Chem

1 1A03

Chemistry 1A03
Introductory Chemistry I
Chemistry in the context of health,
energy and the environment

©2008 – 2020 McMaster University

Unit 11
Intermolecular
Forces – part 1
 Chem
2 1A03
Learning outcomes – IMF part 1
1. Describe the different types of intermolecular forces, including
London (dispersion) forces, dipole-dipole forces, and hydrogen
bonding.

2. Based on the structure of a molecule, rationalize the maximum

and average number of hydrogen bonds that can be formed.

©2008 – 2020 McMaster University

 Chem
3 1A03
Learning outcomes – IMF part 1
3. Explain how molecular structure and intermolecular forces can
influence physical properties.

4. Explain the significance of intermolecular forces in biological

molecules such as DNA and the lipid bilayer.

©2008 – 2020 McMaster University

 Chem
4 1A03
Intermolecular forces (IMF)
• IMF play a significant role in solids and liquids, but not in
gases: molecules are well separated.
• IMF strength affects melting point, boiling point, vapour
pressure, surface tension, enthalpy change of phase
transitions.

©2008 – 2020 McMaster University

• Boiling point increases with increasing IMF strength.
• Recall: polar molecules & electrostatic potential maps,
example acetone
 Chem
5 1A03
Intermolecular forces
In pure substances:
• London (dispersion) forces
e.g. iodine

• Dipole-dipole forces
e.g. acetone

©2008 – 2020 McMaster University

• Hydrogen-bonding forces
e.g. water

In solution: ion-dipole forces

e.g., hydrated ions
 Chem
6 1A03
London (dispersion) forces
• Also called instantaneous dipole-induced dipole forces
(a) nonpolar atom or molecule,
(b) experiences an instantaneous dipole,
(c) which induces a dipole in its neighbour.

©2008 – 2020 McMaster University

• Strength depends on polarizability
 Chem
7 1A03
London (dispersion) forces
• Strength increases with:
- atomic number and size of the molecule (polarizability):
Molecule Boiling point, K
H2 20.4
N2 77.4
Cl2 238.3

©2008 – 2020 McMaster University

- linear versus branched structures (increased intermolecular contact area):

n-butane, Isobutane, 2-methylpropane

b.p. = -1 C b.p. = -11.7 C
 Chem
8 1A03
Dipole-dipole forces
• Occur in polar molecules
• Permanent dipole: bond dipoles and asymmetric shape
• For similar polarizability, polar molecules have stronger
intermolecular forces than nonpolar molecules.
• N2 (77 K), O2 (90 K) (London forces)
• NO (121 K) (London forces and dipole-dipole forces)

©2008 – 2020 McMaster University

acetone
 Chem
9 1A03
Hydrogen bonding

• Between an H atom in a polar bond (i.e., H-N, H-O, or H-F) and another
electronegative atom (i.e., N, O, or F)
• One H-bond is small, but many are mighty.
H-bonding in ammonia Base-pairing in DNA

©2008 – 2020 McMaster University

 Chem
10 1A03
Sample question
• When ethanol (CH3CH2OH) changes phase from
the liquid to the gas, which bond(s)/forces
are being broken?
A. C-H covalent bond
B. O-H covalent bond

©2008 – 2020 McMaster University

C. O∙∙∙∙H hydrogen bond
D. O-C covalent bond
E. More than one of the above
 Boiling point & IMF
1A03
Chem
11

©2008 – 2020 McMaster University

 Chem
12 1A03
Hydrogen bonding

HF H2O NH3
# of δ+ H atoms (H-bond donors) 1 2 3
# of lone pairs on δ- atom (H-bond acceptor) 3 2 1

©2008 – 2020 McMaster University

Maximum # of H-bonds per molecule 4 4 4
average # of H-bonds per molecule in 2 4 2
bulk sample (2 x “LR”)
Boiling point (oC) 19 100 -33
 Chem
13 1A03
Hydrogen bonding
HF H2O NH3
average # of H-bonds per molecule 2 4 2
in bulk sample (2 x “LR”)

“chains”

©2008 – 2020 McMaster University

“chains”

“networks”
 Chem
14 1A03
Strengths of intermolecular forces
• The range of strength for each force type overlaps, but
approximately:
Dispersion < Dipole-dipole < H-bonding < Ionic/Covalent
Interaction Interaction energy (kJ/mol)*
Dispersion 0.05 – 40

©2008 – 2020 McMaster University

Dipole-dipole 5 – 25
Hydrogen bonding 10 – 40 (per bond)
Ionic 400 – 4000
C-C covalent bond 350 (per bond)
 Chem
15 1A03
Sample question
• Which compound is expected to have the highest boiling point
as a bulk compound?

