an atom that has lone pair


electrons which can donate to molecule/ion that has empty
unhybridise orbital.
Following are a few applications of dative bond in covalent
molecules

1. Dative bond in helping molecule to achieve octet.

NH4+

BF3.NH3

Dative bond in forming dimer ~ 2 monomer combine forming a


dimer..
dimer
Forming Al2Cl6

Forming polymer of BeCl2


Cl
Be

Cl
Be

Cl

Cl
Be

Cl

Cl

3.


Dative bond in formation of complex ion.


Molecule / ion form dative bond (also known as coordinative bond)
ligand
by donating lone pair electron, which act as a @@@@..
in the
formation of complex ions. For example

hexaaquacopper (II) ion ;


[Cu(H2O)6]2+

tetraamminenickel (II) ion ; Hexacyanoferrate (III) ion ;


[Ni(NH3)42+]
[Fe(CN)6]3-

6.2.3 Resonance ~ a molecule/polyatomic ion in which two or more


plausible Lewis structure can be written but the actual structure
cannot be written at all
Sulphur dioxide, SO2

Ethanoate ion, CH3COO

Nitrogen dioxide, NO2

Sulphur trioxide, SO3

Carbonate ion, CO32-

2-

O
C
O

2-

O
C

2-

O
C

Since the resonance structure cannot be determined as it does not


have a permanent structure so it is expressed as a combined of
resonance structure known as resonance hybrid

Resonance hybrid

2-

O
C
O

Covalent Bonds : Overlapping of Orbitals


 2 ways in explaining how covalent bond are attached :



Valence bond theory


Valence--shell electron
Valence
electron--pair repulsion theory (VSEPR)

Here we can explain and predict what type of molecular bond


and shape will form through the bonding formation but it does
not explain the stability of covalent bond.
For valence bond theory, it used atomic orbital overlapping
that result the formation of a new molecular orbital embracing
both nuclei. The strength of covalent bond is proportional to
the area where the atomic orbital overlap. Larger the area
overlap, stronger the covalent bond.

Hybrid Atomic Orbitals


 3 basic types of hybrid orbital




sp3 hybrid orbital (tetrahedral arrangement)


sp2 hybrid orbital (trigonal
(trigonal planar arrangement)
sp hybrid orbital (linear arrangement)

6.3.2 sp3 hybridisation


 The term sp3 gives an impression of the hybridisation involved
1 s orbital and _____
3
_____
p orbitals
 Examples of molecules which give sp3 hybridisation are
Methane
sulphate ion


CH4
SO42-

silicon tetrachloride

SiCl4

Perchlorate ion

ClO4-

14
For example, in methane, CH4, since carbon is in Group _____so
2s2 2p2
the valance electron of C is _______

State of
molecules

Orbital diagram

_____ _____ _____


2p
Ground
state

____
2s

Excited
state

____
2s

Hybridisati
on state

____ ____ ____


2p

_____ _____ _____ _____


sp3

Illustration / Explanation

109.50
tetrahedral

6.3.3 sp2 hybridisation


 The term sp2 gives an impression of the hybridisation involved
1 s orbital and _____
2
_____
p orbitals
 Examples of molecules which give sp2 hybridisation are
Sulphur trioxide

SO3

Boron trifluoride

BF3

Nitrate ion

NO3-

Carbonate ion

CO32-

13
Since boron is Group ______
element so the electron valance
2s2 2p1
of B is _________

State of
molecules

Orbital diagram

Illustration / Explanation

_____ _____ _____


2p
Ground
state

Excited
state

Hybridisati
on state

____
2s

____
2s

____ ____ ____


2p

_____ _____ _____


sp2

____
pz

Formation of sp2 Hybrid Orbitals

Shape of molecule
Trigonal planar
Angle between
bond pair
120o

6.3.4 sp hybridisation
 The term sp gives an impression of the hybridisation involved
_____
p orbitals
1 s orbital and _____
1
 Examples of molecules which give sp hybridisation are
Carbon dioxide

CO2

Beryllium chloride

Cyanic acid

HCN

Ethyne

BeCl2
C2H2

Lets use beryllium chloride as example.

