CM1502

Chapter 3
1 CM1502 Sem2-2013-14
Models of
chemical bonding
CM1502 Sem2-2013-14 2
Atomic properties and chemical bonds
Why do atoms bond at all?






Properties of an atom- Electronic config./ Z
eff

Properties of a substance-Type/Strength of chemical bonds
less stable
more stable
P.E. = -K.E.
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Types of Bonding
Along the line IEs are about 8 eV
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Types of Bonding
1. Metal with nonmetal: ionic bonding
Metal loses electrons to form a positive ion (cation).
Non metal gains electrons to form a negative ion (anion).
The electrostatic attraction between the ions draw them
into a three dimensional array to form an ionic solid.
Chemical formula is the empirical formula.
Movie (IVLE workbin-videos-Formation of ionic
compound)
2. Nonmetal with nonmetal:
covalent bonding
The atoms are drawn together as the nucleus of each
atom attracts the electrons of other.
The electrons are shared.
Shared pair of electrons is localized between the atoms.
Chemical formula is the molecular formula
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Types of bonds
3. Metal with metal:
electron pooling and metallic bonding
Outer electrons of metals are losely
held due to shielding.
These electrons move freely through
the entire piece of metal.
Hence electrons in metallic bonding
are delocalized.
CM1502 Sem2-2013-14 6
Lewis electron dot symbol
Steps to write the Lewis symbol for main group elements:
1. Note the group number and is the same as their valence electrons.
2. Place one dot at a time on each of the four sides of the symbol.
3. Keep adding dots, pairing them until all are used up.
Octet rule for representative elements: When atoms bond they lose, gain or share
electrons to attain a filled outer level of eight electrons
7
The Ionic Bonding Model
Lithium Fluoride: The three ways to depict the electron transfer
Electron configurations
Li 1s
2
2s
1

Orbital diagrams
Lewis electron-dot symbols
+ F 1s
2
2s
2
2p
5
Li
+
1s
2
+ F

1s
2
2s
2
2p
6

Li
1s 2s 2p
F
1s 2s 2p
+
Li
+

1s 2s 2p
F
-

1s 2s 2p
+
.
+ F : :
:

Li
. Li
+
+ F

: :
:

:

Problem: Depict the formation of Potassium Oxide and Barium chloride
CM1502 Sem2-2013-14
Ionic Bonding
Begin with a neutral Cl
atom and a neutral Na
atom.
E
ion
is the energy price
to pay to convert both into
its respective noble gas
configuration.
The cation and anion
attract each other, so at
some distance between
Na
+
and Cl
-
the potential
energy of attraction wins
over the positive value
E
ion
.
The cation and anion repel
each other when close
because the e clouds of
both ions can not
interpenetrate due to the
Pauli exclusion principle.
It is the strong Coulomb
attraction that binds all salts
together.
E
ion
= IE(Na) EA(Cl)
Na Na
+
+ e Cl
-
Cl + e
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Lattice energy
Li(s) Li(g) H =161 kJ
F
2
F(g) H = 79.5 kJ
Li
(g)
Li
+
(g)
+e
-
IE
1
= 520kJ
F
(g)
+e
-
F
-
(g)
EA = -328 kJ

The electron transfer
process actually absorbs
energy !
Generally formation of ionic
solids releases energy.
Li
+
(g)
+ F
-
(g)
LiF(s) H
0
= -1050kJ

The energy released when an
ionic solid is formed from its
ions is called Lattice energy.
Hence the overall reaction Li
(s)
+ F
2
LIF
(s)
H = -617.5kJ ; exothermic
Ionic solids exists only
because the lattice energy
10
Periodic trends in Lattice energy
The lattice energy of LiF and MgO are in the ratio 1:4. Why?
Lattice energy = k
Q
1
Q
2
r

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k is the proportionality constant
Q
1
Q
2
are the charges on the ions
R is the shortest distance between the
centers of cation and anion
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Explaining the properties
A typical ionic compound is hard and brittle.
This is because there is strong attractive forces that hold the ions
together.
They have high melting and boiling points
They do not conduct electricity in solid state but do so when melted or
dissolved.
This is because the ions can move in the molten or dissolved state


Compound mp (
0
C) bp (
0
C)
CsBr
661
1300
NaI
MgCl
2

KBr
CaCl
2

NaCl
LiF
KF
MgO
636
714
734
782
801
845
858
2852
1304
1412
1435
>1600
1413
1676
1505
3600
Solid ionic
compound
Molten ionic
compound
Ionic compound
dissolved in
water
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Why do ionic solids crack
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The covalent bonding model
The H
2
molecule
As the two hydrogen atoms are brought together,

