General Chemistry (CHEM 111)

Chapter 8

Bonding and Molecular Structure

Xueying Qin

Chemical Bonds
— Formed by chemical reactions to connect atoms
— Interactions that hold atoms in a molecule together
— Two major bond types
— Ionic bond: electrons are transferred, generally between metal
and nonmetal

Na + Cl Na+ + Cl

— Covalent bond: electrons are shared, generally between

nonmetal and nonmetal

1
 Covalent Bonds
H2O, C6H12O6, C3H8O

§ When two or more non-metals bond with each other, they share
their electrons
§ The resulting bonds are called covalent bonds

Electronegativity (𝝌)
§ The ability of an atom in a molecule to attract (pull) electrons to
itself
𝝌 Increases
𝝌 increases

Δ𝜒 = 0, 𝑛𝑜𝑛𝑝𝑜𝑙𝑎𝑟 Δ𝜒 > 0, 𝑝𝑜𝑙𝑎𝑟 4

2
 Shell Model of Atoms

§ Electron shell model of first 18 atoms in the periodic table

C: 1s2 2s2 2p2

Shell Model of Atoms

§ Electron shell model of first 18 atoms in the periodic table

C: 1s2 2s2 2p2

3
 Lewis Structures
§ the arrangement of valance electrons (both bonding & non-
bonding) & nuclei in covalently bounded molecules and ions
§ Each dot represents a valence electron
§ element symbol represents the nucleus and core electrons

• Electrons are arranged

around the 4 sides of the
element symbol
18
• Show the total # of valence
electrons for an element
• Can be drawn to reflect the
electron configuration of the
element, or not

Bonding vs. Lone Pair

§ HF molecule

H + F H F

H−F

§ bonding electrons: electrons represented as lines connecting

atom symbols
§ A bond (1 line) consists of 2 electrons, The F atom in HF has 2
bonding electrons
§ 1 line: single bound (2e⎯); 2 lines: double bound (4e⎯); 3 lines:
triple bound (6e⎯)
§ Non-bonding electrons (usually in pairs) are called lone pairs,
shown as dots, F has 3 lone pairs 8

4
 Octet Rule

Octet rule: most elements will gain or lose electrons in order to

have a full outer shell of eight electrons (with exceptions)

§ F2 molecule

F + F → F F F F

§ H2 molecule (exception): stability achieved with two electrons

H + H → H H H H
9

Drawing Lewis Structure

§ PF3 molecule
Step 1: count total # of valence electrons (add 1 electron for
each negative charge, subtract 1 electron for each positive
charge.

5 (P) + 3 x 7 (F) = 26 e⎯

Step 2: central atom is usually the one with the lowest

electron negativity (H is never a central atom).

F P F
F
10

10

5
 Drawing Lewis Structure
§ PF3 molecule
Step 3: Add 1 bond between each terminal atom and the
central atom (each bond = 2 e⎯ ).

F P F

F
Step 4: add remaining electrons, in pairs, until octet rule is
satisfied. If additional electrons remain, add to central atom.

F P F Count electrons: total of 26

electrons, all used
F
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Drawing Lewis Structure

§ PF3 molecule
Step 5: Check Octet Rule.
If there is an electron deficiency for an element, change a
nonbonding electron pair (lone pair) on an adjacent atom into
a bonding pair. Continue until octet rule is satisfied for all
elements.

F P F

12

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6
 Drawing Lewis Structure

§ CO2 molecule
1. Count valance e⎯ 4 (C) + 2 x 6 (O) = 16 e⎯
2. Arrange atoms
3. Add single bonds
4. Add remaining e⎯
5. Check octet rule

O C O

O C O

Each double bond = 2 pairs of e⎯

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Drawing Lewis Structure

§ HCN molecule
1(H) + 4(C) + 5(N) = 10 e⎯
1. Count valance e⎯
2. Arrange atoms
3. Add single bonds
4. Add remaining e⎯
5. Check octet rule H C N

H C N

H C N
Each triple bond = 3 pairs of e⎯
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7
 Drawing Lewis Structure

Draw the correct Lewis structure for H2O molecule

2 x 1(H) + 6(O) = 8 e⎯

H O H

iclicker
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Drawing Lewis Structure