2
Since beryllium is Group ______
element so the electron
2s2
valance of Be is ___________

State of
molecules

Ground
state

Excited
state

Orbital diagram

_____ _____ _____


2p
____
2s

____
2s

____ ____ ____


2p

Hybridisati _____ _____


sp
on state

___ ___
py pz

Illustration / Explanation

Formation of sp Hybrid Orbitals

Shape of molecule
Linear
Angle between bond pair
180o

6.4
Hybridisation in organic molecules
 In this subtopic, were going to witness how is the formation of the
bonding that exist in some organic molecules. The 3 organic
molecules which will be discussed in this subsub-topic are :
 methane, CH4

ethene,, C2H4
ethene
 ethyne
ethyne,, C2H2
 All of the molecules above has carbon in it
14 element. It has the electronic configuration
 Carbon is a group _____
2s2 2p2
of ______________
The orbital diagram
 Ground state of carbon : _____
_____ _____ _____
2s
2p

Methane, CH4

Type of hybridisation :

Excited state of carbon

_____

_____ _____ _____

2s
Hybridised state

2p

_____ _____ _____ _____


sp3

Molecular shape

tetrahedral
@@@@@@@@@@@@@
Angle between the bonding pair :
0
109.5
@@@@@@@@@..

Ethene,, C2H4
Ethene

Type of hybridisation :

Excited state of C : _____


2s

Hybridised state

_____ _____ _____


2p

: _____ _____ _____

sp2
Molecular shape
Trigonal planar

Angle between bond


pair bond pair
120o

sp2

_____

pz

Ethyne,, C2H2
Ethyne


Type of hybridisation :

sp

Excited state of C : _____


_____ _____ _____
2s
2p
Hybridised state : _____ _____
_____ _____

sp
Molecular shape
Linear

Angle between bond


pair bond pair
180o

py pz

As a conclusion, the formation of double


one sigma bond
bond (C=C) is due to ______sigma
______
one pi bond (
() and _____pi
_____
( )
 While the formation of triple bond (CC) is
one sigma bond (
two pi
due to ______sigma
______
() and _____pi
_____
bond (
( )






The Hybridisation of s and p orbitals in Carbon atom


Weve discussed methane molecule by using sp3 hybrid
orbitals in forming the C
CH bond in methane
Ethene molecules, C2H4 a planar molecule with a bond
angle of 120o, it can be explain below :


Formation of bonds using sp2 hybrid orbitals ~ Since 2 of the


bond is use to overlap the bonding between C
CH, the third sp2
orbital is use to overlap between C
CC bond. This type of bond is
what we name as sigma, bonds.
Formation of bonds using pz orbital ~ the p orbital which remain
unhybridises (adjacent carbon atom) undergo sideways
overlapping to form a bond. In a bond, electron cloud is
located above and below the C
CC bond. Thus, the double bond
in ethene consist and bonds.

10.5

10.5




Ethyne Molecules C2H2 (Acetylene)


A linear molecule containing triple bond H
HCC
CH. The
bonding in ethyne can be explained as follows.


Formation of bond using sp hybrid orbital ~ as explain earlier,


bond is formed when the remain sp orbital is overlapping with
each other.
Formation of bonds using py and pz orbital ~ each carbon
atom still has 2 unhybridised 2p orbitals oriented at right angles
to each other and to the axis of the sp hybrid orbitals. These p
orbital undergo sideways overlapping to form a pair of bonds.
Thus, the triple bond in ethyne consists of a bond and two
bonds.

10.5




The Hybridisation of s and p orbitals in the Oxygen atom


When we sketch the orbital diagram, we should notice that
theres 2 more space for ee- to fill into the p orbital. In the
bond form within water, H2O, we found that it has
geometrical structure nearly similar to a tetrahedral, but the
angle between 2 O
OH bond is 104.5o instead of 109.5o as in
tetrahedral. Here, we can use bonding pair and lone pair
repulsion theory to explain the situation.

