Atomic Structure and

Bonding

Part II: Bonding (Chapters 9-10)

 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Main group – valence are outer s+p electrons

 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Na Cl

Na Cl

[Ne]3s1 [Ne]3s23p5
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Na Cl

Na Cl

[Ne]3s1 [Ne]3s23p5
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Na Cl

Na Cl

[Ne] [Ne]3s23p6
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Na Cl

Na+ Cl-

[Ne] [Ne]3s23p6
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Na Cl

Na Cl
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Na Cl

Na Cl
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Na Cl

+ -
Na Cl
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Na Cl

+ -
Na Cl
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Na Cl

+ -
Na Cl Ionic bonding
Transfer of electrons
cation anion
 Bonding

Exchange or share electrons – to get filled subshells

eg 1s2 (H, He and Li end with 2 e-)

ns2 np6 (Main group end with 8 e-)

• Lewis Structures
Figure 9.1: Sodium chloride crystals

E.R. Degginger/ www.color-pic.com

Ionic Bonding
Figure 9.2: Energetics of ionic
bonding

Coulombs
law

p23
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Ca

Ca O
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Ca

Ca O
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Ca

2+ 2-
Ca O
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Cl
Ca

Ca Cl
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Cl
Ca

Cl
Ca
Cl
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Cl
Ca

Cl
Ca
Cl
 s2p2 s2p4 s2p6
s1 s2 s2p1 s2p3 s2p5

Cl
Ca

2+ -
Ca 2 Cl
 Use the groups to quickly determine valence electrons
He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Br Kr
 Figure 9.15: Electronegativities
of the elements

To remember: Which are the five most electronegative elements

on the periodic table?
Kelter, Mosher and Scott, Chemistry: The Practical Science, 1/e. Copyright © 2008 by Houghton Mifflin Company. Reprinted with permission.
 Covalent Bonding
• 2 electrons shared to make the bond

H + H → H H H-H

Cl + Cl → Cl Cl Cl-Cl

H + Cl → H Cl H-Cl
 Formation of H-H molecule
H H Molecular Orbital approach
Linear Combination of Atomic Orbitals
L.C.A.O

σ1s

σ1s*
 What happens in terms of energy
levels?

σ1s*

1s 1s

σ1s

First atom second atom

Molecule after
before bonding before bonding
bonding
 What happens in terms of energy
levels?

1s 1s

First atom second atom

Molecule after
before bonding before bonding
bonding
σ2p σ2p *
 What happens in terms of energy
levels?

σ2p*

2p 2p

σ2p

First atom second atom

Molecule after
before bonding before bonding
bonding
π2p π 2p*
 What happens in terms of energy
levels?

π2p*

2p 2p

π 2p

First atom second atom

Molecule after
before bonding before bonding
bonding
 π – bonds
• Electron occupies both lobes

• π bond is more reactive

H H Br Br
C C + Br2 H C C H
H H H H

• π bond cannot rotate

H H H Br
C C C C
Br Br Br H
cis trans
Figure 10.31

Bond order = ½ (2 – 0) = 1
Figure 10.32: The energies of
the molecular orbitals of Li2

Bond order = ½ (2-0) = 1

Paramagnetic or diamagnetic?
Figure 10.32: The energies of
the molecular orbitals of Li2

Still get the same bond order = ½ (4-2) = 1

 LCAO diagram for N2
N2
 LCAO diagram for N2
N2

2p 2p
 LCAO diagram for N2
N2

Bond order = ½ (6-0) = 3

Paramagnetic or diamagnetic?
 Figure 10.34
N2
 Understanding the Geometry of
Atoms in Molecules
• Hybridization
orbitals working together to create new
geometries

• Valence Shell Electron Pair Repulsion

electron groups around atoms “try” to get as
far apart as possible
 Shapes of molecules (VSEPR)

No of groups 2 3 4 5 6
Hybridization sp sp2 sp3 sp3d sp3d2

Bond angle 180° 120° 109.5°

 Hybridization
• Hybrid orbitals Covalent bonding is far
more complex than 2 orbitals overlapping.
Overlap occurs between several orbitals.
Hybridization

sp

sp2

sp3
 Hybridization
sp3 – three p orbitals and one s orbital
“create” four new hybrid sp3 orbitals

Tetrahedral
http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/hybrv18.swf
 Hybridization
sp2 – two p orbitals and one s orbital “create”
three sp2 orbitals. The remaining p orbital is
unchanged

