Bonding and Molecular

Geometry
CHM 171
SYLLABUS THEME 3
Prescribed Text Book:
Kotz, Treichel and Townsend 9th Ed.

NOTE: Do not use the text book method when doing the Lewis
Chapter 8 structures:
Listen attentively in class and watch the video on click-up

Do end of the chapter exercises:

5,11,15,19,21,25,37,43,37,47,61,75,77,77,78
 What is a chemical bond

A chemical bond is a lasting attraction between atoms that enables the formation
of chemical compounds.
The bond may result from
1. the electrostatic force of attraction between atoms with
opposite charges – ionic bond
2. or through the sharing of electrons - covalent bonds
Ionic bond Covalent bond
 Why do atoms bond and how do they bond?
Aim: Lower energy

Destination: (ns2np6) valence shell configuration – noble gas

behaviour - Stability

When atoms react, they tend to achieve an

Octet rule outer shell having eight electrons.

Main group atoms will

gain
loose or
share
electrons to obtain an octet
3
Ionic vs covalent bonding

4
 Ionic vs covalent bonding
Electronegativity, ∆E
A measure of the ability of an atom in a molecule to attract the shared electrons in a
covalent bond.
 Lewis symbols of atoms
A representation of electrons
in the valence shell, i.e. valence
electrons
Ionic bonding – Lewis structures
When sodium loses an electron
to form Na+, its effective size
decreases to about half.

When chlorine gains an electron

to produce the octet structure Cl-,
its size increases to almost
double.
 Covalent bonding-Lewis structures

H
x
H Hx H H H H2
Lewis dot Lewis dot Structural Chemical
symbol structured formula formula

Replace bonded
electrons with a
line

Are NB valence e’s Influence molecular shape

8
 Lewis structures and multiple bonds
Sometimes octet is achieved by using more than one bond – shared
electrons are more than 2.
Lewi Structure for Covalent Compound
Write a Lewis structure for the ammonia
molecule.
Lone Pair

H N H  H–N–H

–
H
Bond Pair
H

Orbitals with unpaired electrons

overlap  Covalent bonds
10
 Coordinate/ Dative Covalent Bonds
Covalent bond where the 2 electrons involved in the bond
come from only one atom
H H
H N + H Cl H N H Cl
H H
HCl bond breaks with Coordinate covalent bond
Cl taking both electrons of the bond

Lone pair used to form coordinate covalent bond.

11
 Coordinate/ Dative Covalent Bonds

BF3 is described as being electron deficient

The lone pair on the nitrogen of an ammonia

molecule can be used to overcome that deficiency,
and a compound is formed involving a co-ordinate
bond
 Multiple Covalent Bonds
1. Single Bond – Sharing of one pair of e-‘s, sigma bond
E.g. H2
H + H H H H H
2. Double Bond – composed of 1 sigma & 1 pi bond
Eg. O2
O + O O O O O

3. Triple bond – composed of 1 sigma & 2 pi bonds

Eg. N2
N + N N N N N

Lone Pair – Pair of e-’s that are not involved in bonding

Bond Pair – Pair of e-’s that overlap to form a bond 13
 Polar Covalent Bonds
Polar covalent bond
Bond that involves the unequal sharing of bonding electrons

 H ••F 

∆EN = 4.0-2.1 = 1.9

Nonpolar covalent bond

Bond that involves the equal sharing of bonding e-‘s;

14
 Electronegativity (EN)
A measure of the electron-attracting power of a bonded
atom

• the atom’s ability to attract electrons of a bond

towards itself

• Metals have low electronegativity, & nonmetals

have high electronegativity

Difference in EN (EN)
- indicates the degree of bond polarity 15
 Electronegativity (EN)
EN: ↑ across period (left to right) on Periodic Table
EN: ↓ down group (top to bottom) on Periodic Table
• Larger difference = more polar bond
• negative end toward more electronegative atom

Indicates direction
of polarity with
arrow head towards
+ -  Negative end

16
 Exercise:
• Arrange elements in the following sets in order of
increasing electronegativity:
a. As, Br, Se, I
b. B, C, Al, Si
c. Ge, As, P, Sn
d. Li, Rb, Be, Sr