Ground State

Hybridised State




Hybridisation of s and p orbital in Nitrogen Atom


Same as oxygen case, nitrogen also uses a sp3 hybrid orbital
for forming covalent bond between N and 3 H atoms. One of
the lone pair electron occupied the orbital and this will cause
repulsion of bonding to occur that makes the angle of the
bond become 107o instead of 109.5o. The shape of molecule
is pyramidal where 3 H form the base of pyramid

Ground State

Hybridised State

From the 2 examples above, we can tell how the lone pair
electrons affecting the angle between the bonding pair and
bonding pair. In ammonia, not only that there is the repulsion
between bonding pair and bonding pair but theres also the
repulsion between bonding pair and lone pair.
Since the angle between the bonding pair and bonding pair
decrease, theres a probability that its due to the effect of
stronger repulsion between the bonding pair and lone pair
electron. This statement is supported as in the repulsion
between the H
HOH in water is smaller than in ammonia,
NH3. as a conclusion, we can conclude that

lone-pair vs. lone pair


lone-pair vs. bonding
bonding-pair vs. bonding
>
>
repulsion
pair repulsion
pair repulsion

Valence Shell Electron Pair Repulsion (VSEPR) Theory


 ~ state that the electronelectron-pair repulsion stated that electron
pairs around central atom repel each other
 3 main rules



Bonding pairs and lone pairs of electrons arrange themselves to be


as far apart as possible.
The order of repulsion strength of lone pair and bond pair are
lone--pair & lone
lone
lone--pair > lone
lone--pair & bond
bond--pair > bond
bond--pair & bond
bond--pair
Double / triple bond are considered as 1 bonding pair when predicting
the shape of molecules or ions

Diagram below shows the type of bonding and the molecular


shape predicted.

