Chemical Bonding

and
Molecular Structure
(Chapter 9)

Ionic vs. covalent bonding

Molecular orbitals and the covalent bond (Ch. 10)
Valence electron Lewis dot structures
octet vs. non-octet
resonance structures
formal charges
VSEPR - predicting shapes of molecules
Bond properties
polarity, bond order, bond strength
18, 20 Oct 97

Bonding and Structure

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?
18, 20 Oct 97

Bonding and Structure

Forms of Chemical Bonds

There are 2 extreme forms of connecting
or bonding atoms:

Ioniccomplete transfer of electrons

from one atom to another

Covalentelectrons shared between

atoms

Most bonds are somewhere in between.

18, 20 Oct 97

Bonding and Structure

Ionic compounds
- essentially complete electron
transfer from an element of low IE
(metal) to an element of high
electron affinity (EA) (nonmetal)

Ionic
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
18, 20 Oct 97

Bonding and Structure

Covalent Bonding
Covalent bond is the sharing of the VALENCE

ELECTRONS of each atom in a bond

Recall: Electrons are divided between core
and valence electrons.
ATOM
core
Na 1s2 2s2 2p6 3s1
[Ne]
Br [Ar] 3d10 4s2 4p5

[Ar] 3d10

valence
3s1
4s2 4p5

Br Br
18, 20 Oct 97

Bonding and Structure

Valence Electrons

1A

2A

3A

4A

5A

6A

8A

7A

Number of valence electrons is

equal to the Group number.
18, 20 Oct 97

Bonding and Structure

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.

6_H2bond.mov

18, 20 Oct 97

Bonding and Structure

Bond Formation
A bond can result from a head-to-head overlap
of atomic orbitals on neighboring atoms.

Cl

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 ( ).

18, 20 Oct 97

Bonding and Structure

Sigma Bond Formation by Orbital Overlap

Two s Atomic Orbitals (A.O.s) overlap to form
an s (sigma) Molecular Orbital (M.O.)
H

sigmabond( )
6_H2pot.mov

18, 20 Oct 97

Bonding and Structure

Sigma Bond Formation by Orbital Overlap

H

sigmabond( )

Two s A.O.s overlap to

from an s M.O.

Similarly, two p A.O.s

can overlap end-on to
from a p M.O.

e.g.
F2

18, 20 Oct 97

Bonding and Structure

10

Electron
Distribution in
Molecules

Electron distribution
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
18, 20 Oct 97

Bonding and Structure

11

Bond and Lone Pairs

Electrons are distributed as shared or BOND
PAIRS and unshared or LONE PAIRS.

Cl

Unshared or
lone pair (LP)
shared or bond pair

This is a LEWIS ELECTRON DOT structure.

18, 20 Oct 97

Bonding and Structure

12

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
18, 20 Oct 97

Bonding and Structure

13

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
18, 20 Oct 97

Bonding and Structure

4 pairs
14

Building a Dot Structure

3. Form a sigma bond
between the central atom
and surrounding atoms.
4. Remaining electrons form
LONE PAIRS to complete
octet as needed.

H N H
H

H N 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, 20 Oct 97

Bonding and Structure

15

Sulfite ion, SO32Step 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 eor 13 pairs

Step 3. Form sigma bonds

10 pairs of electrons are left.
18, 20 Oct 97

Bonding and Structure

O
16

Sulfite ion, SO32- (2)

Remaining pairs become lone pairs,
first on outside atoms
then on central atom.

Each atom is surrounded by an octet of electrons.

NOTE - must add formal charges (O-, S+) for complete dot diagram
18, 20 Oct 97

Bonding and Structure

17

Carbon Dioxide, CO2

1. Central atom = __C____
2. Valence electrons = _16_ or _8_ pairs
3. Form sigma bonds.

This leaves __6__ pairs.

4. Place lone pairs on outer atoms.

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Bonding and Structure

18

Carbon Dioxide, CO2 (2)

4. Place lone pairs on outer atoms.

5. To give C an octet, form DOUBLE BONDS

between C and O.

The second bonding pair forms a pi

18, 20 Oct 97

Bonding and Structure

() bond.
19

H2CO

Double and even

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

SO3

C2F4
18, 20 Oct 97

Bonding and Structure

20

Sulfur Dioxide, SO2

1. Central atom = S
2. Valence electrons = 6 + 2*6 = 18 electrons

or 9 pairs

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

note that there are two ways of doing this.
OR bring in
right pair

bring in
left pair

18, 20 Oct 97

Bonding and Structure

21

Sulfur Dioxide, SO2

bring in
left pair

Equivalent structures
called:

OR bring in
right pair

S O

RESONANCE
STRUCTURES

S O

The proper Lewis structure

is a HYBRID of the two.

A BETTER representation of SO2

is made by forming 2 double bonds

O=S=O
18, 20 Oct 97

Bonding and Structure

Each atom has

- OCTET
- formal charge = 0
22

Urea (NH2)2CO
1. Number of valence electrons = 24 e2. Draw sigma bonds.

H N

Leaves 24 - 14 = 10 e- pairs.

N H
H

3. Complete C atom octet with double bond.

4. Place remaining electron pairs on oxygen
and nitrogen atoms.
O
H N
H
18, 20 Oct 97

N H
H

Bonding and Structure

23

Violations of the Octet Rule

Usually occurs with:
Boron

BF3
18, 20 Oct 97

elements of higher periods.

SF4
Bonding and Structure

24

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

The B atom has a share

in only 6 electrons (or 3
pairs). B atom in many
molecules is electron
deficient.

18, 20 Oct 97

Bonding and Structure

25

Sulfur Tetrafluoride, SF4

Central atom = S
Valence electrons = 6 + 4*7 = 34 eor 17 pairs.
Form sigma bonds and distribute
electron pairs.

5 pairs around the S

S
F

atom. A common

occurrence outside the

F
F

2nd period.

18, 20 Oct 97

Bonding and Structure

26

Formal Atom Charges

Atoms in molecules often bear a charge (+ or -).

Formal charge = Group no.

- 1/2 (no. bond electrons)
- (no. of LP electrons)
The most important dominant resonance structure
of a molecule is the one with formal charges
as close to 0 as possible.
18, 20 Oct 97

Bonding and Structure

27

Carbon Dioxide, CO2

At OXYGEN

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

At CARBON
18, 20 Oct 97

4 - (1/ 2)(8) - 0 = 0
Bonding and Structure

28

Carbon Dioxide, CO2 (2)

An alternate Lewis structure is:
6 - (1/ 2)(2) - 6 = -1

C atom
charge is 0.

6 - (1/ 2)(6) - 2 = +1
AND the corresponding
resonance form
18, 20 Oct 97

Bonding and Structure

29

Carbon Dioxide, CO2 (3)

Which is the predominant resonance structure?

OR

Answer ?
Form without formal charges is
BETTER - no +ve charge on O

REALITY: Partial charges calculated

by CAChe molecular modeling
system (on CD-ROM).
18, 20 Oct 97

Bonding and Structure

C
C

-0.73

+1.46

-0.73
30

Boron Trifluoride, BF3

What if we form a BF double

bond to satisfy the B atom octet?
18, 20 Oct 97

Bonding and Structure

31

Boron Trifluoride, BF3 (2)

fc = 7 - 2 - 4 = +1

Fluorine

fc = 3 - 4 - 0 = -1

18, 20 Oct 97

Boron

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
Bonding and Structure

32

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:

-0.52
18, 20 Oct 97

-0.16

-0.32

Bonding and Structure

C>A>B
33