10

Chemical Bonding 2: Modern Theories

of Chemical Bonding

............................................................................

10.1 VSPER Theory: Molecular Geometry and the Shapes of Molecules

As discussed in Chapter 9, Lewis structures can account for the formulas of covalent compounds
by showing the number and types of bonds between atoms. However, Lewis structures alone do
not indicate the geometry or shapes of molecules or polyatomic ions.
The Valence Shell Electron Pair Repulsion (VSEPR) theory fills this lack and provides a
simple method for predicting the shape or geometry of small molecules and molecular ions.

10.1.1 VSEPR theory

VSEPR theory is a model first proposed by Sidgwick and Powell in 1940 and developed by
Gillespie and Nyholm in 1957. The premise of the VSEPR model is that the valence electron
groups or pairs surrounding the central atom of a molecule will mutually repel each other.
Consequently, the molecule will adopt a spatial arrangement that minimizes this repulsion, thus
determining the shape of the molecule or molecular ion.

10.1.2 Assumptions of the VSEPR theory

• The least electronegative atom in a polyatomic molecule (i.e. one consisting of three or
more atoms) is identified as the central atom to which all other atoms in the molecule are
bonded.
• For polyatomic molecules with more than one central atom (e.g. acetone, CH3 COCH3 ,
with three central atoms), the VSEPR model assigns an individual geometry to each central
atom.
• The geometry or shape of the molecule is determined by the total number of valence shell
electron pairs or electron groups around the central atom.
• Electron pairs directly involved in connecting the atoms in a molecule are called bonding
pairs. In multiple bonding (double and triple bonds), more than one pair of electrons may
bind any two atoms together.
• Some atoms in a molecule may also possess lone pairs—nonbonded pairs of electrons not
involved in bonding.

Chemistry in Quantitative Language: Fundamentals of General Chemistry Calculations. Second Edition.

Christopher O. Oriakhi, Oxford University Press. © Christopher O. Oriakhi 2021.
DOI: 10.1093/oso/9780198867784.003.0010
 Chemical Bonding 2: Modern Theories of Chemical Bonding 103

• The electron pairs tend to orient themselves in a way that minimizes the repulsion between
them, which maximizes the distance between them.
• Lone pairs occupy more space than bonding electron pairs, and double or triple bonds
occupy more space than single bonds.
• Repulsive forces decrease rapidly with increasing inter-pair angle. Forces are greatest at
90o , much weaker at 120o , and very weak at 180o .
• Where resonance occurs, the VSEPR theory can be applied to each resonance structure of
a molecule.
• After identifying the basic shape of a molecule, adjustments must be made to account for
the differences in electrostatic repulsion between bonding regions and nonbonded electron
pairs. Repulsions follow the order:
Lone pair–lone pair > Lone pair–bonding pair > Bonding pair–bonding pair

10.2 VSEPR Theory: Predicting Electron Group Geometry and Molecular Shape with
the VSEPR Model

1. Draw the Lewis structure of the molecule or polyatomic ion (for molecules with resonance
structures, use any of the structural forms to predict the molecular structure).

Table 10.1 Electron geometries around an atom yielding minimum repulsion

Number of electron Arrangement of electron Electron group
groups groups geometry Bond angle
2 A Linear 180o
3 Trigonal planar 120o

4 Tetrahedral 109.5o

5 Trigonal bipyramidal 120o Equatorial, 90o axial

A

6 Octahedral 90o

A
104 Chemistry in Quantitative Language

2. Count the number of electron groups (lone pairs and bonds) around the central atom.
3. Identify the electron group geometry based on the total number of electron groups as
linear, trigonal planar, tetrahedral, trigonal bipyramidal, or octahedral. Use Table 10.1 and
Table 10.2 as guides.
4. Use the angular arrangement of the bonded atoms to determine the molecular geometry.
If the central atom has no lone pairs, the molecular geometry is the same as the electron
group geometry. However, if one or more lone pairs exist on the central atom, the visible
molecular geometry will be different than the electron geometry.

10.2.1 Electron group geometries

The central atoms in most molecules have 2, 3, 4, 5, or 6 electron pairs or groups around them.
Table 10.1 shows the electron group geometry for each of these cases.