§ NO2+ ion For ions, the structure is placed within square brackets
and the ion charge is shown outside the brackets

5(N) + 2 x 6(O) - 1 = 16 e⎯
1. Count valance e⎯
2. Arrange atoms
3. Add single bonds +
4. Add remaining e⎯
5. Check octet rule
O N O

+
O N O

16

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8
 Drawing Lewis Structure

§ OH- ion
1(H) + 6(O) +1 = 8 e⎯

1. Count valance e⎯
2. Arrange atoms
3. Add single bonds
4. Add remaining e⎯
5. Check octet rule ⎯
H O

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Drawing Lewis Structure

§ CN⎯ ion 4(C) + 5(N) +1 = 10 e⎯

1. Count valance e⎯ ⎯
2. Arrange atoms
3. Add single bonds C N
4. Add remaining e⎯
5. Check octet rule
⎯
C N

⎯
C N
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9
 Exceptions to Octet Rule

Expanded octets/valence: elements have more than 8 electrons

(often 10 or 12) in a Lewis structure

3rd period and below due to

availability of d orbitals

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Exceptions to Octet Rule

Examples: SF6, IBr3, PF5

6(S) + 6x7(F) = 48 e⎯ 5(P) + 5x7(F) = 40 e⎯

F F 10 e⎯ F

F S F F P F

F F Br F F
I Br

12 e⎯ Br 10 e⎯
7(I) + 3x7(Br) = 28 e⎯ 20

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10
 Exceptions to Octet Rule
Incomplete Octet: elements have less than 8 electrons in a Lewis
structure
Molecules containing H, B and Be
BF3 molecule

F B F
⎯
3(B) + 3x7(F) = 24 e

6 e⎯
Good electron acceptor
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Exceptions to Octet Rule

BeCl2 molecule

Cl Be Cl
2(Be) + 2x7(Cl) = 16 e⎯

4 e⎯

HCl molecule

1(H) + 7(F) = 8 e⎯ H Cl

2 e⎯
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11
 Formal Charge (FC)
§ Formal Charge is a measure of the extent to which an atom has
gained or lost an electron in the process of forming a covalent bond
§ We can assign formal charge to each atom in a molecule or ion:

Formal Charge = # valence e⎯ - [# lone pair e⎯ + ½ (# bonding e⎯)]

1
Cl B Cl 𝐹𝐶 𝑜𝑓 𝐵 = 3 – (0 + ×6) = 0
2
1
Cl 𝐹𝐶 𝑜𝑓 𝐶𝑙 = 7 – (6 + ×2) = 0
2

Formal charge ≠ oxidation number

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Formal Charge (FC)

The sum of the formal charges for all the atoms in a molecule or
ion is equal to the charge on the molecule or ion
Formal Charge = # valence e⎯ - [# lone pair e⎯ + ½ (# bonding e⎯)]

[ CN ]⎯ ⎯
C N

1
𝐹𝐶 𝑜𝑓 𝐶 = 4 – (2 + ×6) = −1
2
1
𝐹𝐶 𝑜𝑓 𝑁 = 5 – (2 + ×6) = 0
2
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12
 Using FC to Decide Lewis Structure
Lewis structure in which the formal charge is least separated
represents the lowest energy (most stable) structure

[CNS]- 𝜒! = 2.5, 𝜒" = 2.5, 𝜒# = 3.0,

4(C) + 6(S) + 5(N) +1 = 16 e⎯

⎯ ⎯
C S N S C N

⎯ ⎯
C S N S C N
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Using FC to Decide Lewis Structure

Formal Charge = # valence e⎯ - [# lone pair e⎯ + ½ (# bonding e⎯)]

⎯ ⎯
C S N S C N

1 1
𝐹𝐶 𝑜𝑓 𝐶 = 4 – (4 + ×4) = −2 𝐹𝐶 𝑜𝑓 𝐶 = 4 – (0 + ×8) = 0
2 2
1 1
𝐹𝐶 𝑜𝑓 𝑆 = 6 – (0 + ×8) = 2 𝐹𝐶 𝑜𝑓 𝑆 = 6 – (4 + ×4) = 0
2 2
1 1
𝐹𝐶 𝑜𝑓 𝑁 = 5 – (4 + ×4) = −1 𝐹𝐶 𝑜𝑓 𝑁 = 5 – (4 + ×4) = −1
2 2
Least charge separation,
most stable 26