VSEPR

Class

# of atoms
bonded to
central atom

# lone
pairs on
central atom

Arrangement of
electron pairs

Molecular
Geometry

AB2

linear

linear
trigonal
planar

AB3

trigonal
planar

AB4

tetrahedral

tetrahedral

AB5

trigonal
bipyramidal

trigonal
bipyramidal

AB6

octahedral

octahedral

VSEPR

Class

# of atoms
bonded to
central atom

# lone
pairs on
central atom

AB3

AB2E

Arrangement of
electron pairs

Molecular
Geometry

trigonal
planar
trigonal
planar

trigonal
planar
bent

VSEPR

Class

# of atoms
bonded to
central atom

# lone
pairs on
central atom

AB4

tetrahedral

tetrahedral

AB3E

tetrahedral

trigonal
pyramidal

Arrangement of
electron pairs

Molecular
Geometry

VSEPR

Class

# of atoms
bonded to
central atom

# lone
pairs on
central atom

AB4

Arrangement of
electron pairs

Molecular
Geometry

tetrahedral

tetrahedral

AB3E

tetrahedral

trigonal
pyramidal

AB2E2

tetrahedral

bent
O
H

VSEPR

Class

AB5
AB4E

# of atoms
bonded to
central atom

5
4

# lone
pairs on
central atom

Arrangement of
electron pairs

Molecular
Geometry

trigonal
bipyramidal

trigonal
bipyramidal

trigonal
bipyramidal

See-saw

VSEPR

Class

AB5

# of atoms
bonded to
central atom

# lone
pairs on
central atom

AB4E

AB3E2

Arrangement of
electron pairs

Molecular
Geometry

trigonal
bipyramidal

trigonal
bipyramidal

trigonal
bipyramidal
trigonal
bipyramidal

distorted
tetrahedron
T-shaped
F
F

Cl
F
10.1

VSEPR

Class

AB5

# of atoms
bonded to
central atom

# lone
pairs on
central atom

AB4E

AB3E2

AB2E3

Arrangement of
electron pairs

Molecular
Geometry

trigonal
bipyramidal

trigonal
bipyramidal

trigonal
bipyramidal
trigonal
bipyramidal

distorted
tetrahedron

trigonal
bipyramidal

T-shaped
linear
I
I
I

VSEPR

Class

# of atoms
bonded to
central atom

# lone
pairs on
central atom

AB6

octahedral

AB5E

octahedral

Arrangement of
electron pairs

Molecular
Geometry

octahedral
square
pyramidal
F
F
F
Br
F

VSEPR

Class

# of atoms
bonded to
central atom

# lone
pairs on
central atom

AB6

octahedral

octahedral

AB5E

octahedral

AB4E2

octahedral

square
pyramidal
square
planar

Arrangement of
electron pairs

Molecular
Geometry

F
Xe

5 GENERAL STEPS TAKEN WHEN WRITING LEWIS


STRUCTURE FOR MOLECULES AND IONS
Calculate the total number of valence electrons from all atoms
 Arrange all the atoms surrounding the central atom by using a
pair of electron per bond
 Assign the remaining electrons to the terminal atoms so that
each terminal atom has 8 electrons (H = 2 ee -)
 Place any leftleft-over electron on the central atom.
@ Form multiple bonds if there are not enough electrons to give the
central atom an octet of electrons.


6.6
Electronegativity and Polar Molecules
 Electronegativity are measurement of ability of an atom in
molecules to attract a pair of electron
 For 2 identical atoms, since they have same electronegativity so
they have no difference in electronegativity
electronegativity.. These molecules are
called polar molecules
 While if 2 not identical form a covalent bond, the bonding electrons
will attracted more strongly by more electronegative element. We
can indicate the polarity of hydrogen chloride molecules in 2 ways.




Cl

The separation of charge (between + and ) in a poplar


molecule is called dipole
When 2 electrical charges of opposite sign are separated by small
distance, dipole moment is established





Molecules that are polar have large dipole moments.


Molecules that are non polar have zero dipole moment.
Still, for some molecules, even there are different in
electronegativity but it doesnt mean that these molecules there
are polar molecules. When the surrounding atom are
symmetrically surrounded by identical (same) atom, they are
non--polar
non
Example of molecules which are non polar

Dipole Moments and Polar Molecules

electron poor
region

electron rich
region

=Qxr
Q is the charge
r is the distance between charges
1 D = 3.36 x 10-30 C m

Which of the following molecules have a dipole moment?


H2O, CO2, SO2, and CH4
O

dipole moment
polar molecule

dipole moment
polar molecule
H

no dipole moment
nonpolar molecule

H
no dipole moment
nonpolar molecule

Nitrogen dioxide, NO2

Methane, CH4

Ethene, C2H4

Benzene, C6H6

Boron trifluoride, BF3

Cyanide acid, HCN

Sulphur dioxide, SO2

Sulphur trioxide, SO3

Ammonia, NH3

Ammonium ion, NH4+

Ethane, C2H6

Chloroethane, C2H5Cl

N
H

H
H

Cyclohexane, C6H12

Chlorocyclohexane,
C6H11Cl

Carbon dioxide, CO2

Carbonate ion, CO32-

2-

O
C
O
Phosphorous
trichloride, PCl3

Phosphorous
pentachloride, PCl5

cisbut-2-ene

transbut-2-ene

H3C

H
C

C
CH3

A simple experiment which can


be used to determine either a
molecule is polar or non polar
is illustrated below
By using the liquid form of the
compound, it is flow out slowly
from burette while a negative
charged rod is bring close to
the flow of the liquid.
If the liquid is deflected to the
direction of negative charged,
polar
this liquid is @@@@
If it remain undeflected,
undeflected, this
non--polar
non
liquid is @@@@@.

