Chapter 11 – Liquids, Solids and

Intermolecular Forces

Jim Ghoshdastidar
Department of Chemistry and Biology
Ryerson University, Toronto, ON

CHY 113 – General Chemistry II

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MODULE 11B – PHASE CHANGES
FORCES OF ATTRACTION & REPULSION

CHY 102 – General Chemistry I 2

 11.0 Learning Objectives
 11.5 Vaporization and Vapor Pressure
 Understand the process of vaporization and how it changes with temperature, surface area, and the
degree of intermolecular forces.
 Understand that molecules or atoms have a distribution of thermal energies that changes as a function
of temperature.
 Know that the heat of vaporization, ΔHvap, is a quantitative measure for the process of vaporization.
 Calculate and interconvert mass, moles, and energy using the heat of vaporization.
 Know and understand how vapor pressure and dynamic equilibrium dictate vaporization and
condensation.
 Know that the vapor pressure of a liquid depends on temperature and that the boiling point of a liquid
depends on the external pressure.
 Use the Clausius-Clapeyron equation to relate temperature and vapor pressure.
 Define critical temperature and critical pressure.

CHY 113 – General Chemistry II 3

 11.0 Learning Objectives
 11.6 Sublimation and Fusion
 Define and understand sublimation and deposition.
 Define and understand fusion in the context of phase changes.
 11.7 Heating Curve for Water
 Understand the different segments in the heating curve for H2O that ranges from below the melting
point to above the boiling point.
 Calculate the energy changes associated with heating a substance (like H2O) through a series of
temperature changes and phase changes.
 11.8 Phase Diagrams
 Know that a phase diagram relates the states of matter for a substance to temperature and pressure.
 Identify the main regions and significant points in a phase diagram.
 Understand the effect of changes in temperature and changes in pressure on the phase of a substance
as shown by its phase diagram.

CHY 113 – General Chemistry II 4

 11.2 Vapour Pressure Revisited
The molecular view of vapour
pressure:
 Some molecules on the surface
of a liquid have enough energy
to escape the bulk liquid and go
into the gas phase.
 As number of gas phase
molecules increase, some Question: What
strike the surface and return to factors affect the
the liquid (condensation). rate of vaporization?

CHY 113 – General Chemistry II 5

 11.2 Phase Change Equilibria

Pvap

The vapor pressure is the pressure exerted by the vapor

In a closed flask, the system reaches on the liquid. The pressure increases until equilibrium is
reached; at equilibrium the pressure is constant.
a state of dynamic equilibrium,
where molecules are leaving and
entering the liquid at the same rate. 6
 11.2 Vapour Pressure
vaporization
liquid condensation
vapor
Vapour Pressure –
the partial pressure
of molecules in the
gaseous state at a
given temp

𝑃𝑣𝑎𝑝 = 0 𝑃𝑣𝑎𝑝 < 𝑃𝑏𝑎𝑟 𝑃𝑣𝑎𝑝 = 𝑃𝑏𝑎𝑟

The rate of vaporization depends on temperature, IFs and the surface area
of the liquid, and is independent of the rate of condensation, which
depends on the vapour pressure. 7
 11.2 Volatility, Vapour Pressure and Temperature
 A substance with a high vapour pressure will vapourize more quickly than a
substance with a low vapour pressure.
 The word volatile is used to describe liquids that vapourize readily.
 A liquid boils when its vapour pressure equals the external pressure acting
on the surface of the liquid.
 The normal boiling point is the boiling point at 1 atm and he standard boiling
point is the boiling point at 1 bar.
 The heat of vaporization, ΔvapH⁰,
is the energy required to vaporize
one mole of a liquid to a gas.

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 11.2 Volatility and Intermolecular Forces
A volatile substance has a vapor pressure at ordinary temperatures.
These substances have weak IFs. Diethyl
Clausius - ∆𝐻𝑣𝑎𝑝 1 Ether Water
Clapeyron relates ln 𝑃 = −
vapour pressures 𝑅 𝑇
to temperatures
Toluene

Benzene

Aniline

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 11.2 Clausius-Clapeyron Equation
Vapor pressure increases with increasing temperature
because: T2 > T1 is positive, and In (P2/P1) is positive too
because enthalpy of vaporization is positive.

ΔHvap° is a measure of the intermolecular interaction

strength (ion–dipole, dipole–dipole, hydrogen bonding,
London forces).

