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CHEMISTRY SEMESTER 1 CHEMISTRY SEMESTER 1

CHAPTER 3 CHAPTER 3
CHEMICAL BONDING CHEMICAL BONDING CHEMICAL BONDING CHEMICAL BONDING
CHAPTER 3 : CHEMICAL BONDING
3.1 Ionic bonding
3.2 Covalent bonding
3.3 Metallic bonding
3.4
Intermolecular forces : Van der Waals forces and
hydrogen bonding
Topic
2007 2008 2009 2010 2011 2012
2013
Sem 1
2014
Sem 1
P1 P2 P1 P2 P1 P2 P1 P2 P1 P2 P1 P2 A
B,
C
A
B,
C
3.
Chemical
Bonding
4
3c,
6a
4 5a 3
3b,
c
1 2
2,
5b
2
1b
5c
7a
3
19
b
3 19
INTERACTION
BETWEEN ELEMENTS
Metal and
non-metal
Non - metal and
non-metal
Metal and
metal
A Lewis dot symbol consists of the symbol of an element and
one dot for each valence electron in an atom of the element
3.1 Ionic Bonding
The central idea of the ionic bonding model is the transfer of
electrons from metal atoms to non-metal atoms to form
ions that come together in a solid ionic compound, where
ionic bond is formed in between oppositely charged ions
by electrostatic attraction forces.
For example, in the formation of sodium fluoride, NaF
Sodium atom Fluorine atom Sodium fluoride
Electronic
configuration
Na (1s
2
2s
2
2p
6
3s
1
) F (1s
2
2s
2
2p
5
)
Na
+
F
-
(1s
2
2s
2
2p
6
) (1s
2
2s
2
2p
6
)
Orbital
diagrams Na F Na
+
F
-
Lewis
diagram
1s 2s 2p 3s
The interaction between sodium atom and fluorine atom
occur, where sodium atom (with low ionisation energy)
donates electron to fluorine (with high electron affinity) to form
sodium ion, Na
+
, and fluoride ion, F
-
, respectively. Note that
both ions have achieved octet arrangement of ns
2
np
6
, as it is
the most stable form of an ion formed.
The oppositely charged Na
+
and F
-
form a giant ionic crystal
lattice, with very high melting point, via electrostatic attraction
forces. forces.
i. Magnesiumchloride, MgCl
2
ii. potassium oxide, K
2
O
iii. Calciumsulphide, CaS iv. aluminiumoxide, Al
2
O
3
According to Coulumb's Law, electrostatic energy between
two oppositely charged substance (A and B) is directly
proportional to the charge carried by each ions yet inversely
proportional to the distance between them
This relationship helps us predict trends in lattice energy and
explain the effects of ionic size and charge
( )
+
+

r r
Q Q
energy lattice or Energy tic Electrosta
n n
a) Effect of ionic size : As we move down a group in the
periodic table, the ionic radius increases. Therefore, the
electrostatic energy between cations and anions decreases
because the inter-ionic distance is greater; thus, the lattice
energies of their compounds should decrease as well. This
prediction is borne out by the alkali-metal halides. note the
regular decrease in lattice energy down a group whether we
hold the cation constant (LiF to LiI)
b) Effect of ionic charge : When we compare lithium fluoride
with magnesium oxide, we find cations of about equal radii
(Li
+
= 76 pm and Mg
2+
= 72 pm) and anions of about equal
radii (F
-
= 133 pm and O
2-
= 140 pm). Thus, the only
significant difference is the ionic charge: LiF contains the
singly charged Li
+
and F
-
ions, whereas MgO contains the
doubly charged Mg
2+
and O
2-
ions. The difference in their
lattice energies is :
H
lattice
of LiF = - 1050 kJ mol
-1
H
lattice
of LiF = - 1050 kJ mol
H
lattice
of MgO = - 3923 kJ mol
-1
This nearly fourfold increase in H
lattice
reflects the fourfold
increase in the product of the charges (1 x 1 vs. 2 x 2) in the
numerator of equation above
3. Properties of Ionic Compound.
a) Melting point - Ionic compound has giant ionic crystal lattice,
which are hold by strong electrostatic attraction forces by
repeating of oppositely charged ions
Therefore, the melting point of ionic compounds are usually
very high as a lot of energies are required to overcome the
electrostatic attraction forces, and melted to form free moving
ions. Therefore, ionic compounds have very high melting
point
b) Conductivity of electricity - Most ionic compounds do not
conduct electricity (insulator) in the solid state but do
conduct it when melted or when dissolved in water. (except
some super-ionic conductors, such as AgI, which have
remarkable conductivity in the solid state.) Solid ionic salt
consists of immobilized ions. When it melts or dissolves,
however, the ions are free to move and carry an electric
current
c) Hardness and brittleness of ionic compound - All ionic solids c) Hardness and brittleness of ionic compound - All ionic solids
are hard (does not dent), rigid (does not bend), and brittle
(cracks without deforming). These properties are due to the
powerful attractive forces that hold the ions in specific
positions throughout the crystal. Moving the ions out of
position requires overcoming these forces, so the sample
resists denting and bending. If enough pressure is applied,
ions of like charge are brought next to each other, and
repulsive forces crack the ionic solid suddenly
3.2 Covalent bond
Studies of covalent bond, was widely developed ever since
Lewis suggested that a chemical bond exist in a hydrogen gas
occur by sharing en electron between two hydrogen atoms.
Electron pair that connect the 2 hydrogen atoms is called
covalent bond, a bond in which two electrons are shared by
two atoms, and the electron pair that bond between the two two atoms, and the electron pair that bond between the two
hydrogen atoms is also called as bonding pair electrons.
In a covalent bond, each electron in a shared pair is attracted to
the nuclei of both atoms. This attraction holds the two atoms in
H
2
together and is responsible for the formation of covalent
bonds in other molecules.