1. The electrons in the two atoms repel each other
because they have the same charge (E > 0);
2. The protons in adjacent atoms repel each other (E > 0);
3. The electron in one atom is attracted to the oppositely
charged proton in the other atom, and vice versa (E < 0);

At the observed bond distance the repulsive and attractive
interactions are balanced
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Covalent bond formation in H
2
Movie: IVLE-work bin-videos-covalent bond _2
CM1502 Sem2-2013-14 15
Properties of covalent bond
Bond order: is the number of electron pairs being shared by a
given pair of atoms.
Bond energy: Also called Bond enthalpy or bond
strength. It is defined as the standard enthalpy
change for breaking the bond in 1 mol of gaseous
molecules.
A-B
(g)
A
(g)
+ B
(g)
H = BE
A-B
(always >0)
Stronger bonds have higher bond energy and
weaker ones have lower bond energy
Bond length: The distance between the nuclei of the
bonded atoms
H H :
H F : :
:

:

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Relationship between bond order, bond length and bond energy.
For a given pair of atoms, a higher bond order results in shorter bond length
and higher bond energy
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17
Most covalent substances melt and boil at low temperatures
Pentane
The two forces in covalent molecules are
1. Strong bonding forces that hold the atoms together with the molecule and
2. Weak intermolecular forces that act between the molecules.
When the covalent liquid boils it is the weak forces between the molecules are
overcome and not the strong bonds within the molecule. Hence it needs less energy.
Explaining the Physical properties
Network covalent solids have exceptional behavior
Melts at 1550C Melts at 3550C
Most of the covalent substances are poor electrical conductors.
Reason: 1. electrons are localized
2. No ions are present
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Bond energy and enthalpy.
The heat released or absorbed during a chemical change is due
to differences between reactant and product bond energies.
H
o
reaction
= H
o
bonds broken
+ H
o
bonds formed

H
o
reaction
=
reactant bonds broken
-
product bonds formed
H
2
(g) + F
2
(g) 2HF(g) H
reaction
= -546kJ
H
o
reaction
= [1x H-H + 1xF-F] [2xH-F]
=[432 + 159] [2x565]
= -539 kJ

Test your self:Calculate the H
o
rxn
for chlorination of methane to form chloroform.
CM1502 Sem2-2013-14
CM1502 Sem2-2013-14 19
Bond energies and food/fuel
A fuel generally consist of C-H,C-C C-O and O-H bonds.
Of which C-H and C-C bonds are weaker and C-O and O-H bonds are stronger.
Generally a fuel reacts with O
2
, all the bonds break and form C=O and O-H bonds.
If a fuel consist of many C-C and C-H bonds and fewer C-O , O-H bonds, said to
release Higher energy and these are known as good fuels.

20
Between the two extremes
EN is the relative ability of a bonded atom to attract shared electrons.
432kJ/mol
H-H + F-F 2 H-F
159kJ/mol
Expected BE of H-F is 296kJ/mol
Actual BE of H-F is 565kJ/mol
The reason for increased BE is Electrostatic attraction
Arbitrary cutoff divides ionic
from covalent bonds
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CM1502 Sem2-2013-14 21
Polar covalent bonds
Figure 9.23

E
N

3.0
2.0
0.0
Electrons are not transferred
completely.

Electrons are not shared
equally.

One atom has a stronger
attraction for the shared
electron than the other atom.
CM1502 Sem2-2013-14 22
Bond polarity and dipole moment
A molecule that has a positive center of charge of
magnitude Q and a negative center of charge of
magnitude Q separated by a distance R has a
dipole moment() of QR

Dipole moment = = QR

SI Unit = C m (coulomb meter)

Often used unit = debye

1debye(D) = 3.336 x 10
-30
Cm)

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23
Molecules with polar bonds and a dipole moment
Molecules with polar bonds and no resulting dipole moment
CM1502 Sem2-2013-14 24
Metallic bonding
All the metal atoms in the sample contribute their valence
electrons to form a delocalized electron sea.
The piece is held together by the mutual attraction of the
metal cations and the mobile electrons.
The metal ion array is regular but not rigid.
Not rigid hence cannot come under ionic bonding

No localized sharing - hence cannot be covalent bond.
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Properties of metals
Melting points are only moderately high.
Reason: the cations can move without
breaking the attraction to the
surrounding

Boiling points are very high
Reason: Higher energy is needed to break
the cation from all the valence electrons.
Periodic trends:

M.Pt decrease down the group.
Reason: Larger metal ions have a weaker
attraction to the electron sea.