Trigonal planar

http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/hybrv18.swf
 Hybridization
sp – one s and one p “create” two sp hybrid
orbitals. Two p orbitals are unchanged

http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/hybrv18.swf
 Polar molecules

Dipole Moment
A measure of the degree of charge separation in a
molecule
Polar molecules

Non Polar Polar

H H H Cl

δ+ δ-
Cl Cl

H Cl

Draw the dipole moment

pointing towards negative side
 Polar molecules
• EN: H-2.1; C-2.5; O-3.5; Cl-3.0; Br-2.8

Br H

Br Br Br
Br Br
Br
 Polar molecules
• EN: H-2.1; C-2.5; O-3.5; Cl-3.0; Br-2.8

Br H H H
C C C C
H Br Br Br
A no electric field; B, electric field;
 Dipole-dipole interaction
•(a van der Waals force)
 Use the groups to quickly determine valence electrons
He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Br Kr
 Lewis Structures for sp 3
central
atom (tetrahedral arrangement of
electron groups)
CH4 CCl4
NH3 CH3F
H2O CHCl3
NH4+ OF2
NCl3
NH2OH
H C Lewis Structures
H
CH4
H C H

H
H C Lewis Structures
H
CH4
H C H

H
H C Lewis Structures
H
CH4
H C H

H
H N Lewis Structures

NH3 H N H

H
H N Lewis Structures

NH3 H N H

H
H N Lewis Structures

NH3 H N H

H
H O Lewis Structures

H2O H O

H
H O Lewis Structures

H2O H O

H
H O Lewis Structures

H2O H O

H
H N Lewis Structures
H
NH4+
H N H

H
H N Lewis Structures
H +
NH4+
H N H

H
H N Lewis Structures
H +
NH4+
H N H

H
H N Lewis Structures
H +
NH4+
H N H

H
Cl C Lewis Structures
Cl
CCl4
Cl C Cl

Cl
Cl C Lewis Structures
Cl
CCl4
Cl C Cl

Cl
Cl C Lewis Structures
Cl
CCl4
Cl C Cl

Cl
CH3F F CHCl3 H

H C H Cl C Cl

H Cl
OF2 NCl3
F O Cl N Cl

F Cl
NH2OH

H N O

H H

H N H H O

H H
•Hydrogen bonding arises when H is
covalently bonded to a very electronegative
atom
—O—H . . . O—

—N—H . . . N—

F—H . . . F—H
Not just about electronegativity
Not just about electronegativity
 Difficult structures
• Place H, O, F, Cl on the outside of structures
• Find total valence electrons available (correct
for charge)
• Use some of these electrons to draw the
molecule skeleton.
• How many electrons do you have left?
• How many electrons do you still need for the
octet rule?
• For every 2 electrons you are short, there is a
double bond.
 F B Lewis Structures
- 4 x 7 (F)=28
BF4 1 x 3 (B)=3
1 x 1 (-ve)=1

F Total 32 electrons

F B F

Step 1,2 : Place O,Cl,F etc outside. Count the valence electrons
 F B Lewis Structures
- 4 x 7 (F)=28
BF4 1 x 3 (B)=3
1 x 1 (-ve)=1

F Total 32 electrons
24 electrons left

F B F

Step 3 : Draw the skeleton (this requires 4 pairs of bonding electrons)

 F B Lewis Structures
- 4 x 7 (F)=28
BF4 1 x 3 (B)=3
1 x 1 (-ve)=1

F Total 32 electrons
24 electrons left

F B F

Step 4 : How many do you need for each atom? (six to make octet)
 F B Lewis Structures
- 4 x 7 (F)=28
BF4 1 x 3 (B)=3
1 x 1 (-ve)=1

F Total 32 electrons
24 electrons left
18 electrons left
F B F

Step 4 : How many do you need for each atom?

 F B Lewis Structures
- 4 x 7 (F)=28
BF4 1 x 3 (B)=3
1 x 1 (-ve)=1

F Total 32 electrons
24 electrons left
12 electrons left
F B F 6 electrons left

Step 4 : How many do you need for each atom?

 F B Lewis Structures
- 4 x 7 (F)=28
BF4 1 x 3 (B)=3
1 x 1 (-ve)=1

F Total 32 electrons
24 electrons left
12 electrons left
F B F 6 electrons left
0 electrons left
F

Step 4 : How many do you need for each atom?

 F B Lewis Structures
- 4 x 7 (F)=28
BF4 1 x 3 (B)=3
1 x 1 (-ve)=1
Total 32 electrons
F -
24 electrons left
12 electrons left
F B F 6 electrons left
0 electrons left
F

Step 4 : How many do you need for each atom?