17
 Electronegativity & Bond type

Classification of chemical compounds:

EN  2  Ionic

EN ˂ 2 & > 0.4  Polar covalent

EN = 0-0.4  Nonpolar covalent

18
 Writing Lewis Structures
1. Count the total number of valence e-‘s(Ve) in the
structure, for ions: add anion charge; OR subtract
cation charge;

2. Identify the central atom

3. Draw skeletal structure, without bonds

4. Use single bonds to join the atoms, (2 e-‘s/bond);
subtract these Be from the total Ve;
5. Place Lone pairs(LPe) on the terminal atoms to satisfy
the Octet rule; subtract LPe’s from remaining Ve; place
any remaining Ve on the central atom.
6. If the Octet rule for the central atom is NOT satisfied,
form multiple covalent bonds by converting LP’s on
the terminal atoms into bond pairs. 19
 Exercise
Question:
Write a plausible Lewis structure for nitrogen
trifluoride, NF3.

Solution:
Step 1. Count the total number of valence electrons:
F – group 17 .: 7 valence electrons
N – group 15 .: 5 valence electrons

Total Ve = (3 x F) + (1 x N)
= (3 x 7) + (1 x 5)
= 26 e-
Step 2. Identify the central atom:
ENN = 3.0, and ENF = 4.0
.: N is the central atom
20
 Exercise cont…
Step 3. Draw a skeletal structure:

F N F
F
Step 4. Subtract 2 electrons for each bond formed
from the total Ve:
Remaining electrons = 26 – (3 bonds x 2 e-/bond)
= 26 – 6
= 20 e-
21
 Exercise cont…
Step 5. Complete the octets for the terminal atoms,
by placing lone pairs on the atoms:

F N F
F
Step 6. Subtract the Lone pair electrons from the
Remaining electrons
Rem. e-’s = 20 – 3 x (3 Lone pairs x 2 e-/LP)
= 20 – 18
= 2 e-
22
 Exercise cont…
Step 7. Place any remaining electrons on the
central atom, and check that the Octet rule
is satisfied for ALL atoms

Rem. e-’s = 2 e-

F N F
F

Octet rule for all atoms is satisfied!

23
 Example 10.6
Question:
Write a plausible Lewis structure for cyanogen, C2N2, a
poisonous gas used as a fumigant and rocket
propellant.
Solution:
Step 1. Count the total number of valence electrons:
C – group 14 .: 4 valence electrons
N – group 15 .: 5 valence electrons

Total Ve =2xC+2xN
= (2 x 4) + (2 x 5)
= 18 e-
Step 2. Identify the central atom:
ENC = 2.5, and ENN = 3.0
.: C is the central atom 24
 Example 10.6 cont…
Step 3. Draw a skeletal structure:

N–C–C–N
Step 4. Subtract 2 electrons for each bond formed
from the total Ve:
Remaining electrons = 18 – (3 bonds x 2 e-/bond)
= 18 – 6
= 12 e-

Step 5. Complete the octets for the terminal atoms,

by placing lone pairs on the atoms:

N C C N 25
25
 Example 10.6 cont…
Step 6. Subtract the Lone pair electrons from the
Remaining electrons
Rem. e-’s = 12 – 2 x (3 Lone pairs x 2 e-/LP)
= 12 – 12
= 0 e-

Step 7. The central atoms, only have the 4 Be, so

need another 4 each, .: move LPe to form
multiple bonds

N C C N N C C N
26
26
 Exercise cont..
• Write acceptable Lewis structures for:
1. H2NOH
2. HOClO2
3. O2SCl2
4. H2CO
5. FNO
6. BrO3-
7. C2H2

27
 Example 10.7
Question:
Write the Lewis structure for the nitronium ion, NO2+.

Solution:
Step 1. Count the total number of valence electrons:
N – group 15 .: 5 valence electrons
O – group 16 .: 6 valence electrons

Total Ve = 1 x N + 2 x O – 1e (charge)
= (1 x 5) + (2 x 6) – 1e
= 16 e-
Step 2. Identify the central atom:
ENN = 3.0, and ENO = 3.5

