Chapter 3

Lewis Structure – VSEPR Model

Chapter 13 Bonding: General Concepts
13.2 Electronegativity
13.3 Bond Polarity and Dipole Moments
13.9 The Localized Electron Bonding Model
13.10 Lewis Structure
13.11 Resonance
13.12 Exceptions to the Octet Rule
13.13 Molecular Structure: The VSEPR Model
 Electronegativity

Electronegativity: the ability of an atom in a molecule to attract shared

electrons to itself.

Figure 13.3 - The Pauling electronegativity values. Electronegativity generally increases

across a period and decreases down a group.
 Bond Polarity and Dipole Moments
When a molecule has a center of positive charge and a center of
negative charge is said to be dipolar, or to have a dipole moment.

Figure 13.4 - An electrostatic

potential diagram of HF. Red
indicates the most electronrich
area (the fluorine atom) and blue
indicates the most electron-poor
region (the hydrogen atom).
Bond Polarity and Dipole Moments
 Bond Polarity and Dipole Moments

Polar
molecule

Figure 13.5 - (a) The charge distribution in the water molecule. (b) The water molecule
in an electric field. (c) The electrostatic potential diagram of the water molecule.
 Bond Polarity and Dipole Moments

Polar
molecule

Figure 13.6 - (a) The structure and charge distribution of the ammonia molecule. The
polarity of the NOH bonds occurs because nitrogen has a greater electronegativity than
hydrogen. (b) The dipole moment of the ammonia molecule oriented in an electric
field. (c) The electrostatic potential diagram for ammonia.
 Bond Polarity and Dipole Moments
Some molecules have polar bonds but do not have a dipole
moment. This occurs when the individual bond polarities are
arranged in such a way that they cancel each other out.

Non polar
molecule

Figure 13.7 - (a) The carbon dioxide molecule. (b) The opposed bond polarities cancel
out, and the carbon dioxide molecule has no dipole moment. (c) The electrostatic
potential diagram for carbon dioxide.
Bond Polarity and Dipole Moments
 Bond Polarity and Dipole Moments

Example 13.2

For each of the following molecules, show the direction of the bond
polarities. Also indicate which ones have dipole moments: HCl, Cl2,
SO3 (planar), CH4 (tetrahedral), and H2S (V-shaped)
 Bond Polarity and Dipole Moments

SOLUTION

Cl2

non polar
molecule
Polar
molecule Non polar
molecule

Non polar Polar

molecule molecule
 The Localized Electron Bonding Model
• Assumes that a molecule is composed of atoms that are bound
together by using atomic orbitals to share electron pairs.

• Electron pairs in the molecule are assumed to be localized on a

particular atom or in the space between two atoms. Those pairs of
electrons localized on an atom are called lone pairs, and those
found in the space between the atoms are called bonding pairs.

The LE model has three parts:

- Decsription of the valence electron arrangement in the molecule
using Lewis structures.
- Prediction of the geometry of the molecule (VSEPR)
- Description the types of atomic orbitals used by the atoms to share
electrons or hold lone pairs.
 Lewis Structures

• The Lewis structure of a molecule shows how the

valence electrons are arranged among the atoms in
the molecule.

• The most important requirement for the formation

of a stable compound is that the atoms achieve
noble gas electron configuration.
Noble Gas Electron Configuration – Octet Rule
Noble gas have 8 electrons on the valence shell except He (2
electrons). They have a stable configuration at the ground state.

2He (Helium) : 1s2 ⇒ 2 valence electrons

10Ne (Neon) : 1s2 / 2s2 2p6 ⇒ 8 valence electrons

18Ar (Argon) : 1s2 2s2 2p6 / 3s2 3p6 ⇒ 8 valence electrons

54Xe (Xenon) : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 / 5s2 5p6 ⇒ 8
valence electrons

The Octet is reached by gaining, loosing or sharing one or many

valence electrons
 Noble Gas Electron Configuration – Octet Rule

a) Elements of groups I and II : loosing 1 or 2 electrons to satisfy

the octet rule
-e-
Na : 1s 2 2s2 2p6 / 3s1 Na+ : 1s2 2s2 2p6 ( or [Ne] )
11

b) Elements of groups VI and VII : gaining 1 or 2 electrons to

satisfy the octet rule
+e-
17Cl : 1s2 2s2 2p6 / 3s2 3p5 Cl- :1s2 2s2 2p6/3s2 3p6 (or [Ar])
 Lewis Structures
• Hydrogen follows the duet rule when it forms
a stable molecule.

Two hydrogen atoms each with one electron

combine to form the H2 molecule.