H N Lewis Structures
4 x 1 (H)=4
NH4+ 1 x 5 (N)=5
(+ve)= remove one e
H
Total 8 electrons

H N H

H
H N Lewis Structures
4 x 1 (H)=4
NH4+ 1 x 5 (N)=5
(+ve)= remove one e
H
Total 8 electrons
0 electrons left
H N H

Draw the skeleton (this requires 4 pairs of bonding electrons)

Lewis Structures for sp 2atoms
(trigonal planar arrangement of
electron groups)

C2H4
CH2O
COF2
N2H2
H C Lewis Structures
16 electrons
C2H4
H H
C C
H H
H C Lewis Structures
12 electrons
C2H4 2 electrons
Problem short 2 electrons
H H One double bond
C C
H H
H C Lewis Structures
12 electrons
C2H4 2 electrons
Problem short 2 electrons
H H One double bond
C C 0 electrons

H H
 Lewis Structures

C2H4
H H
C C

H H
H O Lewis Structures
C 12 electrons

CH2O H
C O

H
H O Lewis Structures
C 12 electrons
6 electrons
H Problem short 2 electrons
CH2O
One double bond
C O

H
H O Lewis Structures
C 12 electrons
6 electrons
H Problem short 2 electrons
CH2O
One double bond
C O
4 electrons

H
H O Lewis Structures
C 12 electrons
6 electrons
Problem short 2 electrons
CH2O
One double bond
4 electrons
0 electrons
 Lewis Structures

CH2O
H
C O
H
F O Lewis Structures
C 24 electrons

One double bond

F
COF2 C O

F
H N Lewis Structures
12 electrons
N2H2
N N

H H
 Lewis Structures for sp atoms
(linear arrangement of electron
groups)

N2
HCN
CN-
C2H2
CO
 N Lewis Structures
10 electrons
N2 8 electrons
require 12 electrons

N N 4 electrons short
(2 double bonds)
 N Lewis Structures

N2

N N
H N Lewis Structures
C
10 electrons
6 electrons
HCN
Need 10 electrons
(four short)
H C N Two double bonds
2 electrons
 10 valence electrons total

CN- CO
-
C N C O

C2H2

H C C H
 Lewis Structures that may be
represented in more than one way
(resonance)

CO32-
NO3-
O3
C6H6
 O Lewis Structures
C 24 electrons

One double bond

CO32-
2- 2- 2-

O O O
C O C O C O
O O O
 O Lewis Structures
N 24 electrons

One double bond

NO3-
- - -

O O O
N O N O N O
O O O
Delocalized -bonding

O
N O
O
Delocalized -bonding

O
N O
O
Delocalized -bonding

O
N O
O
 Ozone

O O O O

O O

Each oxygen has three electron groups constant

therefore each oxygen is sp2 hybridized
 Ozone

sp2

sp2
sp2 sp2

sp2 sp2 sp2

sp2
sp2
Ozone

What about the unhybridized

p orbital from each atom?
Benzene - delocalized -bonding

H H
H C H H C H
C C C C
C C C C
H C H H C H
H H
Figure 9.15: Electronegativities
of the elements

Kelter, Mosher and Scott, Chemistry: The Practical Science, 1/e. Copyright © 2008 by Houghton Mifflin Company. Reprinted with permission.
Covalent and Ionic Bonding

H + Cl → H Cl H-Cl

Na + Cl → [ Na] + [ Cl ]-
 Ion Dipole interactions

https://www2.chemistry.msu.edu/courses/cem151/Intramolecularforces_Ch11.pdf
 Dipole-dipole interaction
•(a van der Waals force)
Hydrogen Bonding
 London Forces (instantaneous
dipole) dispersion
•(a van der Waals force)
•Inducing an instantaneous dipole
•All molecules
Intermolecular Forces.
 H

H C H

H N H

H
H O

H +

H N H

H
 Cl

Cl C Cl

Cl

F H

H C H Cl C Cl

H Cl
OF2 NCl3
F O Cl N Cl

F Cl
H N O

H H
 H H
C C
H H

F B F

F
H
C O

F
C O

F
 N N

H H

H C N

N N
 - - -

O O O
N O N O N O
O O O
 O O O O

O O
 LCAO diagram for O2
O O2 O

σ2p*

π2p*
E

2p 2p
π2p

σ2p
 LCAO diagram for O2
O O2 O

σ2p*

π2p*
E

2p 2p
π2p

σ2p
 LCAO diagram for O2
O O2 O

2p 2p