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13
 Drawing Lewis Structure
Draw the correct Lewis structure for CH2O molecule

O O O H

H C H H C H H C
(A) (B) (C)
1 1 1
𝐹𝐶" = 1 – 0 + ×2 = 0 𝐹𝐶" = 1 – 0 + ×2 = 0 𝐹𝐶" = 1 – 0 + ×2 = 0
2 2 2
1 1 1
𝐹𝐶# = 4 – 0 + ×6 = 1 𝐹𝐶# = 4 – 0 + ×8 = 0 𝐹𝐶# = 4 – 2 + ×6 = −1
2 2 2
1 1 1
𝐹𝐶$ = 6 – 6 + ×2 = −1 𝐹𝐶$ = 6 – 4 + ×4 = 0 𝐹𝐶$ = 6 – 2 + ×6 = 1
2 2 2
iclicker
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Resonance
Two or more valid Lewis structures for a species that differ only in
arrangement of electrons, not the arrangement of atoms, are called
resonance structures
Examples: Ozone (O3)

3 x 6 (O) = 18 e⎯

O O O
or

O O O O O O
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14
 Resonance
A B C A B C

O O O O O O
1 1
𝐹𝐶% = 6 – 4 + ×4 = 0 𝐹𝐶% = 6 – 6 + ×2 = −1
2 2
1 1
𝐹𝐶& = 6 – 2 + ×6 = 1 𝐹𝐶& = 6 – 2 + ×6 = 1
2 2
1 1
𝐹𝐶# = 6 – 6 + ×2 = −1 𝐹𝐶# = 6 – 4 + ×4 = 0
2 2

ü Both structures represent the same molecule/ion

ü Have the same atom rearrangement
ü Same geometry
ü Differ only in the arrangement of electrons
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Resonance

O O O O O O

ü Experimental evidence: the two bonds are equal

ü Resonance hybrid: A blend between the resonance structures

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15
 Resonance

NO3- ion ⎯
O N O
5(N) + 3x6(O) +1 = 24 e⎯

⎯ ⎯ ⎯
O N O O N O O N O

O O O

N⎯O : 136 pm N=O : 115 pm In [NO3]⎯ : 126 pm

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Using FC to Decide Lewis Structure

Which resonance structure is the most contributing for SO42-

6(S) + 4x6(O) +2 = 32 e⎯

⎯1
2⎯ ⎯1 2⎯ ⎯1 2⎯
O O O
⎯1 ⎯1 0 ⎯1 0 0
+2 +1 0
O S O O S O O S O

O ⎯1 O ⎯1 O ⎯1

(A) (B) (C)

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 Shapes of Molecules

Are molecules flat?

Methane (CH4) Ammonia (NH3) Water (H2O)

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Valence-Shell Electron-Pair Repulsion

VSEPR

Based on Lewis structure principles that

§ Valence electrons pairs repel each other
§ The geometry around the central atom will be such as to
minimize the repulsion

VSEPR nomenclature
A = central atom
X = bonding atoms/terminal atoms
E = lone pairs on the central atom

structural electron pairs: nonbonding electrons and bonding electrons

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 VSEPR: AX2

BeCl2
AX2
Linear, 180°

180°

CO2 HCN

H C N
180° 180°

multiple bonds are considered as 1 structural electron pairs 35

35

VSEPR: AX3

BF3
120°

CH2O
AX3
Trigonal planar, 120°
120°

36

36

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 VSEPR: AX2E
O3

O AX2E
O O O O O Bent, < 120°
116°

structural electron pairs: nonbonding electrons and bonding electrons

electron pairs geometry: arrangement of the structural electron pairs
molecular geometry (shape): arrangement of atoms around the central atom

Molecules with lone pairs:

Lone-pair/lone- Lone-pair/bonding- bonding-pair/bonding-
pair repulsion > pair repulsion > pair repulsion
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VSEPR: AX4

CH4

109.5°
AX4
tetrahedral,
109.5°

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 VSEPR: AX3E and AX2E2
NH3

AX3E
Trigonal pyramidal,
107.5°
107.5°

H2O
AX2E2
Bent, 104.5°
104.5°
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VSEPR: AX5, AX4E, AX3E2 and AX2E3

Cl
PCl5 Cl
P Cl
Cl
Cl Trigonal bipyramidal

AX4E AX3E2 AX2E3

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 VSEPR: AX6, AX5E, AX4E2 and AX3E3

F
SF6 F F Octahedral
S
F F
F

AX5E AX4E2

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What is the molecular geometry of CS2 ?