.: N is the central atom 28

28
 Example 10.7 cont…
Step 3. Draw a skeletal structure:

O–N–O

Step 4. Subtract 2 electrons for each bond formed

from the total Ve:
Remaining electrons = 16 – (2 bonds x 2 e-/bond)
= 16 – 4
= 12 e-

29
29
 Example 10.7 cont…
Step 5. Complete the octets for the terminal atoms,
by placing lone pairs on the atoms:

O N O
Step 6. Subtract the Lone pair electrons from the
Remaining electrons

Rem. e-’s = 12 – 2 x (3 Lone pairs x 2 e-/LP)

= 12 – 12
= 0 e-

30
 Example 10.7 cont…
Step 7. The central atom, N, has only the 4 Be, so
need another 4, .: move 2 LP’s to form
multiple bonds.
There are 2 possible ways:

O N O OR O N O
Which result in 2 plausible products:

O N O OR O N O
31
 Formal Charge
Describes the electron distribution of the valence
electrons on each atom, and is calculated for EACH
atom in a molecule.

FC = Ve‘s in a Free Atom – LPe –½Be

FC= # of valence electrons of an atom – (# of lone electrons around the atom + # of bonds
around the atom)
Where:
Ve‘s in a Free Atom = “group number”
LPe – the number of lone pair electrons
Be – the number of electrons involved in bonding
32
 Stability of Lewis Structures
Electron distribution = Formal Charge

• The smaller the Formal Charge  the more stable

the molecule

• Negative FC’s on the most Electronegative atom; &

positive FC’s on least EN atom

• The sum of the FC’s (FC) must equal the charge

on molecule/ion 33
 Exercise
Question:
Calculate the formal charges on the atoms in NO2+

O N O
O1 O2
Calculate the formal charge on each atom in the ion:
FC = Ve – LPe – ½ Be
O1 : FC = 6 Ve – 2 LPe – ½ (6 Be) = +1
N: FC = 5 Ve – 0 LPe – ½ (8 Be) = +1
O2 : FC = 6 Ve – 6 LPe – ½ (2 Be) = –1
+1 +1 -1
O N O
Note: the sum of the FC’s = the charge on the ion 34
 Exercise cont..
Question:
Calculate the formal charges on the atoms in NO2+

O N O
O1 O2
Calculate the formal charge on each atom in the ion:
FC = Ve – LPe – ½ Be
O1 : FC = 6 Ve – 4 LPe – ½ (4 Be) = 0
N: FC = 5 Ve – 0 LPe – ½ (8 Be) = +1
O2 : FC = 6 Ve – 4 LPe – ½ (4 Be) = 0
0 +1 0

Note: the sum of the FC’s = the charge on the ion 35

 Stability of Lewis Structures
Question:
Which of the below structures is more stable, .: more plausible?
+1 +1 -1 0 +1 0
O N O OR O N O
A B

Calculate the formal charges:

FC = Ve – LPe – ½ Be

Answer:
Structure B is more stable as there are smaller FC’s
in the structure:
B (0,1,0) compared to A (1,1,-1) 36
Deciding the most stable Lewis structure with formal charges
3 guidelines involving FC: FC= # of valence electrons of an tom – (# of
1. A molecular structure in which all FC bonds around the atom + # of lone electrons
are zero is preferred to one in which around the atom)
some FC are not zero. -1 -1 Add # bond
and # lone
-1 +1 -1 0 0 -1 together
or
2. If the Lewis structure must have and subtract
from the ve
nonzero FC, the arrangement with -1
the smallest nonzero FC is -1
preferred. Atoms ve- #Bonds #Lone e FC
P 5 4 0 +1
-O 6 1 6 -1
3. When we must choose among
several Lewis structures with similar Atoms ve- Bonds Lone e FC
distributions of FC, the structure with P 5 5 0 0
the negative FC on the more -O 6 1 6 -1
electronegative atoms is preferred. =O 6 2 4 0
 Deciding the most stable Lewis structure with formal charges

preferred because it has only formal

charges of zero (Guideline 1).

The structure with a terminal oxygen

atom is preferred.(Guideline 2)

The first arrangement of atoms is preferred because

it has the lowest number of atoms with nonzero
formal charges (Guideline 2).