2. A Lewis structure is a representation of covalent bonding
in which shared electron pairs are shown either as lines
or as pairs of dots between two atoms, and lone pairs
are shown as pairs of dots on individual atoms. Only
valence electrons are shown in a Lewis structure
a) Consider the fluorine molecule, F
2
. The electron
configuration of F is 1s
2
2s
2
2p
5
. The 1s electrons are in
inner shell which is nearest to the nucleus. For this reason
they do not participate in bond formation. Thus, each F they do not participate in bond formation. Thus, each F
atom has seven valence electrons (2s
2
2p
5
). Therefore,
each fluorine atom needed one electron to achieve octet
configuration (ns
2
np
6
)
F : 1s
2
2s
2
2p
5
F : 1s
2
2s
2
2p
5
1s
2
2s
2
2p
6
1s
2
2s
2
2p
6
Oxygen atom has electronic configuration of 1s
2
2s
2
2p
4
. To
achieve stable octet configuration (ns
2
np
6
), each oxygen
atom need 2 electrons. Hence, when 2 oxygen atoms
interact, they shared two electrons in between each other as
described in diagram below.
1s 2s 2p 1s 2s 2p O : 1s
2
2s
2
2p
4
O : 1s
2
2s
2
2p
4
1s
2
2s
2
2p
6
1s
2
2s
2
2p
6
From the structure of oxygen molecule formed, each oxygen
atom shared two electrons from each other to form a double
bond, in order to achieve octet configuration among each
oxygen atom
Nitrogen has electronic configuration of 1s
2
2s
2
2p
3
and
required 3 electrons to achieve octet configuration (ns
2
np
6
).
In this case, each nitrogen atom shared 3 electrons from
each of its atom to form triple bond
N : 1s
2
2s
2
2p
3
N : 1s
2
2s
2
2p
3
1s
2
2s
2
2p
6
1s
2
2s
2
2p
6
Water, H
2
O
H : 1s
1
O : 2s
2
2p
4
Carbon dioxide, CO
2
C : 2s
2
2p
2
O : 2s
2
2p
4
Ammonia, NH
3
H : 1s
1
N : 2s
2
2p
3
Ethene, C
2
H
4
H : 1s
1
C : 2s
2
2p
2
Hydrogen cyanide, HCN
H : 1s
1
N : 2s
2
2p
3
C : 2s
2
2p
2
Ethanoic acid, CH
3
COOH
H : 1s
1
O : 2s
2
2p
4
C : 2s
2
2p
2
Tetrachloromethane, CCl
4
C : 2s
2
2p
2
Cl : 3s
2
3p
5
Ethyne, C
2
H
2
H : 1s
1
C : 2s
2
2p
2
a) Note that in ethene, hydrogen cyanide and ethanoic acid, all
the valence electrons are used in bonding; there are no lone
pairs on the carbon atoms. In fact, most of the stable
molecules containing carbon do not have lone pairs on the
carbon atoms.
b) Multiple bonds (double bond or triple bond) are shorter
than single covalent bonds. Bond length is defined as the
distance between the nuclei of two covalently bonded atoms
in a molecule. For a given pair of atoms, such as carbon and in a molecule. For a given pair of atoms, such as carbon and
nitrogen, triple bonds are shorter than double bonds, which,
in turn, are shorter than single bonds. The shorter multiple
bonds are also more stable than single bonds.
c) Covalent bond not only exist in neutral molecule, but also in
some molecular ions. Table below shows a few example of
molecular ions, which have covalent bonds in its molecule
Carbonate ion, CO
3
2-
C : 2s
2
2p
2
O : 2s
2
2p
4
Cyanide ion, CN
-
N : 2s
2
2p
3
C : 2s
2
2p
2
Sulphate ion, SO
2-
Nitrate ion, NO
-
Sulphate ion, SO
4
2-
S : 3s
2
3p
4
O : 2s
2
2p
4
Nitrate ion, NO
3
-
N : 2s
2
2p
3
O : 2s
2
2p
4
3.2.1 Exception of Octet Rules
1. From the Lewis structure sketched for sulphate ion, SO
4
2-
, we can
see that the center metal atom (sulphur) has more than 8
electrons. For this, the molecule is described as molecule that can
expanded octet. These molecules that have more than 8
electrons are located at Period 3 and below, as these center
atoms have empty d-orbital available to expand the number of
electrons positioned in the center atom. Those center atom from
Period 2, such as C, N, O and F can only allocate a maximum
of 8 electrons, since they do not have d-orbital available. of 8 electrons, since they do not have d-orbital available.
Example : Both phosphorous and nitrogen are elements from Group
15, with the valence electron of ns
2
np
3
. They can both form NCl
3
and PCl
3
respectively when react with limited amount of chlorine,
however under excess chlorine, only PCl
5
can be formed but
not NCl
5
. Explain the statement bolded.
Solution : This is due to, phosphorous, which is from period
3, have empty d-orbital to expand the octet. However,
nitrogen, which is from Period 2, do not have empty
orbital and can only allocate 8 electrons in it's shell.
Phosphorous pentachloride, PCl
5
P : 3s
2
3p
3
Cl : 3s
2
3p
5
Sulphur hexafluoride, SF
6
S : 3s
2
3p
4
F : 2s
2
2p
5
Bromine pentachloride, BrCl
5
Cl : 3s
2
3p
5
Br : 4s
2
4p
5
Xenon tetrafluoride, XeF
4
Xe : 5s
2
5p
6
F : 2s
2
2p
5
2. There are also some stable covalent compounds, which have
less than 8 electrons in their center atom (incomplete octet).
The center atoms are usually metals with great number of
valence electrons with small atomic radius, such as
beryllium, boron and aluminium
BeCl
2
Be : 2s
2
Cl : 3s
2
3p
5
BF
3
B : 2s
2
2p
1
F : 2s
2
2p
5
AlCl
3
Al : 3s
2
3p
1
F : 3s
2
3p
5
These compound possessed stability due to their short bond
length between center atom with surround atom. Furthermore
they can form resonance structure between the center atom
and surrounding atoms
3. There are also some molecules which contain an odd
number of electrons. Among the most common compounds
are nitrogen monoxide (NO) and nitrogen dioxide (NO
2
).
Odd-electron molecules are sometimes called radicals.
Many radicals are highly reactive. The reason is that there
Nitrogen monoxide NO
N : 2s
2
2p
3
O : 2s
2
2p
4
Nitrogen dioxide, NO
2
N : 2s
2
2p
3
O : 2s
2
2p
4
Many radicals are highly reactive. The reason is that there
is a tendency for the unpaired electron to form a
covalent bond with an unpaired electron on another
molecule. For example, when two nitrogen dioxide
molecules collide, they form dinitrogen tetroxide
3.2.2 Dative bond
1. As shown in the Lewis structure of nitrate ion, one of the N-O
bond is drawn as . The bond '' placed is called as dative
bond (also known as coordinative bond), where dative
bond is defined as a covalent bond in which one of the atoms
donate the lone pair electrons available. Although the
properties of a coordinate covalent bond do not differ from
those of a normal covalent bond because all electrons are
alike no matter what their source. alike no matter what their source.
