2.

Chemical Bonding And Molecular

Structure

1
 Learning Objectives
Know about valence electrons
 Learn various types of bond and bond parameters
Lewis Structure
Understand polar and covalent characters of covalent and
ionic bonds
Concept of hybridisation
Study of VSEPR and Molecular Orbital Theory
Know the types of crystalline solid (ionic, molecular,
covalent network, or
metallic) formed by a substance and describe their
properties
2
 What is a chemical bond ?
How is a molecule or polyatomic ion held together?
The attractive forces which holds various constituents
such as atoms, molecules and ions together in different
chemical species is called a Chemical bond
 A covalent bond includes the sharing of electrons between
two atoms.

3
 Valence Electrons
The electrons that are in the highest(outermost) energy
level
 That level is also called the valence shell of the atom
they are held most loosely
The number of valence electrons in an atom determines:
 The properties of the atom
The way that atom will bond chemically
As a rule, the fewer electrons in the valence shell, the
more reactive the element

4
 8A
1A Valence Electrons

2A 3A 4A 5A 6A 7A

Number of valence electrons is equal

to the Group number.
5
 TYPES OF CHEMICAL BONDS:
 There are 2 types of chemical bonds:

i. Ionic Bond (Transfer of electrons)

 The bond formed between two atoms by the complete transfer of

electrons from one atom to another, to form ions {i.e: Anion(-) or

cation(+)}, is called an Ionic Bond. • Explanation of fig. given in
EXAMPLE

6
 Ionic Bonds…
 The force of attraction between positive and negative ions.
 Particles with opposite electrical charges attract each other
 Atom from element group 1 (1+) combines with an atom from
element group 17 (1-) to form an ion.
 Example Na combines with Cl
Na loses 1 electron and Cl gains the electron
Creating an ionic bond
 Ionic bonds form between all nearby ions of opposite charge.
 Ionic bonds form between non-metal and metal atoms
 Ionic compounds are very stable and their crystals are very strong.
 The shape of the crystals formed depends on the ratio of positive to
negative ions and the sizes of the ions

7
 Characteristics of ionic compounds
 Ionic Compounds (losing/gaining e-)
Most have a crystal structure
Solid at room temperature
High melting and boiling points (takes a lot of energy to break
the bond)
Hard, brittle, good conductors of electricity once the ions are
separated
Dissolve easily in water

8
 ii) Covalent Bonds (Sharing of electrons)
 A bond which is formed by the mutual sharing of electrons
between the atom is termed as Covalent Bond
 Forms between non-metal atoms
 Neither atom gains or loses an electron
 The shared electrons are attracted to both positively charged
nuclei. (nucleus has a positive charge because of protons)
 A covalent bond is represented by a line between the two atoms
Cl2

9
 Covalent Bond…
 The number of covalent bonds that an atom can form depends on
the number of electrons that it has available for sharing.
Atoms of Group 16 (O,S…)can form two covalent bonds.
Atoms of group 15 (N,P…) can form three bonds
Atoms of group 14 (C, Si…)can form four bonds
 Covalent bond is further divided into 3:
Single Covalent Bond : A bond in which only 1 pair of electrons
is shared. This bond is represented by s two short lines. (-)
Double Covalent Bond: A bond in which 2 pairs of electrons are
shared. This bond is represented by s two short lines. (=)
Triple Covalent Bond: A bond in which 3 pairs of electrons are
shared. This bond is represented by three short line.

10
 Molecule and their covalent bond structures in terms of single,
double and triple bonds.

11
 Lewis approach to chemical bonding
 Lewis postulated that atoms achieve a stable octet when linked

via chemical bonds.

 In case of bonds formed from H2 , F2 etc. the bond formed from

sharing of electrons between the atoms. In this case each atom

attains a stabler outer octet of electrons.
 Lewis symbols: in the formation of a molecule only outer

electrons or group valence of the electrons take part in chemical

bonding and hence are called valence electrons.


12
 Lewis symbols
 Lewis symbols as shown are given below:

 Lewis symbols only show the group valence or electrons that take

part in chemical bonding and hence it is called valence electrons.

 Significance of Lewis Symbols : The number of dots around the

symbol represents the number of valence electrons. This number

common or group valence of the element.
 The group valence of the elements is generally either equal to the

number of dots in Lewis symbols or 8 minus the number of dots or

valence electrons.

13
Important conditions of the Lewis dot structures
 Each bond is formed as a result of sharing of an electron pair

between the atoms

 Each combining atom contributes at least 1 electron to the shared

pair.
 The combining atoms attain the outer shell noble gas electronic

configuration as a result of the sharing of electrons.