M.Pt increase across the period.
Reason: The charge on the cation increases
from left to right, hence stronger attraction
towards the electron sea.
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Why do metals dent and bend?
When hammered, the metals
slide past each other through
the electron sea and end up in
new positions.
Properties of metals
Metals are good electrical and thermal conductors in both
solid and liquid states because of their mobile electrons.
Presence of foreign atoms disrupt the array and reduce the
conductivity.
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Summary
Atomic properties and type of bond
Features of ionic bonding
lattice energy
properties-ionic compounds are brittle, high melting, conduct
electricity only in molten/dissolved state.
Features of covalent bonding
non metals
bond order bond energy and bond length
Polar covalent compounds
Features of metallic bonding
electron sea
metals bend, have high melting and boiling points and conduct
electricity.

Role of molecular shape
Interactions of reactants during a chemical reaction is
based on the molecular shapes.
Predict the physical and chemical behavior of synthetic
materials.
Molecular shape is a crucial property of living systems
Eg: Hormonal regulation and function of genes.

Sugar Enzyme
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What is Lewis Structure?
Two-dimensional structural formula consists
of electron-dot symbols.

It shows which are the atoms bonded to
each other but it does NOT indicate
the three-dimensional shape.



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Molecular formula to Lewis structure.
Molecular
formula
Atom
placement
Sum of
valence e

Remaining
valence e

Lewis
structure
Place atom with lowest
EN in center
Draw single bonds. Subtract
2e

for each bond.
Give each atom 8e

(2e

for H)
Step 1
Step 2
Step 3
Step 4
31
Molecular
formula
Atom
placement
Sum of
valence e
-

Remaining
valence e
-

Lewis
structure
NF
3

N
F F
F
N 5e
-

F 7e
-
X 3 = 21e
-

Total 26e
-

:
: :
: :
:

:

:

:
:
31
Electrons involved in bonding are called bond
pairs . These are shared between atoms.

Unshared electrons are called lone pairs . They
belong to only one atom.
31 CM1502 Sem2-2013-14









Lewis Structures v1.0

An atoms valency should be satisfied.
N
2
must be a triple bond in order to complete the
octet.
O
2
a double bond in order to complete the octet.
F
2
a single bond in order to complete the octet.
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33
More Lewis Structures
Note the first period nonmetal (H) completed
shell is 2 electrons [He].
CO
2
can be readily explained.
CO, however, can satisfy the octets, but the
valency of C?
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34
Valency Rule CAN be Broken
Octets all completed,
valencies all satisfied
Octets all completed,
but C and O valency
broken.
34 CM1502 Sem2-2013-14
Alert! Issue Formal Charge Patch.
Lewis Structures v1.1
For nonmetals, when an atoms valency is broken, and the
octet rule is satisfied, the atom must possess either fewer
or greater electrons than it has valence electrons.

The difference is accounted for by placing a formal charge
on the offending atoms.
So in

This is because C owns 5 electrons in the above
structure but should own 4, and O owns 5 electrons, but
should own 6.
movie (IVLE /workbin/videos/Formal charge calculation)
- +
35
Formal charge of an atom =
No. of valence e
-
no. of lone pair e
-
no. of bonding e
-

Octets Not Always Completed
If a molecule has an odd number of electrons,
there is no way the octet rule can hold, or the
bond order (BO) can be an integer.
NO (nitric oxide) is an example.
Here the BO is 2 and is consistent
with the bond dissociation energy (D
e
)
of 6.52 eV
H
2
+
also exists, and must
have a BO of .
We will also see later that
He
2
+
also exists and has a
BO also of !
Octet satisfied
Octet not satisfied
Octets satisfied
BO is 2
But need weird
formal charges
-
+
36
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37
Lewis Structures with Multiple Bonds.
Step 5: It follows the other steps in Lewis structure
construction. If a central atom does not have 8e
-
, an octet,
then a lone pair of e
-
can be moved to form a multiple bond.
C C
H
H H
H
37
C C
H
H H
H
:

H C C H
37 CM1502 Sem2-2013-14
Expanding the Octet
Unless required, or stated otherwise, we always stick to the
octet rule.
We are forced in molecules like SO
2
to violate the octet
rule in order to be consistent with the experimental
observation of equal bond lengths.

The octet on S expands.
S is in group 6, so up to 6 valence electrons can be
involved in the bonding.

This is what occurs here.
Note that there are normal octet structures one can write for SO
2
,
but these structure do not account for the experimental fact that
both S-O bond lengths are identical.
The expansion occurs for third and higher period elements.

Other examples include SF
6
, SF
4
, PCl
5
.
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39
Alert! Issue Expanded Octet Patch.
We Now Have Lewis Structures v1.2
For nonmetals in the third and higher periods it may not be
possible to satisfy the octet rule.

In these cases, we are permitted to expand the octet.