2. Dative bond is usually applied for these few circumstances
below
a) To assist atom / molecule / ion that not yet achieved octet
configuration. Making use of atom which has lone pair
electrons to those which are lack of electrons.
Sulphur dioxide, SO
2
Sulphur trioxide, SO
3
Carbon monoxide, CO
Ozone molecule, O
3
Water with hydrogen ion
S
O O
O
Ammonia with hydrogen ion Ammonia with boron trifluoride
b) Formation of dimer - In order for some compounds which
have incomplete octet to achieve stability, they tend to form
dimer or polymer among themselves by using dative bond.
Two of the most common examples are aluminium trichloride
and beryllium dichloride
Monomer of AlCl
3
Dimer of aluminiumchloride, Al
2
Cl
6
Monomer of BeCl
2
Dimer of Be
2
Cl
4
Polymer of (BeCl
2
)
n
c) Formation of coordination compounds - Coordination
compounds are substances that contain at least one complex
ion, a species consisting of a central metal cation (either a
transition metal or a main-group metal) that is bonded to
molecules and/or anions called ligands via dative
(coordinative) bond.
hexaaquacopper (II) ion ; [Cu(H
2
O)
6
]
2+
tetraamminenickel (II) ion ; [Ni(NH
3
)
4
]
2+
Hexacyanoferrate (III) ion ; [Fe(CN)
6
]
3-
Trioxalatocobaltate(III)ion, [Co(C
2
O
4
)
3
]
3-
3.2.3 Hybridisation Theory
Valence bond theory
The basic principle of valence bond theory is that a covalent
bond is formed when orbitals of two atoms overlap and the
overlapped region, which is between the nuclei, is occupied by
a pair of electrons. The central themes of valence bond theory
derive from this principle :
Opposing spins of the electron pair ~ Stated in Pauli's
Exclusion principle, the space formed by the overlapping Exclusion principle, the space formed by the overlapping
orbitals has a maximum capacity of two electrons that must
have opposite spins. For example, when a covalent bond is
formed in molecule of hydrogen, H
2
, the two 1s electrons of
two H atoms occupy the overlapping 1s orbitals and have
opposite spins
Maximum overlap of bonding orbitals ~ The bond strength
depends on attraction of the nuclei for the shared electrons,
so the greater the orbital overlap, the stronger (more
stable) the bond. The extent of overlap depends on the
shapes and directions of the orbitals. An s orbital is spherical,
but p and d orbitals have more electron density in one
direction than in another. Thus, whenever possible, a bond
involving p or d orbitals will be oriented in the direction that
maximizes overlap. For example, in hydrogen fluoride (HF)
bond, the 1s orbital of H overlaps the half-filled 2p orbital of F
along the long axis of that orbital. Any other direction would
result in less overlap and, thus, a weaker bond
Hybridisation of atomic orbitals ~ To account for the
bonding in simple diatomic molecules like HF, we picture the
direct overlap of s and p orbitals of isolated atoms. But how
can we account for the shapes of so many molecules and
polyatomic ions through the overlap of spherical s orbitals,
dumbbell-shaped p orbitals, and cloverleaf-shaped d orbitals?
Linus Pauling proposed that the valence atomic orbitals in the
molecule are different from those in the isolated atoms. The
spatial orientations of these new orbitals lead to more stable
bonds and are consistent with observed molecular shapes.
The process of orbital mixing is called hybridisation, and
the new atomic orbitals are called hybrid orbitals. Two key
points about the number and type of hybrid orbitals are that
i. The number of hybrid orbitals obtained equals the number of
atomic orbitals mixed.
ii. The type of hybrid orbitals obtained varies with the types of
atomic orbitals mixed
3.2.3.1 Type of hybridisation
1. sp
3
hybridisation ~ When four electron groups surround
the central atom, the center atom involved must prepare four
orbitals with equal energies to overlap with the four
surrounding electron groups. Valence Bond theory uses
hypothetical hybrid orbitals, which are atomic orbitals
obtained when two or more non-equivalent orbitals of the
same atom combine in preparation for covalent bond
formation. Hybridisation is the term applied to the mixing of formation. Hybridisation is the term applied to the mixing of
atomic orbitals in an atom (usually a central atom) to
generate a set of hybrid orbitals. In the case of sp
3
, We can
generate four equivalent hybrid orbitals from the center
atom by mixing the s orbital and the three p orbitals.
Explanation Energy level diagram Diagram of orbitals
a) Ground state :
Carbon which act as the
center atom has the valence
electron of 2s
2
2p
2
.
b) Excited state :
One of the electron from 2s
is promote to 2p orbitals -
equal energy level equal energy level
c) Hybridised state :
One orbital of 2s and three
orbitals of 2p combined
(hybrid) and rearrange
themselves to the shape
and orientation of a
tetrahedral shape.
Molecular shape : Tetrahedral
Angle between bond pair : 109.5
0
2. sp
2
hybridisation ~ When three electron groups surround
the central atom, the center atom involved must prepare three
orbitals with equal energies to overlap with the three
surrounding electron groups. In sp
2
hybridisation, three
equivalent (in terms of energy level) from the center atom by
mixing the one s orbital and the two p orbitals. Using boron mixing the one s orbital and the two p orbitals. Using boron
trifluoride (BF
3
) as example, sp
2
hybridisation is explained
Explanation Energy level diagram Diagram of orbitals
a) Ground state :
Boron which act as the center
atom has the valence electron
of 2s
2
2p
1
.
b) Excited state :
One of the electron from 2s is
promote to 2p orbitals - equal
energy level
c) Hybridised state :
One orbital of 2s and two
orbitals of 2p combined (hybrid)
and rearrange themselves to
the shape and orientation of a
trigonal planar shape.