 In many compounds there are multiple bonds present between

them.

14
Electron
Distribution in Electron distribution is

Molecules depicted with Lewis

electron dot
structures
 Electrons are distributed
as:
 shared or BOND PAIRS
and
unshared or LONE
PAIRS.
G. N. Lewis
1875 - 1946

15
 Steps for Drawing Lewis Structures
1) Draw skeletal structure with the central atom being the least
electronegative element.
2) Sum the valence electrons. Add 1 electron for each negative
charge and subtract 1 electron for each positive charge.
3) Subtract 2 electrons for each bond in the skeletal structure.
4) Complete electron octets for atoms bonded to the central atom
except for hydrogen.
5) Place extra electrons on the central atom.
6) Add multiple bonds if atoms lack an octet.
16
 Building a Dot Structure
Ammonia, NH3
1. Decide on the central atom; never H.
Central atom is atom of lowest affinity for electrons.
In ammonia, N is central

2. Count valence electrons

H = 1 and N = 5
Total = (3 x 1) + 5
= 8 electrons or 4 pairs

17
 Building a Dot Structure

3. Form a sigma bond H N H

between the central atom
and surrounding atoms. H
4. Remaining electrons form ••
LONE PAIRS to complete H N H
octet as needed.
H
3 BOND PAIRS and 1 LONE PAIR.
Note that N has a share in 4 pairs (8 electrons), while
each H shares 1 pair.

18
 Sulfite ion, SO32-
Step 1. Central atom = S
Step 2. Count valence electrons
S= 6
3 x O = 3 x 6 = 18
Negative charge = 2
TOTAL = 6 + 18 + 2 = 26 e-
or 13 pairs

Step 3. Form sigma bonds O

10 pairs of electrons are left.
O S O
19
 Sulfite ion, SO32- (2)
Remaining pairs become lone pairs,
first on outside atoms
then on central atom.
••
•
• O ••
•• ••
•
• O S O
••
•
•
•• ••

Each atom is surrounded by an octet of electrons.

NOTE - must add formal charges (O-, S+) for complete dot diagram
20
 Carbon Dioxide, CO2
1. Central atom = __C____
2. Valence electrons = _16_ or _8_ pairs
3. Form sigma bonds.

O C O
This leaves __6__ pairs.
4. Place lone pairs on outer atoms.
•• ••

O C O
• •
• •
•• ••

21
 Carbon Dioxide, CO2 (2)
4. Place lone pairs on outer atoms.
•• ••

O C O
• •
• •
•• ••

5. To give C an octet, form DOUBLE BONDS

between C and O.

•• ••

O C O
• •
O C O
• •
• • •
•
•• •• •• ••

The second bonding pair forms a pi (p) bond.

22
 Lewis Structures and Formal Charge
 Formal charge can be defined as the difference between the

valence electrons of that atom in an isolated or free state and the

number of electrons assigned to that atom in the Lewis structure.
 Formula of calculating formal charge is:

 Formal charge on an atom [F.C]= [total number of electrons in

the free atom] – [total number of non bonding (lone pair)

electrons] -½[total number of bonding(shared pair) electrons]

 Formal charges are not “real” charges.

23
 Formal charges on the ozone molecule

 The central atom marked as 1, on applying the formula we get , 6-2-

½(6) = +1
 The end atom is marked as 2 , on applying the formula we get, 6-4-½(4)
=0
 The end atom marked as 3, on applying the formula we get, 6-6-½(2) =
-1
 Generally the lowest energy structure is the one with the smallest
formal charges on the atoms. The formal charge is a factor based on a
pure covalent view of bonding in which electron pairs are shared
24 equally by neighbouring atoms.
 Formal charge guidelines
A Lewis structure with no formal charges is generally better
than one with formal charges.
Small formal charges are generally better than large formal
charges.
Negative formal charges should be on the more electronegative
atom(s).

25
 Carbon Dioxide, CO2

At OXYGEN 6 - (1 / 2 )(4 ) - 4 = 0

• • • •

O C O
• •
• •

At CARBON 4 - (1 / 2 )(8 ) - 0 = 0
26
 Carbon Dioxide, CO2 (2)

An alternate Lewis structure is:

6 - (1/ 2 )(2 ) - 6 =
-1

+ • •

O C O
• •
• •
• • C atom
charge is 0.
6 - (1/ 2 )(6 ) - 2 =
+1
• • +•
AND the corresponding
O C O
•
• •
resonance form • •

27
 Carbon Dioxide, CO2 (3)

Which is the predominant resonance structure?

