– MOLECULAR STRUCTURE –

Week 2: Modules 4-6

Chapter 9: Sections 9.6 – 9.9
• Lewis structures for molecules and ions.
• Octet Rule, Formal charges and resonance.

Chapter 10 & 11: Sections 10.1 – 10.4 & 11.5

• Molecular shape & polarity (on-line VSEPR Tutorial)
• Hybridization & Intermolecular forces

NOTE: The CourseLink Bonding and Molecular Structure

Lab Activity directly relates to this week’s topics,
covering Lewis structures, formal charges, VSEPR,
polarity and hybridization.

FROM COURSE OUTLINE, Practice on questions:

• Chapter 9: 9.43, 9.45, 9.49, 9.57, 9.59, 9.63, 9.65,

9.69, 9.71, 9.77, 9.93, 9.97, 9.99, 9.128, 9.139.

• Chapter 10: 10.27, 10.31, 10.33, 10.35, 10.39, 10.41,

10.45, 10.49, 10.53, 10.65, 10.69, 10.73, 10.100.
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 – MOLECULAR STRUCTURE –

MODULE 4
Lewis Structures, Formal Charges and Resonance

LEWIS STRUCTURES

1. Chemical properties mostly determined by valence e–’s, electrons in outermost shell of

atom use the periodic table (do not count filled d and f orbitals).

2. Lack of reactivity of inert gases is associated with filled outer s and p shells.

3. Lewis Convention: chemical symbol stands for nucleus and inner electrons; outermost
electrons are represented by dots (or a line signifies an electron pair),

Na , C , F or F

4. Lewis diagrams only useful when only have s and p electrons (not great for d electrons).
5. The first octet period is

6. We now know the Lewis diagrams for ALL atoms in the eight main groups within the
periodic table!

7. To write a Lewis diagram, need to know either electronic configuration or position in

periodic table.

8. Atoms tend to achieve a complete outer shell (octet status) either by:

a) losing or gaining e–’s (ionic bonding) e.g., Na → Na+, Cl → Cl–

b) sharing (covalent bonding) Covalent Lewis Diagrams.

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 SIMPLE RULES FOR DRAWING
COVALENT LEWIS DIAGRAMS
1. Determine the total number of valence electrons, V.

2. Draw skeleton structure using single bonds.

3. Subtract number of electrons used thus far from V and then

4. Distribute the remaining electrons so each atom achieves octet status (access to 8
electrons). [Note: H can only get 2 electrons and F only forms single bonds.] Start with
the most electronegative atoms.

5. If too few electrons to satisfy an octet on all atoms, use double or triple bonds until each
[non-H] atom has 8 electrons.

6. If too many electrons, add extras as lone pairs to the central atom being careful to follow
the octet rule for those atoms in the second period (expanded octet allowed when central
atom has n ≥ 3 (row 3 or greater).

Note: We are just "electron accounting" at present and NOT implying geometry (that comes later).

EXAMPLES:

NF3

C2H4

N2O (N-N-O)

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 FORMAL CHARGES
To deduce the formal charge on an atom:

 Assign 1 electron from each SHARED electron pair (i.e., one per single bond, two for
double, etc.) and then ADD to this the total number of UNSHARED pairs of electrons.

 If atom has FEWER outer electrons than it would as a neutral atom, it has a
POSITIVE charge.

 If atom has MORE outer electrons than it would as a neutral atom, it has a
NEGATIVE charge.

The SUM of all the formal charges from all the atoms:
i) within a NEUTRAL MOLECULE must be ZERO
ii) within an ION must be the CHARGE of the ion

EXAMPLES:

NH4+

(CH3)3NO

RESONANCE AND RESONANCE STRUCTURES

Sometimes it’s not possible to write a single Lewis diagram which correctly reflects the
known chemistry of the molecule, e.g., O3

O V = 3 x 6 = 18

O O
O O O
O

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It’s important to recognize what we mean and what we DO NOT mean by RESONANCE:
 true state of bonding is NEVER correctly represented by ANY ONE Lewis diagram

 instead it exists somewhere BETWEEN these extremes!