From the example above, classified which compounds can be


deflected and which cannot

Compound which can be deflected


by charged rod

Compound which cannot be


deflected by charged rod

Nitrogen dioxide,
Cyanide acid,
Sulphur dioxide,
Ammonia,
Chloroethane,,
Chloroethane
Chlorocyclohexane,,
Chlorocyclohexane
Phosphorous trichloride
CisCis-but
but--2-ene

Methane, ethene
ethene,, benzene,
Sulphur trioxide,
Ammonium ion,
Ethane, cyclohexane
cyclohexane,,
Carbon dioxide,
Carbonate ion,
Phosphorous pentachloride
pentachloride,,
Trans--but
Trans
but--2-ene

Electronegativity and Type of Chemical Bond.


 Actually, the type of bond that would form can be tell by using
the difference of electronegativity (
(EN). More larger the
difference, the more tendency of electron form low EN move
an electron to higher EN atom and ionic compound is formed.
 The relationship between the ionic character and the
difference in the electronegativity of the bonded atom is
shown on next slide (or page 220).
 The presence of dipoles gives ionic character to polar
covalent molecules. When the polarity of the covalent
molecule increases, the ionic character also increase.
 An ionic bond is formed if the cation has a small ionic
radius anion has a large ionic radius both cation & anion
carries a low electrical charge.
 Polarisation ~ the distortion of the charge cloud of the
negative ion by a neighbouring positive ion.

Fig. 9.18

3.6.1


Covalency Properties in Ionic Molecules

From the graph above, the dotted line represent the


arbitrary line between ionic and covalent characteristic of
a molecule. To be more specific, there more likely an
ionic compound may have high covalent characteristic
(exemplified by LiI),
LiI), or conversely covalent compound
having high ionic characteristic (exemplified by HF).
The covalent characteristic of a molecule is dependent
on the ability of a cation to polarise an anion. Polarisation
indicates the ability of a cation to attract the electron
density of an anion when put next to the cation involved.
When a cation is able to pull the electron density of the
anion closer to it, as if the anion wanted to share electron
with cation
cation,, hence increase the covalency of the
molecule

A+

Highly ionic compound


 Large cationic size
 Small anionic size

B+

Highly covalent compound


 small cationic size
 large anionic size

The covalency properties of a molecule is dependent on the


cation and anion where they can be explained qualitatively via

Polarisation power of cation

Polarisability of anion

3.6.1.1
Polarisation Power of Cation
 Polarisation Power of Cation measure the ability of a cation
to polarise the electron cloud of the anion.
 2 factors determining the polarisation power of cation
Charge of cation
Size of cation
Greater the charge of ion, higher the
Smaller the size of cation, closer the
effective nuclear charge of cation,
neighboring anion to the nucleus of
hence it will be able to attract the
cation, hence easier for the cation to
neighboring electron density of anion.
polarise the anion and result an
This will caused the polarization power
increment in the polarization power of
of cation increase, hence increase the
cation, and increase the covalent
covalent characteristic of cation.
characteristic of cation.
Both factors can be explained in another term called as charge density where
Charge Density = Charge / Ionic Radius
From the equation above, Charge Density will have a greater value, provided that
cation has a high charge and small cationic radius.
Greater the charge density, higher the polarization power, greater the covalent
characteristic of the cation.

3.6.1.2
Polarisability of Anion
 Polarisability of an anion ~ ability of the anion to allow the electron
density to be polarised by cation.
cation.
 2 factors determining the polarisability of an anion
Charge of anion

Size of anion

Greater the charge of anion, lower the


Larger the size of anion, further the
effective nuclear charge of anion. This will
outermost electron from the nucleus
weakened the electrostatic attraction forces
of the anion, easier for the cation to
between nucleus and the outermost
polarise the anion, and cause the
electron in anion, and increase the
polarisability to increase, hence
polarisability of the anion, hence increase
increase the covalent characteristic
the covalent characteristic of anion
of anion.