+ • •

O C O
• •
• • • • • •

O C O
• • • •
• • OR
• • +
O C O
• •
Answer ? • •
Form without formal charges is • •
BETTER - no +ve charge on O
REALITY: Partial charges calculated
by CAChe molecular modeling
system (on CD-ROM). -0.73 -0.73
+1.46
28
 Boron Trifluoride, BF3

••

F
• •
• •

••

F B
•
•
••

•
• F
••
•
•

What if we form a B—F double bond to

satisfy the B atom octet?

29
 Boron Trifluoride, BF3 (2)

•• +
F
•
• fc = 7 - 2 - 4 = +1 Fluorine
••

F B
•
• fc = 3 - 4 - 0 = -1 Boron
••

F
• •
• •
To have +1 charge on F, with its very high
••
electron affinity is not good. -ve charges
best placed on atoms with high EA.
Similarly -1 charge on B is bad
NOT important Lewis structure

30
 Thiocyanate ion, (SCN)-
Which of three possible resonance structures
is most important?
A. S=C=N

B. S=C - N

C. S-C N

Calculated partial charges

ANSWER:
C>A>B
-0.16 -0.32
31
-0.52
 Violations of the Octet Rule
 Exceptions to the octet rule fall into three categories:
-Molecules with an incomplete octet
Example: BF3 (boron trifluoride)
- Common with Be, B and Al compounds, but they often dimerize or
polymerize.
-Molecules with an odd number of electrons
Example: NO (nitrogen monoxide or nitric oxide)
-Molecules with an expanded octet
Elements of the 3rd period and beyond have d-orbitals that allow
more than 8 valence electrons

32
 Boron Trifluoride
Central atom = B
Valence electrons = 3 + 3*7 = 24
or electron pairs = 12
Assemble dot structure

••
•
• F
•
• The B atom has a share in
••
only 6 electrons (or 3 pairs).
•
• F B B atom in many molecules is
••
electron deficient.
•
• F
••
•
•

33
 Sulfur Tetrafluoride, SF4
Central atom = S
Valence electrons = 6 + 4*7 = 34 e-
or 17 pairs.
Form sigma bonds and distribute electron
pairs.
•• •• ••
5 pairs around the S atom.
• F S F
• •
•
•• •• A common occurrence
•• ••
outside the 2nd period.
•
•
F
••
F
••
•
•

34
35
 Valence Shell Electron Pair Repulsion Theory
Hypothesis -- The structure of a molecule is that which minimizes
the repulsions between pairs of electrons on the central atom.
“Electron Groups” (EG) = (# of atoms attached to central atom) +
(# of lone pairs, or single electrons, on central atom)

EG Electron Pair Arrangement Molecular Shapes Examples

2 Linear AX2 linear BeCl2, CO2
180°

3 Trigonal planar AX3 trigonal planar BCl3, CH3+

120° AEX2 bent SnCl2, NO2–

4 Tetrahedral AX4 tetrahedral CH4, PO43–

109.5° AEX3 pyramidal NH3, ClO3–
AE2X2 bent H2O, SeF2

36
 Valence Shell Electron Pair Repulsion Theory (cont.)
EG Electron Pair Arrangement Molecular Shapes Examples
5 Trigonal AX5 trig bypyramid PF5, SeCl5+
a bypyramidal AEX4 “see saw” SF4, BrF4+
e 120º & 90º
e AE2X3 T-shaped ClF3, XeO32–
e AE3X2 linear XeF2, ICl2–
a
6 Octahedral AX6 octahedral SF6, PCl6–
90º AEX5 square pyramidal BrF5, SF5–
AE2X4 square planar XeF4, IF4–

(A = central atom, X = terminal atom, E = lone pair)

Related Aspects:
-- In trigonal bipyramid structures, lone e- pairs adopt equatorial positions (e)
-- Order of repulsions: Lp-Lp > Lp - Bp > Bp - Bp
(predicts distortions from ideal geometries)

37
 Sample Problems

 Use VSEPR Theory to predict (and draw) 3-D structures of:

NH3 SF4 BrF4–

38
 Sample Problems
 Use VSEPR Theory to predict (and draw) 3-D structures of:
NH3 SF4 BrF4–

.. .. -
F
F F
N : S F Br F
H H F F
H
..
F
SN = 6
SN = 4 SN = 5
"square planar"
"pyramidal" "see-saw"
(AE2X4)
(AEX3) (AEX4)

39
 VSEPR Theory: The Effect of Lone Pairs

Effect of Lone Pairs on Molecular Geometry

Bond angle is compressed by lone pairs.