We are allowed to expand the octet in these elements
because, allegedly, d AO in the same valence shell (n
quantum number) are not so high in energy for these
elements and can thus participate in bonding.
39 CM1502 Sem2-2013-14
O
O O
O
O O
O
O O
A
B
C
O
O O
A
B
C
Alert! Issue Resonance Patch.
Lewis Structures v1.3
The experimental fact was the bond lengths in O
3
are identical.
Hence the correct description of O
2
is not given by any one of
the two Lewis structures individually but by the superposition of
the two, called a resonance hybrid.

The BO is 1 for each bond.
40
41
Resonance Structures
They have the SAME relative placement
of atoms BUT different locations of
bonding and lone electron pairs.

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42
Benzene C
6
H
6

H
H
H
H
H
H
H
H
H
H
H
H
Experimentally, the bonds in benzene are all of equal length,
between a single and double bond.
The structure of benzene can also be written as......
42 CM1502 Sem2-2013-14
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Benzene C
6
H
6

Experimentally, the bonds in benzene are all of
equal length, between a single and double bond.
CM1502 Sem2-2013-14 44
Criteria for Choosing the More Important Resonance
structure:

Smaller formal charges are preferred over larger ones

(eg, 0 is preferred over -1 or +1)

The same nonzero formal charges on adjacent atoms are
not preferred

A more negative formal charge should reside on a more
electronegative atom


Predicting Structures/shapes of molecules
Lewis structures determine the bond pairs and lone
pairs of electrons among the atoms.
Combining this information with VSEPR (Valence Shell
Electron Pair Repulsion theory) enables us to predict
the shapes of the molecules.

The basis of VSEPR is that the repulsions between
electrons in bonds and lone pairs determines the
overall shape of a molecule
VSEPR assumes that core electrons make no
significant impact on the shape of a molecule, so can
be ignored.
45 CM1502 Sem2-2013-14
VSEPR Rules
1. Draw Lewis structures to determine the bonding
around atoms.
2. Assign an electron group arrangement:
- To do this we count the number of atoms
around the central atom and add it to the
number of lone pairs it possesses.
3. Predict the overall geometry around the central atom.
O in water has two hydrogen atoms
bonded to it, and two lone pairs. So
there is 2+2=4 different directions
electrons are more localized in.
S in SO
2
has two oxygen atoms bonded
to it, and a single lone pair. So there is
2+1=3 different directions electrons are
more localized in.
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CM1502 Sem2-2013-14
VSEPR Rules
4. The final predicted structure is governed by the idea
that electrons in lp repel electrons found in other lp
the most, and electrons found in bonds repel other
electrons found in bonds the least, with lp electrons
repelling bonding electrons intermediate between the
above two.

5. Draw and name the molecular shape by counting
bonding groups and nonbonding groups separately.

6. Predict the bond angle.
movie (IVLE /workbin/videos/VSEPR theory


47
VSEPR Structure Predictions
Electrons in 2 directions
Electrons in 3 directions
Electrons in 4 directions
Electrons in 5 directions
Electrons in 6 directions
Geometry about
central atom
Possible structures
of the molecule
48 CM1502 Sem2-2013-14
AXmEn Geometry structure examples
AX
2
lilnear linear CS
2
,HCN, BeF
2

AX
3
Trigonal planar Trigonal planar SO
3
BF
3
NO
3-
CO
3
2-

AX
2
E Trigonal planar V shaped SO
2
O
3
PbCl
2
SnBr
2

AX
4
Tetrahedral Tetrahedral CH
4
SiCl
4
So
4
2-
ClO
4
-
AX
3
E Tetrahedral Trigonal pyramidal NH
3
PF
3
ClO
3
-
H
3
O
+
AX
2
E
2
Tetrahedral Bent H
2
O OF
2
SCl
2
AX
5
TBP TBP PF
5
AsF
5
SOF
4
AX
4
E TBP Seesaw SF
4
XeO
2
F
2
IF
4
+
IO
2
F
2
-
AX
3
E
2
TBP Tshaped ClF
3
BrF
3
AX
2
E
3
TBP linear XeF
2
I
3
-
IF
2
-
AX
6
Octahedral Octahedral SF
6
IOF
5
AX
5
E Octahedral Squarepyramidal BrF
5
TeF
5
-
XeOF
4
AX
4
E
2
Octahedral Square planar XeF
4
ICl
4
-
A - central atom, X - surrounding atom, E -lone pairs, m, n - integers
49
CM1502 Sem2-2013-14
Molecular shapes with more than one central atom
ethane
CH
3
CH
3

ethanol
CH
3
CH
2
OH
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51
Conclusions
VSEPR Each group of electrons around a
central atom remains as far away from the others
as possible.
5 common geometric shapes result when 2, 3, 4,
5 or 6 electron groups surround a central atom.
Lone pairs and double bonds exert greater
repulsions.
Bond polarity and molecular shape determine
molecular polarity.
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