Unlike cation
cation,, anion does not have a term that combined both
factors of charge and ionic radius. However, information of
polarisability of anion enable the prediction of the covalent
characteristic of a molecule, since in order to form a covalent bond,
it depend on both polarisation power of cation and polarisability of
the anion

3.6.2
Prediction of Chemical Bond ::Fajans
Fajans Rule
 In 1923,
1923, Kazimierz Fajans formulated an easy guidance to predict
whether a chemical bond will be covalent or ionic, and depend on
the charge on the cation and the relative sizes of the cation and
anion. They can be summarized in the following table
Ionic compound

Low positive charge

Large cation

Small anion

Covalent compound

High positive charge

Small cation

Large anion

Based on these guidance, the bonding of a few compounds


shall be discussed to understand the application of Fajans
Fajans
Rule in the chemical bonding

Lithium halide (LiX


(LiX))
 Lithium ion, Li+ (1s2) has a small size due to only 1 shell
present in its ion. But since it has a low charge, so its charge
density is not too high. That is why, all lithium halide are ionic
compound. The covalency of lithium halide varies from a
highly ioniccharacteristic to highly covalency
covalency,, depending on
the polarisability of the anion next to Li+
 When a group of halide, F ; Cl; Br; I is put close to Li+, the
covalency of lithium halide increase when going down to
Group 17 halide. LiF is highly ionic, since the fluoride ion has
small ionic size and low charge, hence has low polarisability
polarisability..
Ionic size increase with the increasing shell when going down
to Group 17 halide, hence increase the polarisability
polarisability,, which
allowed lithium ion to polarise the anions electron density,
hence increase the covalency

Cl
Br

Li+

Aluminium halide (AlX3) and aluminium oxide (Al2O3)


 Aluminium ion (Al3+) has high charge density, due to its high
charge unit and its small ionic radius
radius.. So, depending on the anion,
aluminium has a high tendency to form covalent compound
compound.. For
example, when going down to Group 17 halide, aluminium fluoride
(AlF3) forms ionic compound (since F- has a low polarisability
polarisability),
),
while aluminium trichloride (AlCl3), aluminium tribromide (AlBr3)
and aluminium iodide (AlI3) form covalent compound (since
chloride, bromide and iodide have high polarisability
polarisability)). This
explained why aluminium fluoride has a high melting point
(10400C), while aluminium trichloride and tribromide are 1920C and
780C respectively
respectively..
 As for aluminium oxide (Al2O3), it is an ionic compound with high
covalent characteristic, as aluminium ion has high covalent
characteristic due to its high charge density
density.. This explained the
high melting point of Al2O3 (20500C) yet it is insoluble in water
water.. It
also explained the amphoteric properties of aluminium oxide where
aluminium oxide can act as an acid (covalent characteristic), as
well as a base (ionic characteristic)
characteristic)..

Metallic Bonding
 The properties of metals cannot be explained in terms of the
ionic / covalent bond. In ionic / covalent compound, electron
are not free to move under the influence of applied potential
(charge) difference. Therefore, ionic solid and covalent
compound are insulator
insulator..
 In metal, electron are delocalised and metal atoms are
effectively ionised
ionised..
 Metallic bond ~ electrostatic attraction between the positively
charged metal ion and the electron delocalised
delocalised..
 Because of this, electron now can freely move from cathode
to anode when a metal is subjected to an electrical potential.
The mobile electron can also conduct heat by carrying the
kinetic energy from a hot part of the metal to a cold part. This
electron delocalised can also use to explain the electrical
and thermal conductivities of metal

The Band Theory : Overlapping of Orbital


 The number of molecular orbitals produced is equal to the
number of atomic orbitals that overlap.
 In a metal, the number of atomic orbitals that overlap is very
large. Thus the number of molecular orbital produced is also
very large.
 The energy separations between these metal orbitals are
extremely small. So, we may regard the orbital as merging
together to form a continuous band of allowed energy state.
This collection of very closed molecular orbital energy levels
is called an energy band. This theory for metal is called band
theory

Electrical Conductors
 Molecular orbital model == 2 group of energy level.