By sharing electrons, each hydrogen in H2, in

effect, has two electrons; that is each
hydrogen has filled valence shell.
 Lewis Structures

• Helium does not form bonds because its valence

orbital is already filled; it is a noble gas.
He:

• The second-row nonmetals carbon through

fluorine form stable molecules when they are
surrounded by 8 electrons to fill the valence 2s
and 2p orbitals (octet rule).
 Lewis Structures

Each fluorine atom in F2 is surrounded by eight

electrons, two of which are shared with the other
atom. This is a bonding pair of electrons.
Each fluorine atom also has three pairs of electrons
not involved in bonding. These are the lone pairs.
Lewis Structures
 Lewis Structures
Consider the water molecule:
1) We sum the valence electrons for H2O:

2) Using a pair of electrons per bond, we draw in the two

O–H single bonds.
H–O–H

note that a line instead of a pair of dots is used to

indicate each pair of bonding electrons.
 Lewis Structures
3) We distribute the remaining electrons to achieve a noble gas
electron configuration for each atom.

since four electrons have been used in forming the two bonds,
four electrons (8-4) remain to be distributed.

hydrogen is satisfied with two electrons but oxygen needs eight

electrons to have a noble gas configuration.

→ Thus the remaining four electrons are added to oxygen as

two lone pairs.
 Lewis Structures

Consider CO2:

1) Valence electrons:

2) After forming a bond between the carbon and each oxygen

O–C–O
the remaining electrons (16 – 4) = 12 electrons
→ 6 pairs of electrons to distribute
 Lewis Structures

Suppose we try 3 pairs on each oxygen to give:

Is this correct?
Check the octet rule for each atom.
Each oxygen atom has 8 electrons,
but the carbon has only 4

=> This cannot be the correct Lewis structure.

 Lewis Structures
Suppose there are 2 shared pairs between the
carbon and each oxygen:

Electrons left (16 – 8) = 8 → four lone pairs placed

on the oxygens.

Now each atom is surrounded by 8 electrons.

 Lewis Structures
Consider CN-:
Summing the valence electrons:

Note that the negative charge means an extra

electron is present. (A positive charge means one less
electron is present).

Incorrect structure:

Correct structure:
 Lewis Structures

Example 13.6

Give the Lewis structure for each of the following

a. HF
b. N2
c. NH3
d. CH4
e. CF4
f. NO+
 Lewis Structures
SOLUTION
 Resonance

• If this structure accurately represents the bonding in NO3-,

there should be two types of N–O bonds observed in the
molecule: one shorter bond (the double bond) and two
identical longer ones (the two single bonds).

• However, experiments show that NO3- exhibits only one

type of N–O bond with a length and strength between
those expected for a single bond and a double bond.
 Resonance

• There are really three valid Lewis structures:

• The correct description of NO3- is given by the

superposition of all three.

• NO3- exists as an average of al three structures.

 Resonance
• Resonance occurs when more than one valid Lewis
structure can be written for a particular molecule.
• The structure of the molecule (or polyatomic ion) is given
by the average of these resonance structures.

• Different resonance structures of a compound are linked by

double-headed arrows (↔) that indicate that the actual
electronic structure is an average of those shown and not
that the molecule oscillates between the two structures.
Remember: the arrangement of the nuclei is the same, only the
placement of the electrons differ.
 Resonance

Example 13.7
Resonance

31
 Exceptions to the Octet Rule

• The rules we have used for Lewis structures

apply to most molecules.
• However, some exceptions are inevitable.
• Boron, for example, tends to form compounds
in which the boron atom has fewer than eight
electrons around it.
 Exceptions to the Octet Rule
• Some atoms exceed the octet rule. This
behavior is observed only for those elements
in Period 3 of the periodic table and beyond.

• Example is SF6:
6 + 6(7) = 48 electrons
sulfur exceeds the octet rule

The empty 3d orbitals on S can accommodate

extra electrons.
 Exceptions to the Octet Rule
• Another example is the triiodide ion I3-:

When it is necessary to exceed the octet rule for one of

several third-row (or higher) elements, assume that
the extra electrons should be placed on the central
atom.
 Exceptions to the Octet Rule

Example 13.8

Write the Lewis structure for PCl5

 Exceptions to the Octet Rule
SOLUTION

1- Sum the valence electrons.

5 + 5(7) = 40 electrons
2- Indicate single bonds between bound atoms.

3- Distribute the remaining electrons to satisfy the

octet rule.
 Exceptions to the Octet Rule

Example 13.9
Exceptions to the Octet Rule
Exceptions to the Octet Rule
 Formal Charge

Molecules of polyatomic ions containing atoms that can exceed

the octet rule often have many nonequivalent Lewis structures.

The formal charge can be used to evaluate Lewis structures.

An arithmetic formula for calculating formal charge.