A. Tetrahedral 4 (C) + 2x6(S) = 16 e⎯

B. Trigonal pyramidal
C. Linear
D. Bent
S C S

S C S

AX2: linear

iclicker
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 What is the electron pair geometry and the molecular geometry of
ClF5? 7 (Cl) + 5 x 7(F) = 42 e⎯

F AX5E
F F
Cl
F F

The electron - pair geometry The molecular geometry

A. Trigonal bipyramidal A. Trigonal bipyramidal

B. Octahedral B. Octahedral
C. Square pyramidal C. Square pyramidal
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What is the electron pair geometry and the molecular geometry of

XeF4? 8 (Xe) + 4 x 7(F) = 36 e⎯

F F
Xe AX4E2
F F

The electron - pair geometry The molecular geometry

A. Trigonal bipyramidal A. Tetrahedral

B. Octahedral B. Octahedral
C. Tetrahedral C. Square planar
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22
 Using Lewis structure determine the geometry of the following atoms?

H O H
1 2 3 4 5
H C C C C C O
6
H
H H

A B

1 - Tetrahedral 1, 5 - Tetrahedral
2 - Trigonal pyramidal 2 - Trigonal planar
3, 4 - Trigonal planar 3, 4 - Linear
6 - Linear 6 - Bent

iclicker
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Polar Covalent Bonds

Non-polar covalent bonds: Bonding electrons are shared equally
between the two atoms

Polar covalent bonds: Unequal sharing of bonding electrons are

between the two atoms with different electronegativities (𝝌)

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 Bond Polarity (∆𝝌)
∆𝝌 = 𝟎 for Non-polar covalent bonds

∆𝝌 = 𝟑. 𝟎 − 𝟑. 𝟎 = 𝟎

∆𝝌 ≠ 𝟎 for polar covalent bonds

−1
+1

∆𝝌 = 𝟑. 𝟎 − 𝟐. 𝟐 = 𝟎. 𝟖 ∆𝝌 = 𝟑. 𝟎 − 𝟏. 𝟎 = 𝟐. 𝟎
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Dipole Moment (𝜇) and Molecular Polarity

Asymmetric electron distribution results in an electric dipole (𝜇)

CO2 has polar bonds but is overall

a non-polar molecule because the
net dipole moment is zero

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 Molecular Polarity

𝜹4d
H2O has polar bonds and is a polar
𝜹3d 𝜹3d molecule because the net dipole
moment is non-zero

A compound is non polar if it is symmetrical and has a VSEPR type

AX2, AX3, AX4, AX5,AX6 (all X(s) are the same in the compound)
Exceptions:
AX2E3, linear, nonpolar AX4E2, flat, nonpolar
AX2E4, linear, nonpolar 49

49

What is the geometry of NH3? Is it polar or non polar molecule?

A. Trigonal planar, polar

3 x 1 (H) + 5 (N) = 8 e⎯
B. Trigonal planar, non polar
C. Trigonal pyramidal, polar
D. Trigonal pyramidal, non polar

AX3E

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 What are the nature of CH4 and CCl4 molecules

A. Both are polar

B. Both are non polar
C. CH4 is polar and CCl4 is non polar
D. CH4 is non polar and CCl4 is polar

Both AX4, all X’s are equal

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Which of the molecules below are polar?

AX3 AX2E2 AX2X’2

(A) (B) (C)

A. A only
B. B and C
C. C only
D. A and B
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26
 Which of the molecules below are nonpolar?

