Molecular Structure – Part 1

1
 Lewis Dot Notation

• Element Symbol = Nucleus & inner electrons.

• ‘Dots’ = Valence electrons

• All atoms strive for the OCTET rule (8 electrons).

Molecular Structure – Part 1 2
Bonding Electrons, Lone Pairs & Multiple
Bonds

• Single bond = 1

Bonding e‐ pair

• Double bond = 2

Multiple bond

• Triple bond = 3

Lone pair

Molecular Structure – Part 1 3

Bonding Electrons, Lone Pairs & Multiple
Bonds
• Double bonds typically found in molecules containing:
C, N, P, O, S.

• Triple bonds typically found in molecules containing:

C, N.

Molecular Structure – Part 1 4

 The Octet Rule (Guidelines?)
The octet rule is not without exceptions. Known examples
are:
• Molecules in which the central atom is surrounded by
MORE than 8 electrons
‐ common for elements in period 3 onwards which have
empty d‐orbitals. E.g. SF6

• Molecules in which the central atom is surrounded by

FEWER than 8 electrons ‐ mostly group 2 and 13 ( Be, B, Al
E.g. BF3)

• Compounds with an ODD number of valence electrons (eg.

NO).
Molecular Structure – Part 1 5
Molecular Structure – Part 1 6
 Drawing Lewis Structures – NF3

Draw the Lewis structure for nitrogen trifluoride (NF3).

• Step 1: Determine total valence electrons.

N = 5 e‐
F (x 3) = 7 e‐ (x 3) = 21 e‐ 26 valence e‐

• Step 2: Place the atoms relative to each other to construct a

skeleton structure.

Least electronegative
atom at the centre (typically)

Molecular Structure – Part 1 7

 Drawing Lewis Structures

• Step 3: Place a pair of e‐ between each atom to create

bonding electron pairs and recalculate remaining valence e‐.

26 – 6 = 20 valence e‐
remaining.

• Step 4: Distribute remaining e‐ on outer ligands (atoms) to

satisfy the octet rule and recalculate valence e.

20 – 18 = 2 valence e‐
remaining.

Molecular Structure – Part 1 8

 Drawing Lewis Structures

• Step 5: Place remaining valence e‐ around central atoms to

create lone pairs and check octet structure.

NOTE: Lewis structures DO NOT denote shape!

(we’ll get to this later)

Molecular Structure – Part 1 9

Molecular Structure – Part 1 10
 Drawing Lewis Structures – O3
(Example of Multiple bonds)
Draw the Lewis structure for ozone (O3)

• Step 1: Determine total valence electrons.

O = 6 e‐ x 3 = 18 valence e‐

• Step 2: Place the atoms relative to each other to construct a

skeleton structure.

Molecular Structure – Part 1 11

 Drawing Lewis Structures – O3
(Example of Multiple bonds)
• Step 3: Place a pair of e‐ between each atom to creating
bonding electron pairs and recalculate remaining valence e‐.

18 – 4 = 14 valence e‐
remaining.

• Step 4: Distribute remaining e‐ on outer ligands (atoms) to

satisfy the octet rule and recalculate valence e.

14 – 12 = 2 valence e‐
remaining.

Molecular Structure – Part 1 12

 Drawing Lewis Structures – O3
(Example of Multiple bonds)
• Step 5: Place remaining valence e‐ around central atoms to
create lone pairs and check octet structure.

Only 6 e‐ on central O.
(Clue for multiple bonds)

• Step 6: Relocate e‐ pair from outer atom to central atom.

OR

Concept of Resonance
Molecular Structure – Part 1 13
 Resonance Theory
• Chemical structures are not static. In reality “real”
structure lies somewhere between what we draw.

Molecular Structure – Part 1 14

Resonance Depiction ‐ Movie

Molecular Structure – Part 1 15

Molecular Structure – Part 2

1
 Formal charge / Oxidation number

Formal Charge = Valence e‐ on free atom

– (½ bonding e‐ on atom)
– (lone pair e‐)

N = 5 – (6/2) – 2 = 5 – 3 ‐2 = 0
F = 7 – (2/2) – 6 = 7 – 1 – 6 = 0

i.e. Overall the NF3 is neutral (Expected).