A. London forces, dipole-dipole forces

B. London forces, dipole-dipole forces, H-bonds

©2008 – 2020 McMaster University

C.
London forces, dipole-dipole forces

D.
London forces
 Chem
16 1A03
Lipid bilayer formation
• Cellular membranes are
composed primarily of
phospholipids which
spontaneously form bilayers
• Bilayer formation generates
polar surfaces which maximizes

©2008 – 2020 McMaster University

the number of strong ion-dipole
interactions with water
• Allows for cellular
compartmentalization
 Chem
17 1A03
Summary of key concepts
• Intermolecular forces affect liquids and solids but not gases.
• All molecules exhibit London (dispersion) forces.
• Molecules with similar size: dipole-dipole forces are more
significant than dispersion forces.
• Molecules with different

©2008 – 2020 McMaster University

size: dispersion forces can
be more significant than
dipole-dipole forces.
 Chem
18 1A03

Chemistry 1A03
Introductory Chemistry I
Chemistry in the context of health,
energy and the environment

©2008 – 2020 McMaster University

Unit 11
Intermolecular
Forces – part 2
 Chem
19 1A03
Learning outcomes – IMF part 2
5. Explain how molecular structure and intermolecular forces can
influence physical properties (melting point, boiling point,
vapour pressure, and enthalpy of vaporization).

©2008 – 2020 McMaster University

 Chem
20 1A03
Learning outcomes – IMF part 2
6. Define vapour pressure with respect to equilibrium; define
boiling point with respect to vapour pressure and temperature.

7. Use a pressure-temperature graph to estimate vapour pressure,

temperature, and phase (liquid/gas) of a particular molecule.

©2008 – 2020 McMaster University

 Chem
21 1A03
Properties of Liquids
Physical Property Effect of increasing IMF
Melting point (mp) increases
Boiling point (bp) increases
Standard enthalpy of
increases
vaporization (∆vapH°)
Vapour pressure decreases

©2008 – 2020 McMaster University

Ethanol Ethylene glycol Glycerol
bp 78 oC bp 197 oC bp 290 oC
 Chem
22 1A03
Vaporization
• Vaporization (or evaporation): molecules at the surface of a
liquid have enough energy to overcome intermolecular
forces of attraction and escape to the gas phase
• Vaporization occurs more readily with:
1. Increased temperature

©2008 – 2020 McMaster University

2. Increased surface area
3. Decreased IMF strength
 Chem
23 1A03
Vapour Pressure

Petrucci, 11th ed. Fig 12-16

©2008 – 2020 McMaster University

• Vapour pressure is the equilibrium partial pressure of the
vapour in the space above the liquid.
• A(l) ⇄ A(g) 𝐾 = 𝑃𝐴(𝑔)
 Chem
24 1A03
Sample question
At 25.0 oC, ΔGo = 8.6 kJ/mol for the process:

H2O(l) H2O(g)
What is the vapour pressure of water at 25.0 oC ?
A) 0.0015 bar DGo = –RT ln K K = P(H2O)
B) 0.031 bar

©2008 – 2020 McMaster University

ln K = –DG/RT =
C) 0.259 bar 8600 J mol–1 / (-8.314 J K–1 mol–1 * 298 K)
D) 0.25 bar = –3.4711
K = e–3.4711 = 0.03108
E) 1.0 bar
Therefore P(H2O) = 0.031 bar
 Chem
25
Pvap vs T 1A03

750
Liquid
Standard bp when
Pvap = 1 bar = 750 mm Hg

Vapour (a) Diethyl ether, (CH3CH2)2O

(b) Benzene, C6H6

©2008 – 2020 McMaster University

Mount Everest (c) Water, H2O
(d) Toluene, C6H5-CH3
(e) Aniline, C6H5-NH2

(You are NOT responsible for

the Clausius-Clapeyron eqn)

• Pvap is influenced by IMF strength

 Chem
26 1A03
Sample questions

©2008 – 2020 McMaster University

• Which substance has the higher bp at 1 bar: water or bromine?
• Which substance has the higher VP at 20 oC: water or bromine?
 Chem
27 1A03
Sample question
• Figure (1) below represents a sealed vessel of H2O at 25 °C
connected to a tube filled with mercury to measure vapour
pressure.