1. PF5
F
F
2. CH2Cl2
P F
3. SO2 F
F
A. 1 only AX5, nonpolar AX2X’2, polar
B. 2 and 3
C. 2 only
D. 3 only

AX2E, polar
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Bond Order
Number of bonding electron pairs (number of bonds) between two
bonded atoms

Bond Type Bond Order

Single bond 1

Double bond 2

Triple bond 3

Resonance structures fractional

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 Bond Order: Resonance Structures
bond order of each bond 56789: ;< 8;5=> ?5@;A@9= ?5 :9>;5B5C9
=
in resonance structure 56789: ;< :9>;5B5C9 >D:6CD6:9>

3
O O O O O O 𝐵𝑂 = = 1.5
2

4
𝐵𝑂 = = 1.33
3 55

55

What is the bond order of CO32-

A. 1
B. 2
C. 1.3
D. 1.5

4
𝐵𝑂 = = 1.33
3 56

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 Bond Length
The distance between the atomic nuclei when energy is minimized is
the bond length

nuclear-nuclear + electron-nuclear + electron-electron

P.E. of interaction =
repulsion attraction repulsion
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Bond Length

Bond length increases with increasing atom size

For a series of bonds that differ only in bond order, bond length
decreases with increasing bond order

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 Bond Dissociation Energy
§ Bond energy is the energy required to break a chemical bond in a
gas-phase molecule to individual atoms
§ Always an endothermic (requires energy) process

ΔHo = 436 kJ/mol

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Bond Energies in KJ/mol

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 Bond Energy, Bond order and Bond Length

§ The greater the bond order, the higher the bond strength and the
shorter the bond

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Which molecule has the shortest carbon-carbon bond length among

C2H6, C2H4, C2H2

A. C2H6
B. C2H4
C. C2H2
D. All have the same bond length

62

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 Enthalpy of Reaction (ΔrHo)
§ Enthalpy, H, is the sum of the internal energy of a system plus the
product of pressure and volume

§ The change in enthalpy, ΔH, is equal to the heat exchanged under

constant pressure

§ ΔrHo = Σ (energies of bonds broken) - Σ (energies of bonds formed)

§ ΔrHo = Σ ΔHo(bonds broken) - Σ ΔHo (bonds formed)

§ Combustion of Hydrogen

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Enthalpy of Reaction (ΔrHo)

𝟐𝐇−𝐇+𝐎=𝐎 = 𝟐𝐇−𝐎−𝐇
Potential Energy (KJ)

H, H, H, H, O, O ΔH0()( = 436 kJ/𝑚𝑜𝑙

Atoms ΔH0*+* = 498 kJ/𝑚𝑜𝑙
ΔH0()* = 463 kJ/𝑚𝑜𝑙
2H2(g), O2 (g)
Reactants ΔrHo 2H2O (g)
Products

∆, H0 = Σ∆𝐻- 𝑏𝑜𝑛𝑑𝑠 𝑏𝑟𝑜𝑘𝑒𝑛 − Σ∆𝐻- 𝑏𝑜𝑛𝑑𝑠 𝑓𝑜𝑟𝑚𝑒𝑑

= 2×436 + 498 − 4×463

= −482 𝑘𝐽/𝑚𝑜𝑙
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 Calculate the enthalpy change for the following reaction

H—H = 436 kJ/mol

Cl—Cl = 242 kJ/mol
H—Cl = 432 kJ/mol

∆: H0 = Σ∆𝐻 E 𝑏𝑜𝑛𝑑𝑠 𝑏𝑟𝑜𝑘𝑒𝑛 − Σ∆𝐻 E 𝑏𝑜𝑛𝑑𝑠 𝑓𝑜𝑟𝑚𝑒𝑑

= ΔHBCB + ΔHDECDE − 2×ΔHF4CA

= 436 + 242 − 2×432

= −186 𝑘𝐽/𝑚𝑜𝑙

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Calculate the enthalpy change for the reaction below

Br2 (g) + 3 F2 (g) 2 BrF3(g)

Bond Bond Enthalpy (kJ/mol)

Br-Br 193
F-F 155
Br-F 249

A. +89 kJ
∆: H0 = ΔHGH4I: + 3× ΔHJ4J − 6×ΔHGH4K
B. -836 kJ
C. +99 kJ = 193 + 3×155 − 6×249
D. -99 kJ = −836 𝑘𝐽/𝑚𝑜𝑙
E. +836 kJ
iclicker
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