40
 VSEPR Theory: The Effect of Lone Pairs

41
 Electronegativity and Polarity

42
 Electron density distributions

43
44
 Polarity of Molecules
 Can predict from molecular shape
 Polar or Non-Polar?
In very symmetrical structures (e.g. CO2 or CF4), the individual
bond dipoles effectively cancel each other and the molecule is
non-polar.
In less symmetrical structures (e.g. SO2 and SF4), the bond
dipoles do not cancel and there is a net dipole moment which
makes the molecule polar. ..
+
CO2 O C O SO2
S
+ O O
Linear
Non-Linear
Non-Polar
Polar
45
 Polarity of Molecules, cont.

F F
F
CF4 C SF4 S :
F F F
F F
Tetrahedral Distorted Tetrahedral
"see-saw"
Non-Polar
Polar

Other examples for practice:

Polar: H2 O SnCl2 NH3 SeF2 PF3 BrF5 XeO3

Non-Polar: BeCl2 CH4 PF5 XeF2 XeF4 SO3

46
Theories of Bonding for Covalent
Molecules

47
 Valence Bond Theory
 Basic Concept
Covalent Bonds result from overlap of atomic orbitals
For example, consider the H2 and HF molecules:

48
49
Experimentally it has been found that the magnitude of new
attractive force is more than the new repulsive forces. As a
result, two atoms approach each other and potential energy
decreases.
Ultimately a stage is reached where the net force of attraction
balances the force of repulsion and system acquired hydrogen
atoms are said to be bonded together to form a stable molecule
having the bond length of 74 pm.
Since the energy gets released when the bond is formed
between two hydrogen atoms, the hydrogen molecule is more
stable than that of isolated hydrogen atoms.
The energy so released is called as bond enthalpy, which is
corresponding to minimum in the curve.

50 H2 (g) + 435.8kJmol-1  H (g) + H (g)

 Two Types of Covalent Bonds
s (sigma) bond “head-to-head” overlap along the bond axis

p (pi) bond “side-to-side” overlap of p orbitals:

2p 2p p bond

 Single bond -- always a s bond

 Double bond -- combination of one s bond and one p bond
 Triple bond -- combination of one s bond and two p bonds

51
 s (sigma) bonds
“head-to-head” overlap along the bond axis

52
 p (pi) bonds
“side-to-side” overlap of p orbitals:

53
 Hybrid Atomic Orbitals
VSEPR theory "explains" this -- 4 e- pairs,  tetrahedral

Question: Description of bonding in CH4 molecule?

Experimental fact -- CH4 is tetrahedral (H-C-H angle = 109.5º)

Problem If only s and p orbitals are used, angles ought to be 90º

since the p orbitals are mutually perpendicular!
Solution Modify the theory of atomic orbitals and use:
Hybridization Combination of 2 or more atomic orbitals on the same
54
atom to form a new set of “Hybrid Atomic Orbitals” used in
bonding.
 Types of Hybrid Orbitals
Atomic Orbitals Hybrid Orbitals Geometry Unhybridized p
Orbitals
one s + one p two sp Linear 2
EG = 2 (180º)

one s + two p three sp2 Trigonal planar 1

EG = 3 (120º)

one s + three p four sp3 Tetrahedral 0

EG = 4 (109.5º)

{Note: combination of n AO’s yields n Hybrid Orbitals)

Example: in CH4, C is sp3 hybridized:

ground state - valence shell orbital diagram

C
2s 2p (predicts 90º angles -- wrong!)

C hybridized state
3
55 sp s p3 s p3 s p3 (predicts 109.5º angles -- right!)
 Examples
 Use valence bond theory to describe the bonding in the following
(use clear 3-D pictures showing orbital overlap, etc)
H2O NH3 CH4 PF3
--simple s bonds and lone pairs
H2CNH
--double bond like H2CCH2 ethene and H2CO formaldehyde)
HCN
--triple bond like HCCH ethyne and N2 nitrogen)

56
 Formaldehyde

57
 Nitrogen

58
 Sample Problem
 Fully describe the bonding in NaHCO3 using valence bond theory.

59
 Sample Problem H O
Na
O C O
 Fully describe the bonding in NaHCO3 using valence bond theory.

Answer: The Lewis structure is (and its resonance

equivalent). VSEPR theory gives a trigonal planar
structure at carbon (3 EG), and a bent structure at the central O (4 EG).
At C, the expected hybridization is sp2, with 120° bond angles. For the
terminal O with a single bond, there will be one s bond between the p
orbital (terminal O) and the sp2 orbital (central C).
O C  bond
p sp2
For the C=O bond, there will be a similar s bond, but also one p bond from
the side-on interaction of one p orbital on each atom.