Secondly, it places the least electronegative atom in

the centre, an (Guideline 3).
 Resonance
Cannot write a SINGLE Lewis structure that represents a
molecule accurately.
Eg. Ozone, O3

O O O O O O
Resonance hybrids – two plausible Lewis structures can be drawn for O3.
These structures are equivalent,
BUT neither is correct!
Resonance structure – a “summary” structure showing that the
electrons of the double bond are delocalized.

O O O
39
 Resonance
Question:
Draw the plausible Lewis structures for CO32- ion.

Solution: After assigning all the valence electrons:

1 2
O C O
3
O
.: move lone pair electrons to form a double bond – 3 choices
.: 3 Resonance Hybrids!
2- 2- 2-
O C O O C O O C O
O O O

40
Question:
Write the Lewis structure for the acetate anion, CH3COO-.

41
 Exceptions to the Octet Rule

There are 3 exceptions to the Octet rule:

1. Odd – Electron Species

2. Incomplete Octet

3. Expanded Octets

42
 Odd – Electron Species
These are species that have an unpaired electron in their
structure.
Eg. Nitrogen oxide, NO, has 11 valence electrons:

N O
Unpaired e-  unstable compounds .: very reactive.
Compounds will bond with itself, dimerise, to pair e’s
E.g. NO2 molecules will bond together
O O O O
N N N N
O O O O 43
 Incomplete Octet
Compounds of Groups 1, 2 and 13 (3), which do not have many
valence electrons.
E.g. BF3 Boron is in group 13, and so only has 3 electrons available for
forming bonds.

F–B–F

–
F
Form coordinate covalent bond with a compound that has a lone pair of
electrons.
H F H F

–
–

H – N: B–F H–N–B–F

–
–

H F H F
NH3 donates its lone pair to form coordinate covalent bond
Expanded Octet The Lewis structures where the central atom
ends up with more than an octet,
Elements ≥ n = 3 can use their d orbitals for bonding
E.g. Phosphorus and sulfur:
P [Ne] 3s 2 3p 3  [Ne] 3s 1 3p 3 3d 1
.: 5 unpaired electron .: 5 bonds

S [Ne] 3s 2 3p 4  [Ne] 3s 1 3p 3 3d 2
.: 6 unpaired electron .: 6 bonds

F F F
F F
P S
F F F F
F F
PF5 SF6
 Expanded Octet
Sulfur trioxide, SO3
Plausible Lewis structure:
Ve = 24 e-
-Be -6 -1 +2 -1
= 18 e- O S O 3 resonance structures
-LPe - 18
= 0
0O

BUT Sulfur has n = 3, .: can have an expanded octet!

0 0 0 The more stable structure on
O S O the basis of formal charges

O
0
Decide which is more stable on the basis of formal charges
46
 Expanded Octet
Sulfur dioxide, SO2 2 resonance structures
Plausible Lewis structure: 0 +1 -1
Ve = 18 e-
-Be -4 OR
= 14 e-
-LPe - 12
-1 +1 0
= 2

BUT Sulfur has n = 3, .: can have an expanded octet!

The more
0 0 0 stable
&
structure on
the basis of
formal charges
Decide which is more stable on the basis of formal charges
The resonance structures are best because it satisfies the
47

octet rule but structure 3 is stable based on formal charges

Expanded Octet It is an acid that:
1. contains oxygen
Lewis structure of oxoacids
2. contains at least one other element
3. has at least one hydrogen atom bound
to oxygen
4. forms an ion by the loss of one or more
protons

H will never bond to the oxygen

+ 3H+ → with double bond and will never
bond to the central atom.
Expanded Octet
Sulfuric acid, H2SO4

Plausible Lewis structures:

49
 Expanded Octet
Sulfuric acid, H2SO4

Plausible Lewis structures: 0

-1
O O
0 0 +2 0 0 0 0 0 0
0
H O S O H H O S O H
O O
-1 0
A B

Based on formal charges, structure B is more stable

50
 Isoelectronic species
NO+; N2, CO and CN- are isoelectronic species.

Each has 2 atoms and the same number of electrons (10).

Therefore they will all have the same Lewis structures.

Write the Lewis structure of the other 2.