Molecular Structure – Part 2 2

 Drawing Lewis Structures – H2SO4
(Example of Formal Charge)
NOTE: Formal charge is important for Z > 10! (i.e. S, P)

E.g. Draw the Lewis Structure for sulfuric acid (H2SO4)

• Step 1: Determine total valence electrons.

H = 1 e‐ (x 2) = 2 e‐
S = 6 e‐ 32 valence e‐
O = 6 e‐ (x 4) = 24 e‐

Molecular Structure – Part 2 3

 Drawing Lewis Structures – H2SO4
(Example of Formal Charge)
• Step 2: Place the atoms relative to each other to construct a
skeleton structure.

Molecular Structure – Part 2 4

 Drawing Lewis Structures – H2SO4
(Example of Formal Charge)
Step 3: Place a pair of e‐ between each atom to creating
bonding electron pairs and recalculate remaining valence e‐.

32 e‐ – 12 e‐ = 20 valence e‐ remaining.

Molecular Structure – Part 2 5

 Drawing Lewis Structures – H2SO4
(Example of Formal Charge)
• Step 4: Distribute remaining e‐ on outer ligands (atoms) to
satisfy the octet rule and recalculate valence e.

20 e‐ – 20 e‐ = 0 valence e‐ remaining.

Molecular Structure – Part 2 6

 Drawing Lewis Structures – H2SO4
(Example of Formal Charge)
• Skip step 5 & 6 since no remaining valence electrons.

Molecular Structure – Part 2 7

 Drawing Lewis Structures – H2SO4
(Example of Formal Charge)
• Step 7: Check formal charge on the atoms.
Formal Charge = Valence e‐ on free atom – (½ bonding e‐ on atom) – (lone pair e‐)

H = 1 – (2/2) – 0 = 0
S = 6 – (8/2) – 0 = +2
O = 6 – (4/2) – 4 = 0

H = 1 – (2/2) – 0 = 0

O = 6 – (2/2) – 6 = ‐1

Suggests 2 double bonds to S (1 for each O).

Molecular Structure – Part 2 8
 Drawing Lewis Structures – H2SO4
(Example of Formal Charge)
• Step 8: Modify structure and check the charges
H = 1 – (2/2) – 0 = 0
S = 6 – (12/2) – 0 = 0
O = 6 – (4/2) – 4 = 0

H = 1 – (2/2) – 0 = 0

O = 6 – (4/2) – 4 = 0

This structure produces LOWEST charge ‐ MOST STABLE!

Molecular Structure – Part 2 9
Drawing Lewis Structures – H2SO4
(Example of Formal Charge)

Might see it drawn like this.

Molecular Structure – Part 2 10

 Drawing Lewis Structures – PO43‐
(Example of Formal Charge)
E.g. Draw the Lewis Structure of phosphate (PO43‐) (Z > 10!)

• Step 1: Determine total valence electrons.

P = 5 e‐
O = 6 e‐ (x 4) = 24 e‐ 32 valence e‐
charge = 3 e‐

NOTE: If the charge was positive, SUBTRACT the necessary

amount when calculating the valence e‐s (i.e. molecule loses
valence e‐ s and becomes +).

Molecular Structure – Part 2 11

 Drawing Lewis Structures – PO43‐
(Example of Formal Charge)
• Step 2: Place the atoms relative to each other to construct a
skeleton structure.

Molecular Structure – Part 2 12

 Drawing Lewis Structures – PO43‐
(Example of Formal Charge)
Step 3: Place a pair of e‐ between each atom to creating
bonding electron pairs and recalculate remaining valence e‐.

32 e‐ – 8 e‐ = 24 valence e‐ remaining.

Molecular Structure – Part 2 13

 Drawing Lewis Structures – PO43‐
(Example of Formal Charge)
• Step 4: Distribute remaining e‐ on outer ligands (atoms) to
satisfy the octet rule and recalculate valence e.

24 e‐ – 24 e‐ = 0 valence e‐ remaining.

Molecular Structure – Part 2 14

 Drawing Lewis Structures – PO43‐
(Example of Formal Charge)
• Step 7 (Skip 5&6): Distribute remaining e‐ on outer ligands
(atoms) to satisfy the octet rule and recalculate valence e.

P = 5 – (8/2) = +1
O = 6 – (2/2) – 6 = ‐1

Total charge = ‐1‐1‐1‐1+1

= ‐3
O = 6 – (2/2) – 6 = ‐1

Suggests a double bonds to P.