Molecular shape : Trigonal planar
Angle between bond pair : 120
0
3. sp hybridisation ~ When two electron groups surround
the central atom, we observe a linear shape, which
means that the bonding orbitals must have a linear
orientation. VB theory explains this by proposing that
mixing two nonequivalent orbitals of a central atom, one
s and one p, gives rise to two equivalent sp hybrid
orbitals that lie 180
0
apart. orbitals that lie 180
0
apart.
Explanation Energy level diagram Diagram of orbitals
a) Ground state :
Beryllium which act as the
center atom has the valence
electron of 2s
2
.
b) Excited state :
One of the electron from 2s is
promote to 2p orbitals - equal
energy level
c) Hybridised state :
One orbital of 2s and one
orbitals of 2p combined (hybrid)
and rearrange themselves to
the shape and orientation of a
linear shape.
Molecular shape : Linear
Angle between bond pair : 180
0
4. The concept of hybridisation is also useful to explain molecules with
double/triple bonds. By using the concept of the direct overlapping
orbitals and side-touch lapping orbitals, the formation of multiple
bonds in ethene, C
2
H
4
and ethyne, C
2
H
2
, are described.
a) Ethene C
2
H
4
. - Hybridisation take place for both carbon atoms in
ethene molecule is sp
2
hybridisation
When both hybridised C is bonded together, one of the hybridised
orbital overlapped directly between each other, while the other two
hybridised orbitals overlapped directly with hydrogen atoms
respectively. Meanwhile. the unhybridised p
z
orbitals of both carbon respectively. Meanwhile. the unhybridised p
z
orbitals of both carbon
atoms form a side-touch bond between each other, and form another
bond, as shown in the diagram below.
From the diagram with C=C, there are two types of bond. A sigma-
bond (-bond) is covalent bonds formed by orbitals overlapping end-
to-end, with the electron density concentrated between the nuclei of
the bonding atoms, while the second type is called a pi bond (-
bond), which is defined as a covalent bond formed by sideways
overlapping orbitals with electron density concentrated above and
below the plane of the nuclei of the bonding atoms
Explanation Energy level diagram Diagram of orbitals
a) Ground state :
Carbon which act as the center
atom has the valence electron
of 2s
2
2p
2
.
b) Excited state :
One of the electron from 2s is
promote to 2p orbitals - equal
energy level
c) Hybridised state :
One orbital of 2s and two
orbitals of 2p combined (hybrid)
and rearrange themselves to
the shape and orientation of a
trigonal planar shape.
Note that on unhybridised p
z
orbital, an electron is presence.
Molecular shape : Trigonal planar
Angle between bond pair : 120
0
b) Ethyne, C
2
H
2
, has the Lewis structure of HCCH, which the
bonding can be explain using sp hybridisation. Table below
described how the hybridisation take place on each carbon
atom and how the formation of triple bond occur.
c) From the diagram, formation of -CC- is due to the formation
of one sigma-bond, by direct overlapping of one of the two
hybrid orbitals on each C, while the other two pi-bond bonds
are formed as a result of side-lapping of the each two
unhybridised p and p orbitals unhybridised p
y
and p
z
orbitals
Explanation Energy level diagram Diagram of orbitals
a) Ground state :
Carbon which act as the center
atom has the valence electron
of 2s
2
2p
2
.
b) Excited state :
One of the electron from 2s is
promote to 2p orbitals - equal
energy level
c) Hybridised state : c) Hybridised state :
One orbital from 2s and 2p
orbitals combined (hybrid) and
rearrange themselves to the
shape and orientation of a
linear shape.
Note that on unhybridised p
y
&
p
z
orbitals, electrons are
presence to form two
-bonds.
Molecular shape : Linear
Angle between bond pair : 180
0
sp
p
z
p
y
5. Other examples of applications in valence bond theory includes the
formation of nitrogen molecule, N
2
and hydrogen cyanide, HCN
molecule.
a) Nitrogen gas is Earth's most abundant gas as it cover 78% of the
content of our air. Nitrogen molecule is an inert gas thanks to its
short covalent bond and also its strong triple bond. Therefore,
a lot of heats are required to break the chemical bond of nitrogen
before it can be applied in industries. Using valence bond theory,
the bonding of nitrogen molecule is explained in the diagram
below below
b) So, when the two hybridised nitrogen atom interacting among
each other, they hence formed a linear shape, and two pi-bonds
(bonds) are formed as a result of side-lapping of unhybridised
p
y
and p
z
orbital respectively
N N
Explanation
Energy level
diagram
Diagram of orbitals
a) Ground state :
Both nitrogen which
act as the center atom
has the valence
electron of 2s
2
2p
3
b) Excited state :
One of the electron
from 2s is promote to 2p
orbitals - equal energy orbitals - equal energy
level
c) Hybridised state :
One orbital of 2s and
one orbitals of 2p
combined (hybrid) and
rearrange themselves
to the shape and
orientation of a linear
shape.
Molecular shape : Linear
Angle between bond pair : 180
0
b) Whereas for hydrogen cyanide, HCN, both carbon atom and
nitrogen atom undergoes sp hybridisation, in order to form a
linear structure.
Explanation
Energy level diagram for
carbon atom, C
Energy level diagram for
nitrogen atom, N
a) Ground state :
Valence electron
C : 2s
2
2p
2
N : 2s
2
2p
3
b) Excited state :
One of the electron from
2s is promote to 2p
orbitals - equal energy
level
c) Hybridised state :
One orbital of 2s and one
orbitals of 2p combined
(hybrid) and form sp
hybridisation
N




6. However, there are a few limitation on valence bond theory, such
as when explaining the effect angle of bond-pair and bond-pair
electrons when there is/are presence of lone pair electron in the
center atom, and also the difference of electronegativity.
a) Bonding in ammonia, NH
3
and water, H
2
O. ~ Both NH
3
and
H
2
O undergoes an arrangement similar to sp
3
hybridisation,
similar to that of C in methane. Table below shows the
hybridisation occur for nitrogen in ammonia, and oxygen in water
Explanation
Energy level diagram
Energy level diagram
Explanation
for nitrogen atom, N
for oxygen atom, O
a) Ground state :
Valence electron
N : 2s
2
2p
3
O : 2s
2
2p
4
b) Excited state :
One of the electron
from 2s is promote to
2p orbitals
c) Hybridised state :
One orbital of 2s and
three orbitals from 2p
combined (hybrid) and
rearrange themselves to
the shape and
orientation similar to that
of tetrahedral shape.