Lower energy level valence band form from overlap of outer


most orbital containing valence electron of each atom.
Higher energy level conduction band energy level filled with
mobile electron

But there are some case where valence band can also serve
as conduction band (caused by the movement of delocalised
molecular orbital)
Electrical conductivities decrease when temperature
increase vibration of the lattice of ion impedes the free
movement of electron in conduction band.
conduction band
valence band

Insulator
 Difference between conductors, semisemi-conductors, and
insulator depend on the energy gap between the 2 bands.
 Conductor 2 bands overlaps so conduction band always
partly filled.
 Insulator gap between the band is large and no electron
exist in the conduction band. E.g. insulator diamond
 When 2s and 2p orbital of C is combine to form 2 energy
bands, valence band is filled with electron.
 In insulator, the energy gap between the band is large. Under
normal condition, few electrons in valence band can jump
across to conduction band. If electron cannot reach
conduction band across the gaps, the electrical conduction
cannot take place.

Semiconductor
 Theres still energy gaps between 2 bands in semiconductor,
but it is smaller than insulator.
 In semiconductor, some electrons have sufficient energy to
jump across the energy gaps and electron can move freely
in conduction band thus enable electrical conduction.
 Still, the electrical activity is not as good as metal (conductor)
Increasing temperature can help to improve the conductivity
because electron gain thermal energy and are able to reach
conduction band.
 It can also improve its effectiveness by adding small amount
of substance. This adding is what we called doping. It can
help to increase electrons to fill in valence band.
 Example of doping is Si dope P (n(n-type). Si dope Ge (p(p-type)
Depend on the needs, this process can help to create the
various type of semiconductor in electronic characteristic.

7.1
Van der Waals forces
 Van Der Waals forces are the intermolecular forces formed
between covalently bond molecules which exist as simple
molecules.
 There are 2 types of Van Der Waals forces namely
Permanent Dipole Permanent dipole forces
Temporary dipole induced dipole forces

7.1.1 DipoleDipole-dipole attraction forces


1. Polar molecule possessed dipole moment. Each of the polar
molecules have an overall magnitude. For example in hydrogen
chloride
H Cl
+

2. The dipole inside polar molecules is permanent and the forces


between the molecule form as the positive end of dipole will
attract to the negative end of another molecules dipole.

3. This kind of forced are called permanent dipoledipole-dipole forces.


4. The strength of the attraction depends on two factors : dipole
moment and relative molecular mass

5. Higher the dipole moment the more polar the molecule


stronger the Van Der Waals forces
6. Comparisons were made between 4 molecules that have
nearly equaled of molecular mass, but with different dipole
moment
Compounds
Propane , CH3CH2CH3
Methyl methoxide, CH3OCH3
Chloromethane
Methyl cyanide, CH3CN

RMM
44
44
50.5
41

DM
0.1
1.3
1.9
3.9

Boiling point (C)


- 18.0
4.0
6.0
56.0

7. Methyl cyanide exhibit the highest boiling point among the 3


molecules as it has the highest dipole moment among these
molecules, which makes the attraction between the dipoledipoledipole attraction become stronger, and required a higher
temperature to break the attraction forces among CH3CN----CN----CH3CN.
CN.

8. Another factor which influence the strength of permanent


dipole--dipole forces, are the factor of relative molecular
dipole
mass.
9. Higher the mass, stronger the forces of attraction ( Van Der
Waals forces ), higher the boiling point or melting point of the
substance

Hydrogen chloride, H Cl

36.5

Melting
point (C)
- 114

Hydrogen bromide, H Br

81.0

- 87

- 66

Hydrogen iodide, H I

128

- 51

- 35

RMM

Boiling
point (C)
- 85

7.1.2 Temporary dipole induce dipole forces


 Non
Non--polar molecules have a dipole moment = 0.
Basically, they wont have any attraction between the
molecules as there are no significant poles with
charge in the molecule, so how they interact ??!!!
 For nonnon-polar molecules, they may have a chance to
form asymmetrical structure, as the distribution of
electron within the molecule are not even, giving the
atom a temporary dipole moment.
 During the formation of temporary dipole moment,
moment,
induction process takes place where the distribution of
electron are uneven and give the atom which are
temporary rich of electron to form dipole. These
dipoles also known as induce dipole.
 When induced dipole is formed , a temporary
interaction between the molecules formed and
produces weak forces among them.