Table 10.2 Using VSEPR to predict shapes of AXE molecules

Molecule Electron Bonding Lone Electron Molecular Bond Example
class groups groups pairs geometry geometry angle
AX2 2 2 0 Linear Linear 180o BeCl2 , CO2
AX3 3 3 0 Trigonal planar Trigonal planar 120o BF3 , NO− 3
AX2 E 3 2 1 Trigonal planar Bent < 120o O3 , NO−2
AX4 4 4 0 Tetrahedral Tetrahedral 109.5o CH4 , SO2−4
AX3 E 4 3 1 Tetrahedral Trigonal pyramidal < 109.5o NH3 , AsCl3
AX2 E2 4 2 2 Tetrahedral Bent < 109.5o H2 O, SF2
AX5 5 5 0 Trigonal Trigonal 120◦ Eq PCl5 , AsF5
bipyramidal bipyramidal 90◦ Ax
AX4 E 5 4 1 Trigonal Seesaw < 120◦ Eq SF4 , SeH4
bipyramidal < 90◦ Ax
AX3 E2 5 3 2 Trigonal T-Shaped < 90◦ BrF3 , ICl3
bipyramidal
AX2 E3 5 2 3 Trigonal Linear 180◦ XeF2 , I−
3
bipyramidal
AX6 6 6 0 Octahedral Octahedral 90◦ SF6 , IOF5
AX5 E 6 5 1 Octahedral Square pyramidal < 90◦ BrF5 , XeOF4
AX4 E2 6 4 2 Octahedral Square planar 90◦ XeF4 , BrF−4
 Chemical Bonding 2: Modern Theories of Chemical Bonding 105

10.2.2 VSEPR theory: the AXE system

VSEPR theory uses the AXm En notation where m + n = total regions of electron density
(sometimes also called charge clouds). Here, A is the central atom; m is the total number of
ligands X, and n the number of lone pairs E.

Example 10.1

Predict the electron group geometry, molecular geometry, and bond angles of (a) PF3 and
(b) H2 S.

Solution

PF3 H2 S
Step 1: Draw the Lewis
H P H
structure for the molecule.
H H S H

Step 2: Determine the total The central P atom has four The central S atom has four
number of electron groups electron groups. electron groups.
around the central atom.
Step 3: Determine the number The central atom has three Two of the electron groups
of bonding groups and the bonding groups and one around S are bonding groups
number of lone pairs lone pair. and two are lone pairs.
around the central atom.
Step 4: Determine the Tetrahedral Tetrahedral
electron group geometry
based on the number of
electron groups. P S
H H H
H H
Step 5: Name the molecular Molecular geometry of PH3 Molecular geometry of H2 O
structure based on the is trigonal pyramidal is bent or angular (two
positions of the atoms and (three bonding groups and bonding groups and two
lone pairs. one lone pair). lone pairs).

P S
H H H H
H
Step 6: Bond angles 107o 104.5o
106 Chemistry in Quantitative Language

Example 10.2

Use the VSEPR model to predict the electron group geometry and molecular geometry,
including bond angles, of (a) XeF2 and (b) XeF4 .

Solution

XeF2 XeF4
Step 1: Draw the Lewis
structure for the molecule. F F
Xe
F Xe F F F

Step 2: Determine the total The central Xe atom has five The central Xe atom has six
number of electron groups electron groups. electron groups.
around the central atom.
Step 3: Determine the number The Xe atom has two bonding Four of the six electron groups
of bonding groups and the groups and three lone pairs. around Xe are bonding pairs
number of lone pairs and two are lone pairs.
around the central atom.
Step 4: Determine the Trigonal bipyramidal Octahedral
electron geometry based on
F
the number of electron F F
groups.
Xe Xe
F F
F
Step 5: Name the molecular Molecular geometry of XeF2 is Molecular geometry of XeF4 is
structure based on the linear (two bonding groups square planar (four bonding
positions of the atoms and and three lone pairs). groups and two lone pairs).
lone pairs.
F Xe F F F
Xe
F F
Step 6: Bond angles 180o 90o

Example 10.3

Draw the Lewis structures and predict the molecular shapes of (a) CS2− −
3 and (b) PCl6 .
 Chemical Bonding 2: Modern Theories of Chemical Bonding 107

Solution

CS2−
3 PCl−
6
Step 1: Draw the Lewis structure 2–
S Cl
for any resonance form of the
C Cl Cl
molecular ion. –
P
S S Cl Cl
Cl

Step 2: Determine the total The central C atom has three The central P atom has six
number of electron groups electron groups. electron groups.
around the central atom.
Step 3: Determine the number of The central atom C has three All six electron groups around P
bonding groups and the bonding groups and no lone are bonding groups.
number of lone pairs around pairs.
the central atom.
Step 4: Determine the electron Trigonal planar Octahedral
group geometry based on the 2–
S Cl
number of electron groups.
Cl Cl
C
P–
S S Cl Cl
Cl