Exercise:
• Draw the Lewis structures for each of the following
molecules/ ions. Which do not obey the octet rule?
1. CO2
2. IO3-
3. BH3
4. BF4-
5. XeF2

52
Drawing of molecules using the Lewis structure
NO2F PCl5 COCl2
PF2O+ SF6 ICl4-
 Violation of the octet

Obey octet Obey octet Deficient octet Odd number e- octet

Expansion occurs in
expanded octet
expanded octet expanded octet atoms in P3 and
above.
12 electrons should
be the maximum of
electrons allowed
around the central
atom
Relationship between bond order, bond length and bond energy
Bond order is the number of chemical bonds between a pair of atoms.

Bond length is the average distance between nuclei of two bonded atoms in a
molecule. Related to the atomic size. The smaller the atom, the shorter the bond.
Bond energy is the energy required to break apart a mole of molecules into its
component atoms.

• The stronger the bond, the higher the

bond enthalpy, the shorter the bond.
• Bond breaking (reactant side) is always
+ (endothermic) - energy needed.
• Bond formation (product side) – is
always (exothermic) – energy given off.
• Lattice energy –the breaking of bond in
an ionic structures.
 Calculating bond energy – Self study p328
Use the bond energies to find the ∆H° of the reaction:
H2(g) + Br2(g) 2HBr(g)

H–H + Br–Br 2H–Br

Add on the reactant side
1 x H-H bonds = 436 kJ/mol
1 x Br-Br bond = 193 kJ/mol

Add on the product side

2 x H-Br bonds = 2 x 366 kJ/mol

= (436 kJ/mol + 193 kJ/mol) - (2 x 366 kJ/mol)

= (629 - 732) kJ/mol
= -103 kJ/mol [Exothermic reaction]
 Calculating bond energy - Self study p328
Use bond enthalpies to calculate the enthalpy change of the following reaction:

C2H5OH(g) + 3O2(g) 2CO2 + 3H2O(g)

Add on the reactant side
5 x H-C bonds = 5 x 413 kJ/mol
1 x C-C bond = 1 x 346 kJ/mol
1 x C-O bond = 1 x 358 kJ/mol
1 x O-H bond = 1 x 463 kJ/mol
346
3 x O=O bonds = 3 x 498 kJ/mol
463
Add on the product side
4 x C=O bond = 4 x 745 kJ/mol
6 x O-H bond = 6 x 463 kJ/mol
= (4731 kJ/mol) - (5782 kJ/mol)
= -1051 kJ/mol [Exothermic reaction]
 Calculating the bond energy/enthalpy - Self study p328
Use bond enthalpies to calculate the enthalpy change of the following reaction

Add on the reactant side:

6 x H-C bonds = 6 x 413 kJ
2 x C-C bond = 2 x 346 kJ
1 x C=O bond = 1 x 745 kJ
1 x H-H bond = 1x 436 kJ

Add on the product side

+ 7 x H-C bonds = 7 x 413 kJ
2 x C-C bond = 2 x 346 kJ
1 x C-O bond = 1 x 358 kJ
1 x O-H bond = 1 x 463 kJ

Ans: -53 kJ/mol

 Practice exercise - Self study p328
Use the bond energy values to calculate the enthalpy (heat) of reaction at 298 K for
the following reaction.
Br2(g) + 3F2(g)  2BrF3(g) Single bond dissociation enthalpy, kJ/mol
Br F
Br 191 197
F 159
– 𝟓𝟏𝟑 𝒌𝑱

Use the bond energy values to calculate the enthalpy (heat) for the following reaction.

+
-82 kJ/mol
 Practice exercises
Write resonance forms that describe the distribution of electrons in each of these
molecules or ions.
(a) selenium dioxide, OSeO
(b) nitrate ion, NO3−
(c) nitric acid, HNO3
(d) benzene, C6H6:

Toothpastes containing sodium hydrogen carbonate (sodium bicarbonate) and

hydrogen peroxide are widely used. Write Lewis structures for the hydrogen
carbonate ion and hydrogen peroxide molecule, with resonance forms where
appropriate.