O C  bond and  bond

p sp2
p p
60 continued…
 Sample Problem, cont.
For the C-OH bond there will be one s bond between the O sp3
orbital and the C sp2 orbital.
C O  bond
3
sp2 sp

At the central oxygen there is sp3 hybridization (EG = 4). Each

lone pair lies in one sp3 hybrid orbital. The O-H bond is a s bond
between the O sp3 hybrid and the H 1s orbital.

O H  bond
sp3 s

61
 Limitation of VBT
The theory is unable to adequately explain
 electronic and magnetic properties
Electron delocalization
Conductivity of metals

62
 Molecular Orbital Theory

63
 Molecular Orbitals for Simple Diatomic Molecules
In H2 the 1s atomic orbitals on the two H atoms are
combined into:
a bonding MO -- s1s and an antibonding MO --
s*1s 
 1s
MO energy level diagram for H2 (only the bonding MO is
filled): 1s 1s

1s
H H2 H

64
 Simple MO Diagrams
 In contrast, the MO diagram for the nonexistent molecule, He2, shows that both
bonding and antibonding MO’s are filled:
1s

1s 1s

1s
He He2 He

Bond Order = 1/2[(# of bonding e–’s) - (# of antibonding e–’s)]

 For H2 = 1/2 [2-0] = 1 (a single bond)

 For He2 = 1/2 [2-2] = 0 (no net bonding interaction)

65
 MO’s for 2nd Row Diatomic Molecules
 (e.g. N2, O2, F2, etc)
 AO combinations -- from s orbitals and from p orbitals

66
 MO Energy Level Diagram

67
 Examples
 e.g. Fill in MO diagram for C2, N2, O2, F2 and Ne2 and
determine bond order for each:

Molecule C2 N2 O2 F2 Ne2
Bond order 2 3 2 1 0

 General “rules”
Electrons fill the lowest energy orbitals that are available
Maxiumum of 2 electrons, spins paired, per orbital
Hund’s rule of maximum unpaired spins applies*
*(accounts for paramagnetism of O2 (VB theory fails here!)

68
 MO diagram for oxygen, O2

69
 MO diagram for oxygen, O2

70
 Sample Problem
Write the MO diagram for HCl. Predict the bond
order and sketch the bonding and antibonding MO’s.
[note: H 1s energy = -13 eV, Cl 3s energy = -25 eV, Cl
3p energy = -14 eV]

71
 Sample Problem
 Write the MO diagram for HCl. Predict the bond order and
sketch the bonding and antibonding MO’s. [note: H 1s energy =
-13 eV, Cl 3s energy = -25 eV, Cl HCl
3p energy = -14 eV]
Cl H
 Answer:
*

-13 eV
-14 eV 3p nb 1s

b

-25 eV
3s
nb

b Cl H

The bond order is 1.

72
* Cl H
 Crystal Chemistry
 A crystal is a piece of a solid substance that has plane surface,
sharp edges, and a regular geometric shape.
Crystals can be classified into 4 types:
1. Molecular Crystals
Neutral molecules held together by weak van der Waals bonds
Rare as minerals
Mostly organic
Weak and readily
decompose, melt,
cleave, etc.
Example: graphite

73
 Crystal Chemistry
2. Covalent Crystals
Atoms of similar high e-neg and toward right side of Periodic
Table
Also uncommon as minerals (but less so than molecular)
Network of strong covalent
bonds with no weak links
Directional bonds  low
symmetry and density
Example: diamond

74
 Crystal Chemistry hard-sphere model

The diamond structure

All carbon atoms in IV coordination

FCC unit cell polyhedral model

75 blue C only
ball-and-stick model
 3. Metallic Crystals
Crystal Chemistry
Atoms of similar e-neg and toward left side of Periodic Table
Metallic bonds are directionless bonds  high
symmetry and density
Pure metals have same sized atoms
Closest packing  12 nearest mutually-touching neighbors
Cubic Closest Packing (CCP) abcabcabc stacking = FCC cell
(face-centered cubic AKA cubic close packed)
Hexagonal Closest Packing (HCP) ababab = hexagonal cell
Also BCC in metals, but this is not Closest Packing
More on coordination and closest packing next time

76
 Crystal Chemistry
4. Ionic Crystals
Most minerals
First approximation:
Closest-packed array of oxygen atoms
Cations fit into interstices between oxygens, balance the negative
charges. Negative charges mostly due to oxide ions O-
Different types of interstitial sites available
Cations occupy only certain sites where can fit
Only enough cations to attain electrical neutrality

77
78