Similar to arrangement in
tetrahedral
Similar to arrangement in
tetrahedral
Diagram of overlapping Diagram of overlapping
of ammonia, NH
3
and
water, H
2
O
Shape and angle
Shape : trigonal pyramidal
Angle : 107
0
Shape : bent
Angle : 104.5
0
Number of bond pair &
lone pair electrons
Bond pair electron : 3
Lone pair electron : 1
Bond pair electron : 2
Lone pair electron : 2
The angle of bond pair - bond pair electrons in ammonia and
water are 107
0
and 104.5
0
respectively, which is lesser than in
methane molecule (109.5
0
). This can be explained by the fact
of the presence of lone-pair electrons in both ammonia and
water. Since the lone pair - lone pair electron repulsion is
stronger than lone pair - bond pair electron repulsion than
bond pair - bond pair electron repulsion, it is expected that the
repulsion between lone pair - bond pair electrons in ammonia
is stronger than bond pair - bond pair electrons repulsion,
hence caused the angle to "squeeze" to a smaller angle. As
for water, since there is a presence of lone pair - lone pair
electrons repulsion, it results the bond pair - bond pair
electron repulsion to be much smaller, hence caused the
angle to "squeeze" to a smaller angle. Though, valence bond
theory does not actually explain the hybridisation especially
when it relates to the repulsion occur involving lone pair
electron, another theories shall be applied to study such
effect. All these shall be discussed further in VSEPR theory
b) Effect of electronegativity and bonding angle between bond pair
- bond pair electrons ~
i. As discussed earlier, in the bonding of water (H
2
O), the
molecular shape and angle is described in the diagram below.
Sulphur, which is also an element from Group 16, formed hydrogen Sulphur, which is also an element from Group 16, formed hydrogen
sulphide, H
2
S when sulphur react with hydrogen. However, unlike
water, the bonding angles is much smaller compare to water. This is
due to the difference of electronegativity and also the bond length
between O and S in molecule. Since O is more electronegative
compare to S, the O-H bond is pulled closer toward O. Furthermore,
the bond length of O-H is shorter compare to S-H. As a result, the
bonding pair-bonding pair electrons repulse greater with each other in
H-O-H, and caused the angle become greater
ii. Another example is between NH
3
and PH
3
. The orbital
diagram for both NH
3
and PH
3
are described below. Both
nitrogen, N, and phosphorous, P, are from the same group,
which is Group 15.
Similar to the above case, P in phosphine is less
electronegative than N in ammonia, and bond length of N-H
is shorter than P-H. As a result, H is pull closer to N and
repulsion between bonding of H-N-H is greater, compare to
H-P-H, and caused the angle between H-N-H is greater
compare to H-P-H
3.2.4 Valence Shell Electron Pair Repulsion (VSEPR) Theory
1. Molecular geometry is the three-dimensional arrangement of atoms
in a molecule. A molecules geometry affects its physical and
chemical properties, such as melting point, boiling point, density,
and the types of reactions it undergoes. The basic concept of
VSEPR theory is based on the three general rules below
a) As far as electron-pair repulsion is concerned, double bonds and
triple bonds can be treated like single bonds. This approximation is
good for qualitative purposes. However, you should realize that in
reality multiple bonds are larger than single bonds; that is, reality multiple bonds are larger than single bonds; that is,
because there are two or three bonds between two atoms, the
electron density occupies more space.
b) If a molecule has two or more resonance structures, we can apply
the VSEPR model to any one of them. Formal charges are usually
not shown.
c) The order of repulsion strength of lone pair and bond pair are :
lone-pair & lone-pair electrons repulsion are the strongest,
followed by lone-pair & bond-pair electrons repulsion, while
bond-pair & bond-pair electrons repulsion is the weakest.
2. In order to deduce the geometry of molecule or ion, we should
know the number of electrons surrounding a central atom in its
Lewis structure.
Step 1 : Calculate the total number of valence electrons from all
atoms in a molecule. If it is a molecular ion, depend on the type of
ions, the number of electrons are added / subtracted. If the
molecular ion is positively charged, the total number of electrons
are subtracted, however, if its negatively charged, the total number
of electrons are added.
Step 2 : Arrange all the atoms surrounding the central atom by Step 2 : Arrange all the atoms surrounding the central atom by
using a pair of electron per bond (- 2 electrons per bond formed)
Step 3 : Assign the remaining electrons to the terminal atoms so
that each terminal atom has 8 electrons [except for hydrogen] (- 6
electrons per surround atom)
Step 4(a) : Place any left-over electron on the central atom. (or)
Step 4(b) : Form multiple bonds if there are not enough electrons
to give the central atom an octet of electrons
Class
No of
surroun
d
atoms
No of
lone
pair
electro
n
Molecular
geometry
Diagram of the molecular
shape
Example of
molecules
AB
2
2 0 Linear
CO
2
BeCl
2
AB
3
3 0
Trigonal
planar
AlCl
3
BF
3
NO
-
planar
NO
3
-
AB
2
E 2 1
Shape :
Bent
SO
2
O
3
NO
2
-
AB
4
4 0
Shape :
Tetrahedral
CH
4
SiCl
4
SO
4
2-
AB
3
E 3 1
Shape :
Trigonal
pyramidal
NH
3
PCl
3
SO
3
2-
AB
2
E
2
2 2
Shape :
Bent
H
2
O
SCl
2
H
2
O
2
AB
5
5 0
Shape :
Trigonal
bipyramidal
PCl
5
SbF
5
AB
4
E 4 1
Shape :
See-Saw
SCl
4
PF
4
-
AB
3
E
2
3 2
Arrangeme
nt:
Trigonal
bipyramidal
Shape :
T-shape
ICl
3
BrF
3
AB
2
E
3
2 3
Arrangeme
nt:
Trigonal
bipyramidal
Shape :
linear
I
3
-
BrCl
2
-
AB
6
6 0
Arrangeme
nt
& Shape :
Octahedral
SF
6
AB
5
E 5 1
Arrangeme
nt:
Octahedral
Shape :
SbCl
5
2-
IF
5
Shape :
Square
pyramidal
IF
5
AB
4
E
2
4 2
Arrangeme
nt:
Octahedral
Shape :
Square
planar
XeF
4
BrF
4
-
a) phosphorous trichloride, PCl
3
S1. Total valence electrons
P = 5 e- ; 3 Cl = 3 x 7e
-
Total electrons = 26
S2. Electrons used / bond = 3 x 2e-
Electrons left = 26 - 6 = 20 e-
S3. e- at surround atom = 3 x 6e-
Electrons left = 20 - 18 = 2 e-
S4a ) The 2e- remain is placed at
the center atom P
Since molecule contain 3
surrounding atom and 1 lone pair
electrons, hence
Arrangement : tetrahedral
Shape : trigonal pyramidal
b) Carbonate ion, CO
3
2-
.