Draw the structure of hydroxylamine, H3NO, and assign formal charges; look up the
structure. Is the actual structure consistent with the formal charges?
 Practice exercises
Draw the Lewis structure of each of the molecules listed below.
CH3+, NH2−, CH3−, NH4+, BF4−
In each case, use the method of calculating formal charge described to satisfy
yourself that the structures you have drawn do in fact carry the charges shown.

Give the formal charges for all non-hydrogen atoms in the following molecules:
BH4−, H2O, CH3O−
BH4− (B = −1);H2O (O = 0); CH3O− (C = 0, O = −1)
Valence Shell Electron Pair Repulsion Theory
(VSEPR)
Valence shell e- pairs (electron domains) keep as far
apart as possible to minimise the electron-electron
repulsion.
Most important factor in determining geometry is the
relative repulsion between electron pairs

Electron Group Geometry – arrangement of all electron pairs,

including both lone pairs(LP’s) & bonding pairs (Be’s)

Molecular Geometry – 3-Dimensional

arrangement of atoms – what you see
62
 Determining the Geometry of a Molecule

To apply VSEPR theory:

1. Draw a plausible Lewis structure

2. Determine the Electron Domain/Group Geometry

3. Determine the number of e- pairs, & write a formula (AXyEz)

4. Determine the Molecular geometry

63
 Electron Domains
• We can refer to the electron pairs as electron domains.

• A double or triple bond count as ONE electron domain

64
 Possibilities for Electron Group Geometries
Electronic and molecular geometries are based on
these 5 basic shapes
Number of Electron
Pairs/ Electron Domain Geometry Bond Angles
Bonding Domains
2 Linear 180o
3 Trigonal planar 120o
4 Tetrahedral 109.5o
5 Trigonal bipyramidal 90o, 120o, 180o
6 Octahedral 90o, 180o
65
66
 Drawing conventions 3D structures

Let the plane of the

paper pass through the H
central atom.
C
H
H H
Single line – bond in plane of paper

Solid wedge – bond in front of plane of paper

or ------ Dashed lines – behind the plane of the paper

Include the bond angle, the charge and the direction of the dipole moment (𝝁). 67
 Terminology
Basic VSEPR Formula:

AXyEz

Where: A – central atom

X – terminal atom
E – lone pairs on the central atom

Molecule adopts the shape that minimizes the electron pair

repulsion 68
69
70
Examples of VSEPR Formulae

4 electron domains 4 electron domains 4 electron domains

Electron Domain Electron Domain Electron Domain
Geometry - Geometry - Geometry -
Tetrahedral Tetrahedral Tetrahedral
Molecular Geometry Molecular Geometry Molecular Geometry
AX4 AX3E AX2E2
Tetrahedral Trigonal pyramidal Angular/bent
Bond angle 109.5o Bond angle 107o Bond angle 104.5o
No LPs 1LP - repulsion between 2BPs & 2LPs– repulsion
Angles between Hs LP and BPs between LPs greater
maximum Angle between Hs than repulsion between
decrease LP and BP
LP- Lone pair 71
BP- Bonding pair
The effect of non-bonding electrons on bond
angles
• Non-bonding pair occupy larger volume than
bonding pair:
 Bonding pair attracted by both nuclei

• Non-bonding pair exert greater repulsive forces on

adjacent electron domains: this compresses the
bond angles

72
The effect of multiple bonds on bond angles
• Electron domains for double and triple bonds exert
greater repulsive force on adjacent electron domains
than single bonds, therefore, they also affect bond
angles.

73
Molecular Geometry (learn!)

74
 Example
Question:
Predict the molecular geometry of the polyatomic anion, ICl4.

Cl
Cl I Cl
Cl

EDG - 6 electron domains Octahedral

MG - AX4E2 – Square planar

75
 Example
Question: Predict the molecular geometry of PCl5 and
SF6
F F F
F F
P S
F F F F
F F
EDG - 5 electron domains, – Trigonal bipyramidal
MG – AX5 – Trigonal bipyramidal

EDG - 6 electron domains, – Octahedral

MG – AX6 – Octahedral
76
Structures with Multiple Covalent Bonds
Treat double and triple bonds as single bonds.
E.g. CO2
O C O
EDG - 2 electron domains – Linear
MG – AX2 – Linear
Question: Predict the molecular geometry of SO2
(draw all Lewis structures)