Molecular Structure – Part 2 15
 Drawing Lewis Structures – PO43‐
(Example of Formal Charge)
• Step 8: Modify structure and check charges.

P = 5 – (10/2) = 0
O = 6 – (2/2) – 6 = ‐1

Total charge = ‐1‐1‐1

O = 6 – (4/2) – 4 = 0 = ‐3

Molecular Structure – Part 2 16

 Drawing Lewis Structures – PO43‐
(Example of Formal Charge)

Might see it drawn like this.

Molecular Structure – Part 2 17

 Drawing Lewis Structures – PO43‐
(Example of Formal Charge)

Might see it drawn like this.

Molecular Structure – Part 2 18

Coordinate Covalent Bond or Dative Bond

• So far, we’ve seen examples where each atom contributes

at least one electron to the covalent bond. It possible,
however, that BOTH electrons in a particular covalent bond
originates from only ONE atom. This is called a Coordinate
Covalent Bond or a Dative Bond.

Coordinate/Dative Bond N = 5 – (8/2) – 0 = +1

a proton
(H without
ammonia
it’s electron) positive ammonium ion

Molecular Structure – Part 2 19

Molecular Structure – Part 3

1
 Molecular Shape & VSEPR Theory

• Valence Shell Electron Pair Repulsion (VSEPR) Theory is

applied (to the Lewis structures) in order to obtain the
molecular shape (3‐D arrangement of nuclei joined by the
bonding groups).

• VSEPR theory aims to minimise electron repulsions by

arranging each group of valence electrons (i.e. double bond
is considered as a single ‘group’ even though there are 4 e‐)
around the central atom as far as possible from the others.

• NOTE!! Only electrons around the CENTRAL ATOM

influence molecular shape.

Molecular Structure – Part 3 2

 Electron‐Group Arrangements

• Central atoms have 2, 3, 4, 5 or 6 ligands (bonded atoms)

attached to it – AXnEm.

AX2 AX3 AX4 AX5 AX6

Molecular Structure – Part 3 3

Two Electron Groups ‐ Linear

• Minimal repulsions at 180 °

• Linear arrangement.

Eg. CS2

Molecular Structure – Part 3 4

 Three Electron Groups

• 1) AX3 ‐ Minimal repulsions at

120 ° (think ‘triangle’).

Eg. BF3

AX3
Resulting shape is Trigonal Planar.
Examples:
SO3, BF3, NO3–, CO32–

Molecular Structure – Part 3 5

 Three Electron Groups

• 2) AX2E – Lone pair repulsion is

AX2E
more than a ‘bond’ and
therefore decreases bond
angle.

Eg. SnCl2 Repulsion by lone pair

Examples:
SO2, O3, PbCl2, SnBr2

Results in Bent or V shape geometry.

Molecular Structure – Part 3 6
 Four Electron Groups

• 1) AX4 – Minimum repulsions at 109.5o

Eg. CH4 (methane)

AX4

Tetrahedral shape.
Examples:
CH4, SiCl4,
SO42–, ClO4–
Molecular Structure – Part 3 7
 Four Electron Groups

AX3E • 2) AX3E – Replace one ligand with a lone

pair. Increases repulsions and decreases
bond angle.

Eg. NH3 (ammonia) Repulsion by lone pair

Examples:
NH3, PF3
ClO3–, H3O+

Trigonal pyramidal
Molecular Structure – Part 3 8
 Four Electron Groups

AX2E2 • 3) AX2E2 – Replace two ligands with lone

pairs. Further increases repulsions and
decreases bond angle.