S1. Total valence electrons
C = 4 e- ; 3 O = 3 x 6e
-
+ 2e- accept ;
Total electrons = 24
S2. Electrons used / bond = 3 x 2e-
Electrons left = 24 - 6 = 18 e-
S3. e- at surround atom = 3 x 6e- S3. e- at surround atom = 3 x 6e-
Electrons left = 18 - 18 = 0 e-
S4b) Since the center atom C not
yet achieved octet, a double bond
is form using any e- from O
Since molecular ion contain 3
surrounding atom and 0 lone pair
electrons, hence
Arrangement and
Shape : trigonal planar
c) iodine tetrachloride ion, ICl
4
-
S1. Total valence electrons
I = 7 e
-
; 4 Cl = 4 x 7e
-
; + 1e- accept ;
Total electrons = 36
S2. Electrons used / bond = 4 x 2e-
Electrons left = 36 - 8 = 28 e-
S3. e- at surround atom = 4 x 6e- S3. e- at surround atom = 4 x 6e-
Electrons left = 28 - 24 = 4 e-
S4a ) The 2e- remain is placed at
the center atom P
Since molecular ion contain 4
surrounding atom and 2 lone pair
electrons, hence
Arrangement : octahedral
Shape : square planar
a) Iodide ion, I
3
-
b) Antimony pentachloride ion,
[SbCl
5
]
2-
c) Bromine trifluoride, BrF
3
d) sulphur tetrafluoride, SF
4
Arrangement : trigonal
bipyramidal
Shape : linear
Arrangement : octahedral
Shape : square pyramidal
c) Bromine trifluoride, BrF
3
d) sulphur tetrafluoride, SF
4
Arrangement : trigonal
bipyramidal
Shape : T-shape
Arrangement : trigonal
bipyramidal
Shape : see-saw
3.2.5 Electronegativity and Polarity of Molecules
1. From all the chemical bonding discussed so far, ionic and
covalent bonding models portray compounds as being
formed by either complete electron transfer or complete
electron sharing. However, in most real compounds, the
type of bonding lies somewhere between these extremes.
Thus, the great majority of bonds are more accurately
thought of as polar covalent, that is, partially ionic and
partially covalent. partially covalent.
Pure ionic compound Pure covalent compound Polar covalent compound
2. One of the most important concepts in chemical bonding is
electronegativity (EN), the relative ability of a bonded atom to
attract the shared electrons. Electronegativity is a relative concept,
meaning that an elements electronegativity can be measured only
in relation to the electronegativity of other elements. Linus Pauling
devised a method for calculating relative electronegativities of most
elements
Molecule Fluorine, F
2
Hydrogen fluoride, HF
Lewis
structure
+
Polarity Non-polar molecule Polar molecule
EN 4.0 - 4.0 = 0 4.0 - 2.1 = 1.9
Since there are no
different between the EN,
Since F is more electronegative than H,
therefore, the bonding pair electrons
Explanatio
n
different between the EN,
therefore bonding pair
electrons was not pulled to
either atom, hence remain
in the middle between 2 F
atom
therefore, the bonding pair electrons
were pulled closer to F atom. This will
caused F to have greater electron
density compare to H. Therefore, F has
partial negative charge () while H
carries partial positive charge (+)
Dipole
moment,
magnitude
and
vector.
Since there is no
difference between EN,
the dipole moment is 0,
and no resultant dipole
moment nor vector
Since F is more electronegative than H.
There is presence of dipole moment in
HF and the vector of resultant dipole
moment is pointed to the direction of F
(symbolised by I ).
a) Comparisons above are basically the difference between an
element with compound, where diatomic molecules
containing atoms of different elements (for example, HCl,
CO, and NO) have dipole moments and are called polar
molecules while diatomic molecules containing atoms of
the same element (for example, H
2
, O
2
, and F
2
) are
examples of non-polar molecules because they do not
have dipole moments. However, not necessarily, a covalent
bond compound is guaranteed a polar molecule.
b) For a molecule made up of three or more atoms both the
polarity of the bonds and the molecular geometry determine
whether there is a dipole moment. Even if polar bonds are
present, the molecule will not necessarily have a dipole
moment. For example, comparison between sulphur dioxide
and sulphur trioxide
Molecules
Sulphur trioxide, SO
3
Sulphur dioxide, SO
2
Lewis
structure
and shape
Polarity Non-polar molecule Polar molecule
EN S = 2.5 ; O = 3.5 S = 2.5 ; O = 3.5
the dipole moment of the entire molecule
is made up of three bond moments, that is,
the dipole moment of the entire molecule
is made up of two bond moments and one
Bond
moment,
dipole
moment
magnitude
and vector
is made up of three bond moments, that is,
individual dipole moments in the polar
SO bonds. The bond moment is a vector
quantity, which means that it has both
magnitude and direction. The measured
dipole moment is equal to the vector sum
of the bond moments. The three bond
moments in SO
3
are equal in magnitude.
Because they point in opposite directions
in a planar SO
3
molecule, the sum of
resultant dipole moment would be zero
is made up of two bond moments and one
lone pair electron. Even though two bond
moments in SO
2
are equal in magnitude,
however, the presence of the lone pair
electrons which caused the repulsion of
bond pair electrons to be lesser. Because
they point in downward directions in a bent
SO
2
molecule, the overall vector points
downward and the sum of resultant
dipole moment would not be zero,
hence a polar molecule
From the example of SO
2
and SO
3
used, we can tell that if a
polyatomic molecule is a symmetrical molecule (molecule
with no lone pair electrons in it), it may be a non-polar
molecule. However if a polyatomic molecule is an
asymmetrical molecule (molecule with lone pair electrons in
it), it may be a polar molecules.
c) Even though, a polyatomic molecule may be symmetrical, if
the surrounding atoms are not the same, molecule may be a the surrounding atoms are not the same, molecule may be a
polar molecule, as the bonding moments are different, and
caused the magnitude of dipole moment of the molecule is not
equal to zero. However, if the surrounding atoms are the
same, bonding moments are equal in magnitude, and the
resultant vector cancel-off each other, causing the dipole
moment is equal to zero, hence form a non-polar molecule.