Expanded octet

EDG - 3 electron domains – Trigonal planar

MG – AX2E – Angular or bent
Structures with More than One Central Atom
Determine the molecular geometry around each central
atom in H2SO4

Derive the VSEPR formula for Oxygen (1&2) & Sulfur:

O1&2: AX2E2 S: AX4
Look up the molecular geometry from the table:

O1&2: angular/bent S: tetrahedral 78

Summary
 General
# Regions Electron pair geometry Molecular geometry
Formula
AX2 2 Linear Linear

AX3 3 trigonal planar trigonal planar

AX2E1 3 trigonal planar bent

AX4 4 tetrahedral tetrahedral

AX3E1 4 tetrahedral trigonal pyramidal

AX2E2 4 tetrahedral bent

AX5 5 trigonal bipyramidal trigonal bipyramidal

AX4E1 5 trigonal bipyramidal seesaw

AX3E2 5 trigonal bipyramidal T-shaped

AX2E3 5 trigonal bipyramidal Linear

AX6 6 octahedral octahedral

AX5E1 6 octahedral square pyramidal

AX4E2 6 octahedral square planar

 Practise exercises
Draw the 3D structures and predict the molecular geometry of the following molecules,
ions and oxoacids. Show the effect of the lone pairs on central atom.

CS2 NO2F ClO3F HNO3 H2SO3

PCl3F2 IOF5 CH3CN H2PO4- HClO3

O3 XeF2 BrF5

PF2O+ CO32- ICl4-

NH4+ XeO64- AsO43-

 Polar bonds v/s polar molecules
Dipoles: Molecules that have a the separation of
charges within a molecule - slightly positive
charge on one end and a slightly negative charge
on the other.
• The polarity of the molecule is the sum of
all of the bond polarities in the molecule.

• Molecular polarity is dependent on bond

polarity and on the molecular geometry.

• If the atoms in the molecule are

symmetrical, the charges are balanced by
each other. The molecules are considered to
be nonpolar.

• However, if the molecule is asymmetrical, it

is considered to be polar.
 Polarity
“The tractor pull”
SNAP-Symmetrical Nonpolar - Asymmetrical Polar
If all the regions surrounding an atom are
similar in their electronegativity, the
molecule will be non-polar.
Nonpolar molecule can have polar bonds,
but the molecular geometry is symmetrical
allowing the bond dipoles to cancel each
other.
If the regions are different, then the
molecule will be polar.

A polar molecule results when a molecule

contains polar bonds in an unsymmetrical
arrangement.
 Molecular polarity examples
PF5 (Trgonal bipyramidal)
There is a shift in electron density from P to
F because F is more electronegative than P.
The bond moment pointing up is equal in
magnitude and opposite in direction to the
bond moment pointing down. These bond
moments cancel.
If we sum together two of the bond XeF2 (Linear)
moments in the trigonal plane, the resultant All 3 lone pairs will occupy the
moment is equal and opposite to the third equatorial regions will cancel each
bond moment in the trigonal plane. These other. The F atoms on the axial
two moments cancel. positions will cancel each other.
The molecule is nonpolar (the dipole The molecule is nonpolar (the dipole
moment is zero). moment is zero).
 Molecular polarity examples

SF6, XeF4
The Lewis structures of SF6 and XeF4 have 6
pairs of electrons around the central atom, the
electron pair arrangement about the central
atom is octahedral.
The molecular geometry of SF6 is octahedral,
but due to the lone pairs on Xe, the molecular
geometry of XeF4 is square planar.
Both are non polar.
 Practice examples
5. Draw one Lewis structure of ICℓ2O2–. Use different symbols for the valance electrons
of the different elements. Show all lone pairs. Do not use lines (dashes) for bonds.
6. Draw the Lewis dot structure of XeOF3-. Use different symbols for the valance
electrons of the central atom (e.g. dots) and terminal atoms (e.g. crosses). Show all
lone pairs. NB! Do not use lines (dashes) for bonds. Your drawing must clearly
show the positions of the electrons.
7. Draw three possible resonance structures for HNO3. Use structural formulas (use
lines for bonds) only. All valence electrons must be represented. Allocate formal
charges to all atoms. Which of your structures probably don’t exist? Motivate your
answer.
8. (a) Draw the perspective three-dimensional structural formula of CℓF5. Use lines,
wedges and broken lines (dashes) for bonds. Include: all valence electrons in your
structure, sizes of all bond angles, polarity of the molecule. (b) What is the
molecular geometry of this molecule?