Eg. H2O (water) Repulsion by additional

lone pair

Examples:
H2O, OF2, SCl2

Bent or V shaped
Molecular Structure – Part 3 9
 Five Electron Groups
AX5 Examples: AX4E Examples:
PF5, AsF5, SF4, XeO2F2
SOF4 IF4+, IO2F2–

AX3E2 AX2E3
Examples: Examples:
ClF3, BrF3 XeF2, I3–, IF2–

Molecular Structure – Part 3 10

 Six Electron Groups
AX6
Examples:
SF6, IOF5

AX5E AX4E2

Examples: Examples:
BrF5, TeF5–, XeF4, ICl4–
XeOF4

Molecular Structure – Part 3 11

 Molecular Structure – Part 4
Balloon Experiment
Visualizing molecular geometry

Video kindly provided with permission by:

https://www.flinnsci.com/
https://www.youtube.com/user/FlinnScientific

1
Molecular Structure – Part 5

1
Lewis Structures Revisited – Getting Into Shape

• Nitrogen Trifluoride

AX3E

Trigonal pyramidal

Molecular Structure – Part 5 2

Lewis Structures Revisited – Getting Into Shape

• Ozone

AX2E Bent or V Shaped

Molecular Structure – Part 5 3

Lewis Structures Revisited – Getting Into Shape

• Sulfuric acid
Bent or V Shaped around O

AX2E2

Tetrahedral around S
AX4

Molecular Structure – Part 5 4

Biological Importance

Molecular Structure – Part 5 5

 Molecular Polarity
• Molecular shape has a strong influence on
molecular polarity.
Influences:
‐ Melting points Think about the effect of
‐ Boiling points molecular polarity on
‐ Solubility intermolecular interactions
‐ Chemical reactivity
‐ Biological function

Molecular Structure – Part 5 6

 Molecular Polarity
Dipole moment (µ)
Units = debye (D)
1 D = 3.34 x 10‐30 C∙m

Molecules become oriented when

Molecules are randomly oriented.
the field is turned on.

Molecular Structure – Part 5 7

 Molecular Polarity – CO2
• Molecular shape is crucial in determining polarity.
Copyright © The McGraw‐Hill Companies, Inc. Permission required for reproduction or display.

Eg. CO2
AX2 linear Negative

Positive

=0D
180° bond angle:
Nett effect is
no dipole moment
= nonpolar.

Molecular Structure – Part 5 8

 Molecular Polarity – H2O

• Molecular shape is crucial in determining polarity.

Copyright © The McGraw‐Hill Companies, Inc. Permission required for reproduction or display.

Eg. H2O
Negative
Nett 
Positive

 = 1.85 D
Strong dipole exists = polar molecule.

Molecular Structure – Part 5 9

 Molecular Polarity – AX4

CCl4 CHCl3

Bonds are polar, but individual Bond polarities do not cancel.

bond polarities cancel. This molecule is polar (μ = 1.01 D).

Molecular Structure – Part 5 10

Molecular Structure – Part 6

1
 6. Valence Bond Theory and Orbital
Hybridisation
• RECALL ‐ Covalent Bonding: A covalent bond involves the
Sharing of electrons between two atoms such that there is a
balance between all attractive and repulsive forces between
the atoms.

Eg. Ammonia

What about the orbitals (s, p, d)??

Molecular Structure – Part 6 2

 Valence Bond Theory
• Valence Bond Theory states that a covalent bond forms
when the orbitals of two atoms overlap and a pair of
electrons occupy the overlap region (between the nuclei).

• The interactions of atomic orbitals to form a new “hybrid”

orbitals.

• Two overlapping wave functions in phase.

• Maximum of 2e‐ in the overlap and with opposite spins

(exclusion principle).

• The greater the overlap, the stronger/more stable the bond.

Molecular Structure – Part 6 3
 Valence Bond Theory

Examples:

For these linear

molecules, these
overlaps seem
reasonable!

Molecular Structure – Part 6 4

 Thought Experiment – The Case of CH4
C: 2s22p2

Add H

BUT I know methane is CH4… I’ve SEEN IT!!

C only has 2p orbitals (px & py)
And it’s bond angle should be 109.5° NOT 90°!
to share with H …??

Add H

Molecular Structure – Part 6 5

 Hybridisation
The valence atomic orbitals that are involved in bonding in a
molecule are DIFFERENT from those in the isolated atoms.
RULES:
• The number of hybrid orbitals obtained equals the number of atomic
orbitals mixed.
• The type of hybrid orbitals around a central atom varies with the types of
atomic orbitals mixed.
# electron groups around Shape of molecule around central Type of hybridization
the central atom atom (new hybrid orbital)
2 Linear (180o) sp
3 Trigonal planar (120o) sp2
4 Tetrahedral (109.5o) sp3
5 Trigonal bipyramidal (120o & 90o) sp3d
6 Octahedral (90o) sp3d2

Molecular Structure – Part 6 6

 Hybridisation – sp3
The valence atomic orbitals that are involved in bonding in a
molecule are DIFFERENT from those in the isolated atoms.