©2008 – 2020 McMaster University

• Which diagram (2, 3, or 4) represents:
I. H2O at 50 °C?
II. Bromine at 25 °C?
 Chem
28 1A03
Summary of key concepts
• Vapour pressure is related to boiling point, pressure-temperature
diagrams, and thermodynamics
• Vapour pressure is the equilibrium partial pressure of a vapour in the
space above a liquid.A(l) ⇄ A(g) 𝐾 = 𝑃𝐴(𝑔)
• Boiling point is the temperature at which vapour pressure equals
atmospheric pressure.

©2008 – 2020 McMaster University

• Vapour pressure curves:
• given P, determine bp
• given T, determine VP
• As IMF strength increases,
vapour pressure decreases.
 Chem
29 1A03

Chemistry 1A03
Introductory Chemistry I
Chemistry in the context of health,
energy and the environment

©2008 – 2020 McMaster University

Unit 11
Intermolecular
Forces – part 3
 Chem
30 1A03
Learning outcomes – IMF part 3
8. Identify the six phase transitions and the corresponding sign for
ΔH.

9. Explain why sweating helps the body cool down.

©2008 – 2020 McMaster University

 Chem
31 1A03
Learning outcomes – IMF part 3
10. Identify and define key aspects of a phase diagram, including
phases, phase boundaries, critical point, and triple point. Using
a phase diagram, predict the change in state that a substance
undergoes upon a change in temperature or pressure.

11.Identify properties and applications of the triple point and

critical point.

©2008 – 2020 McMaster University

 Chem
32 1A03
Phase Changes
Endothermic
DH >0
Sublimation

Melting Evaporation
Solid Liquid Gas
Freezing Condensation

©2008 – 2020 McMaster University

Deposition
Exothermic

DH < 0
 Chem
33 1A03
Sweating
• Molecules at the surface are able to evaporate
• Energy is required to overcome intermolecular forces
• Evaporation is endothermic

©2008 – 2020 McMaster University

https://pixabay.com/vectors/expressions-fran%C3%A7aises-sun-sweat-1300623/
 Chem
34 1A03
Phase Diagram of CO2

©2008 – 2020 McMaster University

Sublimation

25 °C

See: Figure 12-28 General Chemistry: Principles and Modern Applications, 11th Edition
 Chem
35 1A03
Sample question
What phase changes are occurring on the arrows labeled 1
and 2?

2 1 Freezing
Melting
Condensation

©2008 – 2020 McMaster University

Evaporation
Sublimation
Deposition
See: Figure 12-30 General Chemistry: Principles and Modern Applications, 11th Edition
 Chem
36 1A03
Triple and Critical Points
O - Triple point
Three phases in
equilibrium

C - Critical point
A temperature and
pressure beyond which

©2008 – 2020 McMaster University

liquid and gas are
indistinguishable

Phase Diagram of CO2

Triple point of water video: https://www.youtube.com/watch?v=HEzkHqWIiKM

 Chem
37 1A03
Properties of Supercritical Fluids
At the critical point:
• Density of liquid and vapour are equal
• Surface tension of liquid approaches zero
• The interface between (l) and (g) disappears!

gas

©2008 – 2020 McMaster University

interface

liquid

Below Tc Approaching Tc At Tc
Supercritical fluid video: https://www.youtube.com/watch?v=yBRdBrnIlTQ
 Chem
38 1A03
Supercritical Fluid Solvents
• Replace organic solvents (e.g. dichloromethane,
tetrachloroethylene) in extraction and dry
cleaning
• Avoid release of Cl-containing compounds into
the atmosphere
• Extract natural products (e.g. caffeine) from
sources (e.g. tea/coffee beans) using supercritical

©2008 – 2020 McMaster University

carbon dioxide
• Biocompatible

dichloromethane tetrachloroethylene
 Chem
39 1A03
Summary of key concepts
• Six different phase changes and signs of ΔH.
• Phase diagrams show phases, phase boundaries, phase
changes, triple point, critical point.
• Experiments & real-world applications of triple point and
critical point.

©2008 – 2020 McMaster University

 • STOP HERE!
40
1A03
Chem

©2008 – 2020 McMaster University