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 Practise exercises

Draw the 3-D structures of the following molecules/ions and oxoacids.

Clearly indicate the direction of the dipole moment, the angle and the charge in the
structures.

1. BF3 2. I3– 3. NO2– 4. CℓF3

5. CℓFO3 6. XeOF4 7. NF3 8. IOF5

9. I3+ 10. BeCℓ2 11. OSF4 12. CℓF4–

13. SF4 13. NO2 15. H2PO4– 16. CℓSF5

 Exercise
Use the chlorine atom as central atom, other elements from the
periodic table, but not hydrogen and construct the following
species in i, ii and iii:
i. A polar compound with octahedral molecular geometry. Show
clearly the Lewis dot structure, the 3D Lewis line structure, the
direction of the dipole moment in the Lewis line structure as well
as bond angles.
ii. A cation with see-saw molecular geometry. Draw the Lewis line
structure and calculate the formal charge on chlorine.
iii.An anion with trigonal bipyramidal molecular geometry. Draw the
Lewis line structure and calculate the formal charge on chlorine.
 Practice examples

1. The structure of BrO3F is determined by gas phase electron diffraction. The

following bond lengths are measured: 158 pm and 171 pm. The measured bond
angles are: 103 and 115. The averaged single bond lengths are given in the table
in pm.
a.Suggest a structure that will fit the experimental data. Start with the Lewis dot
structure and complete the Lewis line structure with the data indicated on this
structure.
b.What is the molecular geometry of your structure? Averaged single bond
c.What is the bond order of BrF and BrO? lengths (pm)
Show the calculation thereof. H O F Br
d.Is this compound polar? If yes, indicate the direction H 74 94 92 142
of the dipole moment on the Lewis line structure
O 132 130 180
and illustrate how you reached the answer.
F 128 178
Br 228
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 Practice examples
2.Use S, O and any other element from the periodic table, but NOT the hydrogen
atom and construct a compound (can be an ion) with molecular geometry square
pyramidal. Give the Lewis dot as well as the Lewis line structure, the latter
dimensionally correct.

3.Explain the concept of resonance using PO43-.

4. Use the chlorine atom as central atom, other elements from the periodic
table, but not hydrogen and construct the following species in i, ii and iii:
i. A polar compound with octahedral molecular geometry. Show clearly the Lewis
dot structure, the 3D Lewis line structure, the direction of the dipole moment
in the Lewis line structure as well as bond angles.
ii. A cation with see-saw molecular geometry. Draw the Lewis line structure and
calculate the formal charge on chlorine.
iii. An anion with trigonal bipyramidal molecular geometry. Draw the Lewis line
structure and calculate the formal charge on chlorine.
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 Practice examples
9. The three Cℓ-O bonds in the chlorate anion, CℓO3–, have identical bond lengths,
closer to (but not equal to) that of a double bond than a single bond. (a) Draw
resonance structures of this molecule to support a brief explanation (only the first
15 words will be marked) of this observation. (b) What is Cℓ-O bond order in this
ion? Show how you determine this.
10.(a) Draw the Lewis dot structure and Lewis line structure for TeBr42-. Show all
lone pairs and bond angles. (b) Draw the line structure in 3D if applicable, using
lines, wedges and broken lines for bonds. (c) What is the name of the electron pair
geometry for TeBr42-? (d) What is the name of the molecular geometry for TeBr42-?
11.Determine whether POH3 is polar or not. Support your arguments with a three-
dimensional Lewis structure.
12.Use sulfur as the central atom and any other element(s) except hydrogen to
construct a molecule with a +1 charge and a tetrahedral molecular geometry. Draw
the three dimensional structure of this molecule and indicate all bond angles. Write
the
2017
formal charge next to each of the atoms in your structure. 91