• The Case for methane – CH4:

• C is sp3 hybridised – Since we mixed 1

‘s’ and 3 ‘p’ orbitals.

• AX4, AX3E, AX2E2 (i.e. 4 ‘groups’) = sp3

hybridisation.
Molecular Structure – Part 6 7
 Key to Success ‐ Hybridisation

• Key steps to the ‘hybridisation questions’.

1. Write the Lewis formula
2. Use the Lewis formula to determine arrangement of
electron pairs by VSEPR model
3. From geometric arrangement deduce hybridisation
4. Assign valence electrons to orbitals one at a time-
pair them when necessary
5. Form  bonds by overlapping singly occupied orbitals
of other atoms with singly occupied hybrid orbitals

Molecular Structure – Part 6 8

 Hybridisation – sp2

• Boron trifluoride – BF3:

• B is sp2 hybridised – Since we mixed 1 ‘s’

orbital and 2 ‘p’ orbital.

• AX3, AX2E (i.e. 3 ‘groups’) = sp2 hybridisation.

Molecular Structure – Part 6 9

 Hybridisation – sp

• Beryllium dichloride – BeCl2:

• Be is sp hybridised – Since we mixed 1 ‘s’ orbital and 1 ‘p’ orbital.

• AX2 (linear molecules) = sp hybridisation.

Molecular Structure – Part 6 10

 Table 11.1 Composition and Orientation of Hybrid Orbitals

Trigonal Trigonal
Linear Planar Tetrahedral Bipyramidal Octahedral
Atomic orbitals one s one s one s one s one s
mixed one p two p three p three p three p
one d two d

Hybrid orbitals two sp three sp2 four sp3 five sp3d six sp3d2
formed

Unhybridized two p one p none four d three d

orbitals
remaining

Orientation

Molecular Structure – Part 6

Molecular Structure – Part 7

1
 Single vs Double Covalent Bonds
• Sigma bonds (σ) are the result of the end‐to‐end bonding of
orbitals. All single bonds are sigma bonds.

Sigma bonds (δ)

+
• Pi bonds (π) are the result of the side‐to‐side bonding of
orbitals. Present in double and triple bonds.
π bond

Molecular Structure – Part 7 2

 Double vs Triple Covalent Bonds
Double bond = 1σ and 1π bond.

Ethylene

Triple bond = 1σ and 2π bonds.

Acetylene

Molecular Structure – Part 7 3

 Double Covalent Bonds
Double bond = 1σ and 1π bond.
Ethylene

overlap in one position - 

p overlap - 

Note: rotation cannot occur around a double bond

Molecular Structure – Part 7

Class example – Provide a Valence Bond
Description of C2H2
• Step 1: Draw the Lewis structure for C2H2 (This should be
straightforward).

• Step 2: Determine the molecular shape and hybridisation.

Linear, AX2 (about carbon) = sp hybridisation

Molecular Structure – Part 7 5

Class example – Use Valence Bond Theory to
Rationalise the Bonding found in C2H2
• Step 3: Construct orbital diagram for one of the carbon atoms.
• Each C is sp hybridized (linear, 2 electron groups each)
• Each C has 4 valence electrons

Bonding orbitals for ONE carbon atom:

Atomic orbitals Hybrid orbitals

Molecular Structure – Part 7 6
Class example – Use Valence Bond Theory to
Rationalise the Bonding found in C2H2
• Step 4: Add corresponding bonding e‐ (4 e‐ : 1 from H, 3
from the bonded carbon – from Lewis Structure).

Indicates 2 σ bonds Indicates 2 π bonds

(1 to H and 1 to C)

• This shows how acetylene contains a triple bond between

the carbons, which is made up if 1 σ and 2 π bonds, as well
as a σ bond to H.

Molecular Structure – Part 7 7

 More practice examples
Given the Lewis dot structures below, identify the geometry and
hybridisation state of each of the atoms marked by arrows:

a H
: O: b C)
A) H C
H
:

:
C C H
H2N C NH2 b
H C C H
a C
H H
d C H

HC c
:O : c
B) a

:
D) H N N H
: :

H3C C OH
a b
b