Chemical Bonding

• Ionic vs. covalent bonding

• Molecular orbitals and the covalent bond
• Valence electron Lewis dot structures
octet vs. non-octet
resonance structures
formal charges
• VSEPR - predicting shapes of molecules

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 Chemical Bonding
Problems and questions —
• How is a molecule or polyatomic
ion held together?
• Why are atoms distributed at
strange angles?
• Why are molecules not flat?
• Can we predict the structure?
• How is structure related to
chemical and physical properties?

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Forms of Chemical Bonds
• There are 2 extreme forms of connecting
or bonding atoms:
• Ionic—complete transfer of electrons
from one atom to another
• Covalent—electrons shared between
atoms

Most bonds are somewhere in between.

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Ionic compounds
- essentially complete electron
transfer from an element of low
Ionic
IE (metal) to an element of high
electron affinity (EA) (nonmetal)
Bonds
Na(s) + 1/2 Cl2(g)  Na+ + Cl-
 NaCl (s)

- primarily between metals

(Grps 1A, 2A and transition metals)
and nonmetals (esp O and halogens)

- NON-DIRECTIONAL bonding
via Coulomb (charge) interaction

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 Covalent Bonding
Covalent bond is the sharing of the VALENCE

ELECTRONS of each atom in a bond

+
Br Br

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 8A
1A
Valence Electrons

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

Number of valence electrons is

equal to the Group number.

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 Covalent Bonding
The bond arises from the mutual attraction
of 2 nuclei for the same electrons.

HA + HB HA HB

A covalent bond is a balance

of attractive and repulsive forces.

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 Bond Formation
A bond can result from a “head-to-head” overlap
of atomic orbitals on neighboring atoms.
•• ••
• •
H + Cl
••
• H Cl •
••

Overlap of H (1s) and Cl (2p)

This type of overlap places bonding electrons in a

MOLECULAR ORBITAL along the line between
the two atoms and forms a SIGMA BOND (s).

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Sigma Bond Formation by Orbital Overlap
H H
• + • •  • Two s A.O.s overlap to
from an s s M.O.
sigma bond ( s)
 
Similarly, two p A.O.s
can overlap end-on to
 from a ps M.O.

e.g.
F2

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 Electron
Distribution in • Electron distribution
Molecules is depicted with
Lewis electron
dot structures
• Electrons are
distributed as:
• shared or BOND
PAIRS and
• unshared or LONE
PAIRS.
G. N. Lewis
1875 - 1946
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 Bond and Lone Pairs
• Electrons are distributed as shared or BOND
PAIRS and unshared or LONE PAIRS.
••
H Cl ••
••
Unshared or
lone pair (LP)
shared or bond pair

This is a LEWIS ELECTRON DOT structure.

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 Rules of Lewis Structures
• No. of valence electrons of an atom =
Group number
• For Groups 1A-4A (Li - C),
no. of BOND PAIRS = group number
• For Groups 5A-7A (N - F),
no. of BOND PAIRS = 8 - group No.
• Except for H
(and atoms of 3rd and higher periods),
#Bond Pairs + #Lone Pairs = 4

• This observation is called the OCTET RULE

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 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

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 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.

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 Carbon Dioxide, CO2
1. Central atom = __C____
2. Valence electrons =
C= 4
O = 6 x 2 = 12
Total : 16 e- (8 pairs)
3. Form sigma bonds.
O C O
This leaves __6__ pairs.
4. Place lone
••
pairs on outer
••
atoms.
• •
• O
••
C O••
•
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 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.

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 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
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 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

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Double and even H2CO
triple bonds are
commonly
observed for C,
N, P, O, and S

SO3

• •

C2F4
• O
••
C O
••
•

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 Sulfur Dioxide, SO2
1. Central atom = S
2. Valence electrons = 6 + 2 x 6 = 18 electrons
•
•• •• ••
•
or 9 pairs
• O
••
S O
••
•

3. Form pi (p) bond so that S has an octet

— note that there are two ways of doing this.
bring in OR bring in
left pair right pair
•• •• ••
• •
• O
••
S O••
•

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 Sulfur Dioxide, SO2
Equivalent structures
bring in OR bring in called:
left pair right pair
•• •• •• RESONANCE
• •
• O••
S O
••
• STRUCTURES
•• •• •• ••
• •
• O S O
•• ••
•
•
•
••
O S O •
•
••
A BETTER representation of SO2
is made by forming 2 double bonds
Each atom has
O=S=O - OCTET
- formal charge = 0

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 Violations of the Octet Rule
Usually occurs with: elements of higher periods.
Boron

BF3
SF4
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 Boron Trifluoride
• Central atom = B
• Valence electrons = 3 + 3x7 = 24
or electron pairs = 12
• Assemble dot structure
••
•
•
• F • The B atom has a share
••
in only 6 electrons (or 3
•
• F B pairs). B atom in many
•• molecules is electron
•
• F •
•
deficient.
••

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Sulfur Tetrafluoride, SF4
• Central atom = S
• Valence electrons = 6 + 4 x7 = 34 e-
or 17 pairs.
• Form sigma bonds and distribute
electron pairs.
•• •• ••
• 5 pairs around the S
• F
•

••
S F••
•
atom. A common
•• ••
• • occurrence outside the
• F F•• •
•• 2nd period.

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 Formal Atom Charges
• Atoms in molecules often bear a charge (+ or -).

Formal charge = Group no. (valence electron)

- 1/2 (sum of bond electrons)
- (sum of LP electrons)

• The most important dominant resonance structure

of a molecule is the one with formal charges
as close to 0 as possible.

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Carbon Dioxide, CO2

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

• • • •
• •
• O C O •

At CARBON 4 - (1/ 2)(8) - 0 = 0

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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
resonance form
• O
• •
C O •

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 Carbon Dioxide, CO2 (3)
Which is the predominant resonance structure?
•
+ • •
•

•
• • • •
•
• O C O •

• O C O • OR • •

•
• •
•
+
Answer ?
Form without formal charges is
•
• •
O C O •

BETTER - no +ve charge on O

• REALITY: Partial charges calculated
by CAChe molecular modeling
system
-0.73 -0.73
+1.46
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 Boron Trifluoride, BF3
••
• •
• F •

••
•
• F
••
B
• •
• F
••
•

What if we form a B—F double

bond to satisfy the B atom octet?

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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
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