Formal charge =
number of valence number of
electrons on the – valence electrons assigned to
free atom the atom in the molecule
 Formal Charge

To compute the number of valence electrons

assigned to the atom in the molecule:
1)Lone pair electrons belong entirely to the
atom in question
2) Shared electrons are divided equally between
the two sharing atoms

(valence electrons)assigned = (number of lone pair

electrons) + ½ (number of shared electrons)
 Formal Charge

One possible structure of SO42-:

Formal Charge
 Formal Charge
A second possible Lewis structure of SO42- is:

44
Formal Charge
 Formal Charge
To evaluate Lewis structures:

1. Atoms in molecules try to achieve formal charges as

close to zero as possible.

2. Structures that have the more negative formal charge

on the more electronegative atom are more stable

For SO42-, the structure with two double bonds is

preferred, it has lower formal charges and the -1 formal
charges are on the electronegative oxygen atoms.
 Formal Charge

Example 13.10

Give possible Lewis structures for XeO3, an explosive

compound of xenon. Determine the formal charges of
each atom in the various Lewis structures.
 Formal Charge

SOLUTION
 Molecular Structure: The VSEPR Model

Valence Shell Electron Pair Repulsion (VSEPR model) is

important to predict the geometries of molecules formed from
nonmetals.

• The structure around a given atom is determined principally

by minimizing electron-pair repulsions.

• Thus, bonding and nonbonding pairs around a given atom

should be positioned as far apart as possible.

ABmEn
A : central atom m : number of B bonded to A
B : atom bonded to A E : free lone pair around A
n : number of free lone pairs around A
 Molecular Structure: The VSEPR Model

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central electron pairs Geometry
atom

linear linear
AB2 2 0
B B
 Molecular Structure: The VSEPR Model

The best arrangement (min

repulsion) places the pairs
on opposite sides of the
beryllium atom at 180
degrees from each other.
 Molecular Structure: The VSEPR Model
# of atoms # lone
Class bonded to pairs on Arrangement of Molecular
central atom central electron pairs Geometry
atom

AB2 2 0 linear linear

trigonal trigonal
planar planar

AB3 3 0
Molecular Structure: The VSEPR Model

The minimum repulsion is when the electron pairs are

farthest apart at angles of 120 degrees.
 Molecular Structure: The VSEPR Model
# of atoms # lone
Class bonded to pairs on Arrangement of Molecular
central atom central electron pairs Geometry
atom

trigonal trigonal
AB3 3 0
planar planar

trigonal
bent
planar

AB2E 2 1
 Molecular Structure: The VSEPR Model
# of atoms # lone
Arrangement of Molecular
Class bonded to pairs on
central atom central electron pairs Geometry
atom

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar

AB4 4 0 tetrahedral tetrahedral

 Molecular Structure: The VSEPR Model

The maximum possible separation of the four pairs around

the central atom, is when they are arranged tetrahedrally.
 Molecular Structure: The VSEPR Model
# of atoms # lone
Class bonded to pairs on Arrangement of Molecular
central atom central electron pairs Geometry
atom

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral pyramidal
 Molecular Structure: The VSEPR Model

Figure 13.16 - (a) The tetrahedral arrangement of electron pairs around the nitrogen
atom in the ammonia molecule. (b) Three of the electron pairs around nitrogen are
shared with hydrogen atoms, as shown, and the fourth is a lone pair. Although the
arrangement of electron pairs is tetrahedral, as in the methane molecule, the hydrogen
atoms in the ammonia molecule occupy only three corners of the tetrahedron. A lone
pair occupies the fourth corner. (c) Note that molecular geometry is trigonal pyramidal,
not tetrahedral.
 Molecular Structure: The VSEPR Model
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central electron pairs Geometry
atom

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

AB2E2 2 2 tetrahedral bent

O
H H
 Molecular Structure: The VSEPR Model

Figure 13.17 - (a) The tetrahedral arrangement of the four electron pairs around
oxygen in the water molecule. (b) Two of the electron pairs are shared between
oxygen and the hydrogen atoms, and two are lone pairs. (c) The V-shaped
molecular structure of the water molecule.
 Molecular Structure: The VSEPR Model
A bonding pair is shared between two nuclei, and the electrons are
relatively confined between the two nuclei, however a lone pair is
localized on only one nucleus.