For example
Molecule
Methane, CH
4
Chloromethane
(chloroform), CH
3
Cl
Lewis
structure
Polarity
Non - polar molecule polar molecule
Polarity
Non - polar molecule polar molecule
Explanation
As methane is a symmetrical
molecule, and the surrounding atoms
are the same, the vector of bond
moment cancel off each other, hence
caused the dipole moment is equal to
zero.
Since a foreign element, Cl, is in the
symmetrical molecule, and Cl is more
EN than the rest of the atoms, the
vector and magnitude is heading to
the direction of Cl, caused a small
dipole moment present in molecule,
hence polar.
Covalent molecule
Diatomic molecule
Same element Different
Polyatomic molecule
Asymmetric Same element Different
element
Non-polar
molecule
Polar molecule
Asymmetric
al
Symmetrical
Polar
molecule
Same surround
atoms
Different surround
atoms
Non-polar
molecule
Polar molecule
3.2.6. Electronegativity and Type of Chemical Bond.
1. The type of bond that would form can be told by using the
difference of electronegativity (EN). Larger the difference, the
more tendency of electron from low electronegativity atom to
move to the atom with higher electronegativity and form ionic
compound.
a) The relationship between the ionic character and the difference
in the electronegativity of the bonded atom is shown in the
diagram and graph below.
b) 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), or conversely covalent
compound having high ionic characteristic (exemplified by HF).
c) 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 density of the anion closer to it, as if the anion wanted to share
electron with cation, hence increase the covalency of the molecule
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
A
+ X

B
+
Y-
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
effective nuclear charge of cation,
hence it will be able to attract the
neighboring electron density of anion.
This will caused the polarization power
Smaller the size of cation, closer the
neighboring anion to the nucleus of
cation, hence easier for the cation to
polarise the anion and result an
increment in the polarization power of This will caused the polarization power
of cation increase, hence increase the
covalent characteristic of cation.
increment in the polarization power of
cation, and increase the covalent
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.
2 factors determining the polarisability of an anion
Charge of anion Size of anion
Greater the charge of anion, lower the
effective nuclear charge of anion. This will
weakened the electrostatic attraction forces
between nucleus and the outermost
Larger the size of anion, further the
outermost electron from the nucleus
of the anion, easier for the cation to
polarise the anion, and cause the
Unlike 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
between nucleus and the outermost
electron in anion, and increase the
polarisability of the anion, hence increase
the covalent characteristic of anion
polarise the anion, and cause the
polarisability to increase, hence
increase the covalent characteristic
of anion.
3.6.2 Prediction of Chemical Bond :Fajans Rule
In 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
Rule in the chemical bonding
Lithium halide (LiX)
Lithium ion, Li
+
(1s
2
) 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, 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 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.
Ionic size increase with the increasing shell when going down
to Group 17 halide, hence increase the polarisability, which
allowed lithium ion to polarise the anions electron density,
hence increase the covalency
Li
+
F

Br

Cl

Aluminium halide (AlX

3
) and aluminium oxide (Al
2
O
3
)
Aluminium ion (Al
3+
) has high charge density, due to its high
charge unit and its small ionic radius. So, depending on the anion,
aluminium has a high tendency to form covalent compound. For
example, when going down to Group 17 halide, aluminium fluoride
(AlF
3
) forms ionic compound (since F- has a low polarisability),
while aluminium trichloride (AlCl
3
), aluminium tribromide (AlBr
3
)
and aluminium iodide (AlI
3
) form covalent compound (since
chloride, bromide and iodide have high polarisability). This
explained why aluminium fluoride has a high melting point explained why aluminium fluoride has a high melting point
(1040
0
C), while aluminium trichloride and tribromide are 192
0
C and
78
0
C respectively.
As for aluminium oxide (Al
2
O
3
), it is an ionic compound with high
covalent characteristic, as aluminium ion has high covalent
characteristic due to its high charge density. This explained the
high melting point of Al
2
O
3
(2050
0
C) yet it is insoluble in 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).
3.3 Metallic Bonding
1. Metallic bonding occurs when large
numbers of metal atoms interact.
Unlike the reaction of metal with
non metal which involve electrons
transfer, when two metal atoms
interact, they can also share their
valence electrons in a covalent
bond and form gaseous, diatomic
molecules of M
2
. The electron-sea molecules of M
2
. The electron-sea
model of metallic bonding
proposes that all the metal atoms
in the sample contribute their
valence electrons to form an
electron sea that is
delocalized throughout the
piece. The metal ions are
submerged within this electron
sea in an orderly array
a) The model we will use to study metallic bonding is band theory
because it states that delocalized electrons move freely through
bands formed by overlapping molecular orbitals.
b) Consider magnesium, for example. The electron configuration of
Mg is 1s
2
2s
2
2p
6
3s
2
, so each atom has two valence electrons in the
3s orbital. In a metallic crystal, the atoms are packed closely
together, so the energy levels of each magnesium atom are
affected by the immediate neighbors of the atom as a result of
orbital overlaps . These molecular orbitals are so closely spaced on orbital overlaps . These molecular orbitals are so closely spaced on
the energy scale that they are more appropriately described as a
band. The closely spaced filled energy levels make up the
valence band. The upper half of the energy levels corresponds
to the empty, delocalized molecular orbitals formed by the overlap
of the 3p orbitals. This set of closely spaced empty levels is called
the conduction band. As a conductor, the conduction band and
valence band are overlapped, hence electrons can travel freely
among the two bands, hence conduct electricity.
c) Theoretically, greater the number of valence electrons in a
metal, greater the number of electrons delocalised, higher
the conductivity. However, the conductivity decrease with
temperature as vibration of the lattice of ion impedes the free
movement of electron in conduction band.