Step 5: Name the molecular CS3 2− is trigonal planar (three Molecular geometry of PCl6 − is
structure based on the bonding groups and no lone octahedral.
positions of the atoms. pairs).
Cl
S 2– Cl Cl
P–
C
Cl Cl
S S Cl

Step 6: Bond angles 120o 90o

10.3 VSEPR Theory: Predicting Molecular Shape and Polarity

A polar molecule is one in which electrons or charges are shared unequally between covalently
bonded atoms, causing the molecule to have a net dipole moment. A nonpolar molecule, on
the other hand, has zero dipole moment, attributed to equal sharing of bonding electrons and
structural symmetry within the molecule.
Two factors determine whether a molecule is polar or nonpolar: the polarity of the bonds and
the shape or geometry of the molecule.
A diatomic molecule (such as Cl2 or HCl) has only one bond between the atoms. Consequently
the polarity of that bond determines the polarity of the molecule. If the bond is polar, the molecule
will be polar, and if the bond is nonpolar, the molecule is nonpolar by default.
108 Chemistry in Quantitative Language

In polyatomic molecules having more than one bond, polarity is determined by both the
arrangement and polarity of the bonds. The presence of a polar bond is a necessary condition
for a molecule to have inherent polarity. However, a molecule can become nonpolar if the polar
bonds present are symmetrically arranged within the molecule or aligned exactly opposite to
each other, because the bond polarities will cancel, for example, CO2 . Because oxygen is more
electronegative than carbon, the bonds are polar, with electron density concentrated on the two
oxygen atoms. However, CO2 is linear, and the symmetrical arrangement of these polar bonds
allows their effects to cancel each other, leaving the molecule nonpolar, as shown.
𝛿– 𝛿+ 𝛿–
O C O

On the other hand, the linear molecules HCN and N2 O are polar because both are structurally
unsymmetrical, and both contain polar bonds.

10.3.1 Steps for predicting molecular polarity

1. Draw a reasonable Lewis structure and a correct geometrical representation for the
molecule.
2. Identify each bond as either polar or nonpolar using the magnitude of the electronegativity
difference. Use Table 9.1 as a guide.
3. Describe the polar bonds with arrows pointing toward the more electronegative elements.
Use the length of the arrow to show the relative polarities of the different bonds.
4. The molecule is considered nonpolar if:
• It contains no polar bonds.
• The central atom has no lone pairs, and all the ligands or terminal atoms bonded to it
are the same, as in linear, trigonal planar, tetrahedral, trigonal bipyramidal, octahedral,
and square planar geometries.
• The molecular structure is symmetrical and the vector arrows showing the relative
polarities are of equal length.
5. The molecule is polar if:
• The central atom has at least one polar bond or lone pair.
• The multiple polar bonds or lone pairs in the molecule are arranged in a way that the
dipole moment does not cancel out.
• It fails to meet all the requirements for being nonpolar.

Example 10.4

Predict whether each of the following molecules is polar or nonpolar.

(a) BF3
(b) OF2
(c) SF6
(d) HCN
 Chemical Bonding 2: Modern Theories of Chemical Bonding 109

Solution

BF3 OF2 SF6 HCN

Step 1: Draw the H C N
F O F
Lewis structure
F F F F
for the S
Linear
B
molecule and F F F F
determine the Bent
F
molecular Trigonal planar
geometry. Octahedral

Steps 2 & 3: F
F
Determine the F H C N
F
polarity of the S
B O F
F
bonds. F F F F HCN contains a
F
polar bond
The three B–F The two O–F The six S–F H–C (χ =
bonds are polar bonds (χ = bonds are polar 0.4) and C–N
(χ = 2.0). 0.5) are polar. (χ = 1.5). (χ = 0.5).
Steps 4 & 5: All groups on B are OF2 has a bent All groups on S Asymmetric
Determine polarity the same; no lone shape, so the are the same; linear
of the molecule. pair on B; BF3 is distribution of no lone pair on geometry.
symmetrical. the polar S; SF6 is Bond vectors
Vectors cancel out bonds is symmetrical. do not cancel
due to symmetry. asymmetrical. Vectors cancel out. HCN is
BF3 is nonpolar. OF2 is polar. out. Therefore polar.
SF6 is
nonpolar.

Example 10.5

Draw Lewis structures for the following molecules and predict the polarity of each.
(a) CF2 Cl2 and CCl4
(b) SO2 and SO3
(c) CS2 and H2 S
(d) SF4 and IF5

Solution

(a) CF2 Cl2 and CCl4

The Lewis structures are:

F Cl

C and C
F Cl Cl Cl
Cl Cl