O
O O

Thus the reason we link the resonance structures by

a double headed arrow.

EXAMPLES OF RESONANCE
NO3–

CH3CO2–

END OF MODULE 4

PLEASE COMPLETE ACTIVITY 4

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 – MOLECULAR STRUCTURE –

MODULE 5
More Lewis Structures and VSPER

RADICALS, OCTET FAILURES & ODD ELECTRON SPECIES

Consider: NO

Distribute electrons to suit electronegativity criteria.

Consider: NO2

Consider: BF3

Consider: XeF4

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 VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR)
THEORY
VSEPR theory provides a framework for molecular geometry predictions
→ Check out the VSEPR Tutorial on web site.

Sequence of steps to determine the stereochemistry:

1. Draw a correct Lewis diagram. (If resonance is involved, you only need one of the
resonance forms to get the correct structure).
2. For the atom whose geometry (often the central atom) you want to determine, count the
number of:
• SINGLE and(or) MULTIPLE BONDS
• LONE PAIRS

Example: SO2, the central S atom has:

(i) 1 single bond (B)
S
(ii) 1 double bond (B) O O
(iii) 1 lone pair (E)
i.e., There are THREE distinct groups of electrons that are 2 “bonds” (B) one lone pair (E)

3. Based on the number of distinct (geometry determining) groups of electrons, + BONDS

(B) and LONE PAIRS (E) determine the stereochemistry of the molecule
i.e. SO2: S has 2 Bonds, 1 Lone pair → AB2E

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Groups
Framework Shape/Geometry Angles
2 Linear Linear – AB 2 H C N 180°
.
Trigonal Trigonal planar - AB 3 O 120°
O C
3 Planar
Bent (angular) - AB 2E O
< 120°
O
S
O

Tetrahedral Tetrahedral -AB 4 H

109.5°
C
H H
H
4 Trigonal pyramidal - AB 3E < 109.5°
N
H
H H
Bent (angular) - AB 2E2 < 109.5°
O
H
H

Trigonal Trigonal bipyramidal AB 5 PCl 5 90°, 120°, 180°

Bipyramidal
Seesaw - AB 4E SeF 4 ~90°,~120°,~180°
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T-shaped - AB 3E2 ClF 3 90°, 180°

Linear - AB 2E3 XeF 2 180°

Octahedral Octahedral - AB 6 SF 6 90°, 180°

6 Square pyramidal - AB 5E XeOF 4 90°, 180°

Square planar - AB 4E2 XeF 4 90°, 180°

Trigonal Bipyramidal (5)

Linear (2)

Tetrahedral (4) Octahedral (6)

AB5
AB2
AB6
AB4
AB4E
Seesaw

Trigonal Planar (3)

AB3E
AB3
AB3E2
T-shape
Trigonal Pyramidal
AB5E
Square Pyramidal

AB2E
Bent AB2E2 AB2E3
Bent Linear

AB4E2
Square Planar

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 POLAR AND NON-POLAR MOLECULES AND IONS
Diatomic molecules are either:
• non-polar if the two atoms are identical: H2, Br2, etc.
• polar if they are different: HCl, CO, etc.

Triatomic molecules
i. a) If LINEAR, with same atoms bonded to the central atom, then non-polar: CO2

b) If terminal atoms are different, then polar: HCN

ii. If the molecule is bent, we will always get a polar system

Example: H2O

Polyatomic Systems
• Look at bond directions
• Look at bond polarities
→ decide if the molecule or ion is polar or non-polar based on the geometry
Examples:
CO32- Non-polar - why?

SO32- Polar - why?

END OF MODULE 5

PLEASE COMPLETE ACTIVITY 5

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 – MOLECULAR STRUCTURE –

MODULE 6
Hybridization

HYBRIDIZATION
The geometry of a molecule tells us how (what direction in space) the bonding (and non-bonding
lone pairs) are arranged.