2. Semiconductors are element that normally are not conductors, but
will conduct electricity at elevated temperatures or when combined
with a small amount of certain other elements. These elements are
usually metalloid such as silicon and germanium.
(a) The energy gap between the conduction band and valence band
of these solids is much smaller than that for insulator. If the energy
needed to excite electrons from the valence band into the conduction
band is provided, the solid becomes a conductor. Note that this
behavior is opposite that of the metals.
(b) Addition of impurities (doping) to semiconductors also increases (b) Addition of impurities (doping) to semiconductors also increases
the conductivity of the semiconductors. Doping can be done by
adding one of the following:
i. dopant atoms containing fewer valence electrons. Hence the
semiconductor formed is positive, p - type semiconductor
ii. dopant atoms with extra valence electrons. Hence the semiconductor
formed is negative, n - type semiconductor
3. Insulators are substances that do not conduct electricity
no matter how high the temperature is applied to the
substances involved. The energy gaps between the
conduction band and valence band of these element is very
large, hence regardless how much energies were applied to
these insulator, it will not be able to conduct electricity nor
heat. Glass and woods are good examples of insulator. In
wood and glass, the gap between the valence band and the
conduction band is considerably greater than that in a metal. conduction band is considerably greater than that in a metal.
Consequently, much more energy is needed to excite an
electron into the conduction band. Lacking this energy,
electrons cannot move freely. Therefore, glass and wood
are insulators, ineffective conductors of electricity
3.4 Intermolecular forces : Van der Waals forces and hydrogen
bonding
1. The nature of the state of matter of substances and their changes
are due primarily to forces among the molecules. Both bonding
(intramolecular) forces and intermolecular forces arise from
electrostatic attractions between opposite charges. Bonding forces
are due to the attraction between cations and anions (ionic
bonding), nuclei and electron pairs (covalent bonding), or metal
cations and delocalized valence electrons (metallic bonding).
Intermolecular forces, on the other hand, are due to the attraction Intermolecular forces, on the other hand, are due to the attraction
between molecules as a result of partial charges, or the attraction
between ions and molecules. The two types of forces differ in
magnitude, and forces explains why:
a) Bonding forces are relatively strong because they involve
larger charges that are closer together.
b) Intermolecular forces are relatively weak because they typically
involve smaller charges that are farther apart
3. Induced dipole Forces (Dispersion forces) - Consider how a helium
atom (monoatomic gas which have dipole moment = 0), interact
with the following species.
Helium with cation
Helium with polar
molecule
Helium with Helium
He
He
a) From the diagram, we can tell that if an ion or a polar
molecule is placed near an atom or a non-polar molecule, the
electron distribution of the atom (or molecule) is distorted by
the force exerted by the ion or the polar molecule, resulting in
a kind of dipole. The dipole in the atom (or non-polar
molecule) is said to be an induced dipole because the
separation of positive and negative charges in the atom
(or non-polar molecule) is due to the proximity of an ion or a
polar molecule. polar molecule.
b) However, the weak attractive interaction between a non-polar
molecule to another non-polar molecule are unlike when
placed near an ion or polar molecule. Between two non-polar
atom, they form among themselves a short induced dipole,
hence attract each other temporary. Therefore, the forces
formed between them are very weak and can be broken
easily. Such interaction is also known as London forces
Alkane CH
4
C
2
H
6
C
3
H
8
C
4
H
10
C
5
H
12
C
6
H
14
C
7
H
16
C
8
H
18
RMM 16 30 44 58 72 86 100 114
Boiling
point
o
C
162 8.6 42.2 0.5 36.3 68.7 98.4 126
point
o
C
162 8.6 42.2 0.5 36.3 68.7 98.4 126
Trend
Relative molecular mass increased
weak Van Der Waals' forces increased
d) For molecules, especially organic compounds, which have the
same molecular mass and functioning group, they may have
different boiling point, depend on the molecular structure. For
example, pentane, C
5
H
12
, with molecular mass 72, has 3 isomers,
as shown in table below.
Molecule 2,2-dimethylpropane 2-methylbutane n-pentane
Molecular Molecular
structure
Boiling point
/
o
C
5.4 21.8 36.3
Total surface area increased
weak Van Der Waals' forces increased
Boiling point increased
4. Dipole-Dipole Forces ~ When polar molecules lie near one
another, as in liquids and solids, their partial charges act as
tiny electric fields that orient them and give rise to dipole-
dipole forces: the positive pole of one molecule attracts the
negative pole of another. These are the forces that give polar
compound a higher boiling point than the non-polar
compound.
Molecule Formula
Molecular
mass
Dipole
moment
Boiling point
(K)
Propane CH
3
CH
2
CH
3
44 0.08 231
Dimethyl
ether
CH
3
OCH
3
46 1.3 248
Methyl
chloride
CH
3
Cl 50.5 1.87 249
Ethanal CH
3
CHO 44 2.69 294
Acetonitrile CH
3
CN 41 3.92 355
Almost the same molecular mass
However, greater the dipole moment
Stronger the dipole-dipole forces
Higher the boiling point
5. Hydrogen bond ~ a special type of dipole-dipole interaction
between the hydrogen atom in a polar bond, as in NH, OH,
or FH, with an electronegative O, N, or F atom. Diagram
below shows a few example of interaction between molecules
using hydrogen bond
Hydrogen bond
Strong
hydrogen
bond
F is more electronegative than N
Hydrogen bond between FH is stronger than NH
Higher the boiling point
Even though F is more electronegative than O &
Hydrogen bond between FH is stronger than OH
However, water form more hydrogen bond
b) 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.
c) Some organic compound form dimer using hydrogen bond.
For example, when glacial ethanoic acid is dissolved in
organic solvent, it form a dimer using hydrogen bond via the
interaction between O-H and C=O in each of the molecule.
d) In some case, hydrogen bond can also be used to form which
is the intermolecular forces and intramolecular forces. For
example, in 2-nitrophenol and 4-nitrophenol, the boiling point
of the 2 compounds can be explain below :
Since 2-nitrophenol form strong hydrogen bond as
intramolecular forces, the interaction between 2-nitrophenol
molecules are weaker among each other, compare to 4-
nitrophenol, which used hydrogen bond as their
intermolecular forces. With stronger hydrogen bond which act
as the intermolecular forces, the boiling point of 4-nitrophenol
is expected to be higher than 2-nitrophenol