Lone pairs require more space than bonding pairs, as the number
of lone pairs increases, the bonding pairs are increasingly
squeezed together resulting in smaller bond angles.
Molecular Structure: The VSEPR Model
 Molecular Structure: The VSEPR Model
# of atoms # lone
Class bonded to pairs on Arrangement of Molecular
central atom central electron pairs Geometry
atom
AB2 2 0 linear linear
trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
 Molecular Structure: The VSEPR Model
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central electron pairs Geometry
atom

trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal See-Saw
AB4E 4 1
bipyramidal (distorted
tetrahedron)
 Molecular Structure: The VSEPR Model
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central electron pairs Geometry
atom

trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal See-Saw
AB4E 4 1
bipyramidal
trigonal
AB3E2 3 2 T-shaped
bipyramidal
F

F Cl

F
 Molecular Structure: The VSEPR Model
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central electron pairs Geometry
atom
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal See-Saw
AB4E 4 1
bipyramidal
trigonal
AB3E2 3 2 T-shaped
bipyramidal
trigonal
AB2E3 2 3 linear
bipyramidal
I

I
I3- I
Molecular Structure: The VSEPR Model
 Molecular Structure: The VSEPR Model
# lone
# of atoms pairs on
Class bonded to central Arrangement of Molecular
central atom atom electron pairs Geometry
AB2 2 0 linear linear
trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
AB6 6 0 octahedral octahedral
Molecular Structure: The VSEPR Model
 Molecular Structure: The VSEPR Model
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central electron pairs Geometry
atom

AB6 6 0 octahedral octahedral

square
AB5E 5 1 octahedral
pyramidal
F
F F
Br
F F
 Molecular Structure: The VSEPR Model
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central electron pairs Geometry
atom

AB6 6 0 octahedral octahedral

square
AB5E 5 1 octahedral
pyramidal
square
AB4E2 4 2 octahedral
planar
F F
Xe
F F
Molecular Structure: The VSEPR Model
 Molecular Structure: The VSEPR Model

Example 13.12

When phosphorus reacts with excess chlorine gas, the

compound phosphorus pentachloride (PCl5) is formed. In the
gaseous and liquid states, this substance consists of PCl5
molecules, but in the solid state, it consists of a 1:1 mixture
of PCl4+ and PCl6- ions. Predict the geometric structures of
PCl5, PCl4+, and PCl6-.
 Molecular Structure: The VSEPR Model
SOLUTION

PCl5

PCl4+
 Molecular Structure: The VSEPR Model

SOLUTION

PCl6-
 Molecular Structure: The VSEPR Model

Example 13.13

Because the noble gases have filled s and p valence orbitals,

they are not expected to be chemically reactive. In fact, for
many years these elements were called inert gases because
of this supposed inability to form any compounds. However,
in the early 1960s, several compounds of krypton, xenon, and
radon were synthesized. For example, a team at the Argonne
National Laboratory produced the stable colorless compound
xenon tetrafluoride (XeF4). Predict its structure and
determine whether it has a dipole moment.
 Molecular Structure: The VSEPR Model
SOLUTION

6 pairs of electrons octahedral arrangement

 Molecular Structure: The VSEPR Model
SOLUTION

Octahedral arrangement of electron pairs but square planar structure

 Molecular Structure: The VSEPR Model
SOLUTION

Although Xe-F are polar bonds, XeF4 has no dipole moment.

 The VSEPR Model and Multiple Bonds
Multiple bonds should be counted as one effective pair.

When a molecule exhibits resonance, any one of the

resonance structures can be used to predict the molecular
structure using the VSEPR model.

Trigonal Planar
 The VSEPR Model and Multiple Bonds

Example 13.14

Predict the molecular structure of the sulfur dioxide

molecule. Is this molecule expected to have a dipole
moment?
 The VSEPR Model and Multiple Bonds

SOLUTION

The Lewis structure of SO2 molecule has 18 valence electrons.

Three effective pairs around the sulfur yield a trigonal planar

arrangement and a V-shaped geometry

Since the molecule is V-shaped, the polar bonds do not cancel

 The VSEPR Model
The following rules are helpful in using the VSEPR model to predict
molecular structure.
1. Determine the Lewis structure(s) for the molecule.
2. For molecules with resonance structures, use any of the
structures to predict molecular structure.
3. Sum the electron pairs around the central atom.
4. When counting pairs, count each multiple bond as single
effective pair.
5. Determine the arrangement of the pairs that minimizes
electron-pair repulsions. These arrangements are shown in
Table 13.8.
6. Lone pairs required more space than bonding pairs. Choose an
arrangement that gives the lone pairs as much room as
possible, although it appears that an angle of at least 120
degrees may produce distortions from the idealized structure.
 HOMEWORK

Chap.13: 57-60-79-88-92-99
57
60
 79
Draw Lewis structures that obey the octet rule for the
following species. Assign the formal charge to each
central atom.
a) POCl3
b) SO42-
c) ClO4-
d) PO43-
e) SO2Cl2
f) XeO4
g) ClO3-
h) NO43-
88
92
 99

Draw Lewis structures, predict the molecular

structures and indicate which of the following
molecules have net dipole moments.
a) OCl2, KrF2, BeH2, SO2
b) SO3, NF3, IF3
c) CF4, SeF4, KrF4
d) IF5, AsF5