𝑃2 −∆𝐻𝑣𝑎𝑝 1 1
ln = −
𝑃1 𝑅 𝑇2 𝑇1
P = pressure (any units)
R = 8.314 J mol-1K-1
T = temperature (K)
ΔvapH⁰ = enthalpy of vaporization (Jmol-1) 10
Enthalpy of vaporization (ΔHvap) > Enthalpy of fusion (ΔHfus)
The magnitude of these ΔH’s increases with ↑ IFs

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 𝒌𝑱
Example Question – The enthalpy of vaporization of 𝑪𝑪𝒍𝟒 is 33.05𝒎𝒐𝒍 , and its vapor pressure at 57.8 °C is 405 Torr. What is
the vapour pressure of tetrachloromethane at 25.0 °C?

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 11.2 Phase Changes
In general, each state of matter (solid, liquid or gas) can change into
either of the other two states under the proper conditions. These
transformations, called phase changes, are accompanied by a change
in the energy of the system.
Change Name Enthalpy Process
Solid to gas Sublimation ΔHsub > 0 Endothermic
Solid to liquid Melting/Fusion ΔHfus > 0
Liquid to gas Vaporization ΔHvap > 0
Gas to solid Deposition ΔHdep < 0 Exothermic
Gas to Liquid Condensation ΔHcon < 0
Liquid to solid Freezing ΔHfre < 0

CHY 113 – General Chemistry II 13

 High Kinetic Energy
Phase changes involve
the forming, breaking or
changing the strength of
intermolecular forces.

Heat of Vaporization

Heat of Fusion

Low Kinetic Energy 14

 Example – Heating Curves
From the data below, calculate the total heat (in J) needed/released to convert 0.333 mol of
ethanol (C2H5OH) at 300 ° C and 1 bar to liquid ethanol at 25 °C and 1 bar.
[Link] at 1 bar: 78.5 °C sgas = 1.43 J g-1 °C-1
∆vapHo = 40.5 kJ mol-1 sliquid = 2.45 J g-1 °C-1

CHY 113 – General Chemistry II 15

 11.2 Critical Point and Supercritical Fluids
Critical Point – liquid and
vapor phases become
indistinguishable and
form a supercritical fluid
with properties of liquids
and gases

Critical Temperature – temperature above which liquid cannot

exist no matter the pressure applied
Critical Pressure – maximum pressure for gas to transition to
liquid 16
Example – Critical Temperatures and Pressures
Substance Critical Temp (K) Critical Pressure (atm)

Nitrogen 126.1 33.5

Oxygen 154.4 49.7
Water 647.6 217.7

n-pentane

CHY 113 – General Chemistry II 17

Phase Diagrams – the stable phases
that a substance occupies at varying
pressure and temperatures

Boundaries – the temperatures

and pressures at which two
phases are in equilibrium

Phase diagrams are different for

every substance and consolidate a lot
of information.

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 11.2 Phase Diagrams and Phase Transitions
Triple Point – the
temperature and pressure at
which three states are in
equilibrium [can be multiple]

If we change P & T, we
can cause the system to
cross phase boundaries. Sublimation
deposition

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 11.2 Phase Transitions and Phase Diagrams

Moving over a transition by

increasing T, at constant P, results in
DHfus
an enthalpy increase.
These transitions are endothermic.
DHvap
Moving over a transition by
increasing P, at constant T, results
in an increase in density.
DHsub
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11.2 Phase Diagram for Carbon Dioxide
The Fusion Curve has a positive slope. As we
increase the pressure on the liquid, the denser
state is favoured which is the solid state

Carbon Dioxide does not have a Normal

Melting Point

At 1 atm, carbon dioxide exists only as a

gas or solid.

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 11.2 Phase Diagrams - Water
The solid-liquid line slants to the
left for H2O, because the solid is
less dense than the liquid. Water
expands on freezing.

At 1 atm, water can exist

as a solid, liquid or gas.

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11.2 Phase Diagrams – Bismuth and Carbon

bismuth
CHY 113 – General Chemistry II 23
Concept Check – Phase Diagram
Which regions represent the
solid forms?
A. A&C
B. B&C
B C. A&B
D. A&D
C
A
How many triple points
are there?
D
A. 1
B. 2
C. 3
D. 0
CHY 113 – General Chemistry II 24
Chapter 13 – Kinetics

Noel George
Department of Chemistry and Biology
Ryerson University, Toronto, ON

CHY 113 – General Chemistry II

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