Relating Hybridization and Geometry

Abbrev. Framework Angles Hybrid

AB2 linear 180° sp

AB3 trigonal planar ~120° sp2
AB2E
AB4 tetrahedral ~109.5° sp3
AB3E
AB2E2
AB5 trigonal bipyramidal ~90°,~120° sp3d
AB4E
AB3E2
AB2E3
AB6 octahedral 90° sp3d2
AB5E
AB4E2

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CH4 is a tetrahedral molecule AB4

→ Must have 4 equivalent bonding orbitals! But How?

C is 1s22s22p2 it should not give rise to tetrahedral geometry??

• we deduce that the 2s and 2p orbitals rearrange to produce 4 new molecular orbitals of equal
energy, oriented at the tetrahedral angle. This process is called hybridization.
• we can visualize the FOUR orbitals (one 2s and three 2p) giving rise to FOUR new orbitals
of identical energy - each called a "sp3 hybrid orbital" (25% s character and 75% p
character).
• These "sp3 hybrid orbital" each contain 1 electron.
• Because we can now form four strong covalent bonds a much lower energy system is
produced.

C C

3
2
V = 2s 2p
2 Four sp “hybrid orbitals"
25% s / 75% p

H 3
C is sp hybridized
It forms 4 SIGMA BONDS
write σ bonds
C H
H H

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All single bonds are called SIGMA bonds and are symbolized by σ-bonds they result from the
overlap of
 Two “s” obital (like in H2)
 One “s” with one “sp” orbital like for a C-H bond
 Two “sp” orbitals like for a C-C bond

Ethylene, C2H4, is a planar molecule, both C are trigonal planar (AB3)

• Lewis diagram implies a trigonal-planar arrangement at each C atom, with bond angles of

120°.
• one 2s orbital, one 2p orbital (with 1 electron) and the empty 2p orbital being hybridized,
i.e., three new hybrid orbitals called sp2 hybrids (33% s/67% p) and leave an original 2p

• Two of these can overlap thus, to produce one SIGMA bond (σ-bond).
• The unused (as yet) p-orbitals on each C atom can now overlap to produce an additional
bond called a π-bond.

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  The carbon atoms are now linked by one σ-bond and by one π-bond
(note that the π-bond has two lobes one above and one below the molecular framework).
 Both Cs are sp2 hybridized
 Each Carbon forms 3 σ (sigma) bonds and one π (pi)
 The geometry is TRIGONAL PLANAR (angles are around 1200)

A double bond is made of:

• One σ (sigma) bond (σ bonds are formed through the “head-on overlap” of the C’s sp2
hybridized Atomic Orbital)
• One π (pi) bond (π bonds are formed through the side overlap of NON HYBRIDIZED p
Atomic Orbitals)

Acetylene, C2H2, is a linear molecule, both C are in a linear arrangement (AB2)

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• We have a linear molecule with bond angles of 180°, which represents sp hybrid orbitals
(50% s character + 50% p character).
• Both Cs are sp hybridized
• Each Carbon forms two σ (sigma) bonds and two π (pi)
• The geometry is LINEAR (angles 1800)
• Further examples: e.g. HCN, CO2
A triple bond is made of:

• One σ (sigma) bond (σ bonds are formed through the head on collision of hybridized
sp Atomic Orbitals)
• Two π (pi) bond (π bonds are formed through the side overlap of NON
HYBRIDIZED p Atomic Orbitals)

e.g., P, S and Xe

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Examples:
1. What is the hybridization state of the carbons and oxygens in the following molecule?

d f
Cl O
H2C CH CH C OH
a b c e g

You have more questions about this molecule in Activity 6

2. What is the hybridization state of Bromine in BrCl3?

END OF MODULE 6

PLEASE COMPLETE ACTIVITY 6

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