This theory is introduced by Frite London in 1930. It is known


as London dispersion forces.

In (a) the nonnon-polar molecule which does not have a dipole


within the molecule begin to fluctuate and thus forming a
temporary dipole as in (b). Thus the forces of attraction will
formed between the temporary dipole and this forces is
named as London Forces

7.2 Effect of the intermolecular forces ( Van der waals ) on the


physical properties of the molecules
 H vapourisation  give a quantitative measurement of strength of
attractive forces present in liquid. So, H
H vapourisation ,  the
boiling point ,  the intermolecular forces among its molecules.
 When a molecule increase in size, the number of electron also
increase, so the attraction between the electron valence and
nucleus become less.
less. This distortion of electron cloud can easily
occur and increase the polarisability of the negative ion.
 This can be relating with the dispersion forces among molecules
therefore H vapourisation  , e.g. : Value of boiling point of
halogen gas increase. ( from F2  I2 )
 In hydrocarbon, boiling point increase with relative molecular
mass (RMM). Molecule with higher RMM will have a higher
boiling point.
 The effect of branched chain in hydrocarbon will also affect the
boiling point of hydrocarbon involved

Structure

RMM

Boiling point
(C)

2,2dimethyl
propane

72

2-methylbutane

72

18

72

36

npentane


CH3 CH2 CH2 CH2 CH3

This is due to a larger surface area in a straight chain of


hydrocarbon, and allows greater forces between the
molecules giving larger Van der Waals forces compare to
branch chain hydrocarbon

7.3
Hydrogen Bonding
 Hydrogen bond is a special dipole
dipoledipole interaction between
H atom with other atom with high electronegativity
electronegativity.. ( N, O, F )

It is extra stable than normal Van der waals forces and


required a high energy to break the bond. This explained why
the boiling point of NH3, H2O and HF are higher than other
hydrogen compound from each of their particular group.

Decreasing

molar mass
Decreasing boiling point

Hydrogen bond can also be used to explain the different of


boiling point of some organic compound. In the diagram above,
the trend of the compound in the same group deviates for N, O
and F, as it form hydrogen bond among themselves.
Hydrogen bond can be compared among NH3 , H2O and HF.
HF has a higher boiling point than NH3 due to higher
electronegativity of fluorine compare to nitrogen. So the dipole
moment of H
HF is greater than N
N
H, which results greater
hydrogen bond. Though, O has a lower electronegativity than F,
but H2O has a greater boiling point compare to HF because in
between H2O ---- H2O molecules, they can form 2 hydrogen
bond between the molecule but between HF --- HF can only
form one hydrogen bond. So, the more the hydrogen formed,
greater the forces, higher the boiling point.
The factors of hydrogen bonding can also use to explain the
solubility of some organic compound in water, like example,
ethane cannot dissolve in water but ethanol can dissolve in
water, due to the hydrogen bonding.

Some of the molecules gain more stability by forming dimer


with its molecules.
molecules. E.g. : When ethanoic acid is brought to
mass spectrometer for detection and it gives a peak at m/e at
120. This indicates the shows that ethanoic acid (CH3COOH)
has a RMM of 120, as CH3COOH , RMM = 60.

This indicate ethanoic acid exist as dimer where interaction of


hydrogen bonding between end of each functioning group
COOH occur.

There is another application of hydrogen bond, which is the


intermolecular forces and intramolecular forces. In 2
2-nitrophenol and 44-nitrophenol, the boiling point of the 2
compounds can be explain below :

Since 22-nitrophenol form strong hydrogen bond as


intramolecular forces, the interaction between 2
2--nitrophenol
molecules are weaker among each other, compare to 44nitrophenol, which used hydrogen bond as their
intermolecular forces. With stronger hydrogen bond which act
as the intermolecular forces, the boiling point of 44-nitrophenol
is expected to be higher than 22-nitrophenol