CHG 2324

Fundamentals and applications of chemical

engineering thermodynamics

Chapter 3

Winter 2025
Prof. Andrew Anstey
Department of Chemical and Biological Engineering
University of Ottawa 1
Outline

Key ideas in this chapter:

• Application of Gibbs phase rule to pure substances

• Interpreting PV and PT diagrams for pure substances
• Understanding fluid behaviour in the critical regime
• Analyzing behaviours in single-phase regimes using equations of state
• Ideal gases and property relationships in the ideal-gas state
• Utilizing the virial and cubic equations of state
• Understanding generalized correlations for liquids and gases

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 The phase rule

Consider a non-reacting physicochemical system consisting of N components

distributed in a number of phases π at equilibrium. The degrees of freedom F in
this system are defined by the Gibbs phase rule:

3.1

The degrees of freedom F represents the number of independent intensive

variables that are needed to fully define the state of the system.

In the case of a pure substance, N = 1 and thus F depends on the number of

phases of that substance that are present.

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 PVT behaviour of pure substances

Using the Gibbs phase rule, a single material existing in a single phase requires
only 2 intensive properties to fully define the system state:

Therefore, any property of a pure substance can be expressed as a function of two

independent variables ie; volume V (T, P), pressure P (V, T), or internal energy
U (P, T).

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 PVT behaviour of pure substances

• The phase behaviour

of a given substance
is presented
graphically using a
phase diagram.

• P-T and P-V

diagrams are most
commonly used.

• P-T diagrams
illustrate the
boundaries between
single-phase regions
for a pure substance.
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Image via Smith and Van Ness, 9th edition
 PVT behaviour of pure substances
• Triple point: liquid,
solid and gas exist
simultaneously

• Critical point: beyond

Pc and Tc we get a
supercritical fluid

• Following the path from

A to B, a substance
can gradually change
from a liquid to a gas
without vaporization –
no abrupt transition.

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Image via Smith and Van Ness, 9th edition
 PVT behaviour of pure substances

P-V diagrams for pure substances provide insight into the volume associated with
a phase transition, as well as the extent of the transition.

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Image via Smith and Van Ness, 9th edition
 PVT behaviour of pure substances

• Solid: highest density (lowest specific

volume), over most pressures.

• Liquid: relatively high density (slightly

lower than solids)

• Vapour: low density (high specific

volume), over most pressures.

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Image via Smith and Van Ness, 9th edition
 PVT behaviour of pure substances

• Vapour/liquid and vapour/solid

equilibrium areas are large because
there is a large change in
volume/density during condensation.

• Liquid/solid equilibrium area is small

because the volume/density change is
small between these phases.

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Image via Smith and Van Ness, 9th edition
 PVT behaviour of pure substances

• What is the difference between vapour

vs. gas?

• Where is the triple point on this graph?

• Where is the critical point on this graph?

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Image via Smith and Van Ness, 9th edition
 PVT behaviour of pure substances

As a substance transits through the liquid/vapour region, the balance between the
two depends on the distance between the equilibrium lines.

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Image via Worcester Polytechnic Institute
 PVT behaviour of pure substances

• Vapour/liquid regions are of greatest

interest for chemical engineering
processes.

• Key features here:

→ Saturated liquid
→ Saturated vapour
→ Subcooled liquid
→ Superheated vapour
→ Isothermal lines T1, T2, TC

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Image via Smith and Van Ness, 9th edition
 PVT surfaces

• Recall: a pure substance existing in a

single phase can be fully defined by two
state variables.

• In these circumstances, we can express

a PVT relationship as a 3-dimensional
surface. Black lines drawn through
surface represent isothermal paths.

• We can imagine our 2-dimensional P-T

and P-V plots as “slices” of this surface.

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Image via Smith and Van Ness, 9th edition
 Application example

• Aerogels are ultra-low density

materials that are derived via
secondary processing of a polymer
gel.

• As the name suggests, aerogels are

made almost entirely of air (in some
cases over 99%)

• Due to their extremely light weight

and excellent insulating properties,
aerogels are highly desirable in
aerospace applications.

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Image via NASA.
 Application example

Solvent exchange and supercritical drying

• Solvent exchange is used to replace aqueous solvent with a CO2 miscible solvent such
as acetone. Next, the CO2 miscible solvent is replaced with liquid CO2
• Pressure is increased to bring CO2 above the critical point. Depressurization causes the
supercritical CO2 to convert directly into the gaseous state, allowing its removal without
collapse.

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Image via Materials 14, no. 7 (2021): 1631.
 Application example

Solvent exchange and supercritical drying

• Solvent exchange is used to replace aqueous solvent with a CO2 miscible solvent such
as acetone. Next, the CO2 miscible solvent is replaced with liquid CO2
• Pressure is increased to bring CO2 above the critical point. Depressurization causes the
supercritical CO2 to convert directly into the gaseous state, allowing its removal without
collapse.

Supercritical Ambient drying

drying

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Image via Journal of Materials Science, 47, pp.2995-3025.
 PVT surfaces

For regions on these diagrams where only a single phase exists, the relationship
between pressure, volume and temperature can be expressed analytically by:

This relationship is known as a PVT equation of state (EOS) – the simplest

example of this being the ideal gas law. This particular EOS is valid for
homogeneous gases at low pressures.

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 PVT surfaces

Using the ideal gas law, consider the case in which we express volume as a
function of temperature and pressure:

We can express a relationship for changes in volume with the derivative of the
function above, where:

3.2
𝑷 𝑻

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 PVT surfaces

The two terms in this partial differential equation have real physical meanings, and
a related to two commonly tabulated properties for liquids:

𝟏 𝝏𝑽
Volume expansivity: 3.3
𝑽 𝝏𝑻 𝑷

𝟏 𝝏𝑽
Isothermal compressibility: 3.4
𝑽 𝝏𝑷 𝑻

Using these terms, we can redefine equation 3.2 as:

3.5

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 PVT surfaces

• Isotherms in the liquid region of this PV

diagram are steep and closely spaced –
hence, and must be small.

• In most cases*, there is not much error if

we assume that and are invariant with
respect to small changes in P and T.
Integrating 3.5 gives:

𝟐
3.6 𝟐 𝟏 𝟐 𝟏
𝟏
Image via Smith and Van Ness, 9th edition
*at conditions far from the critical point 20
 Ideal gas and ideal-gas state

• The ideal gas equation is the equation of state for gases, and is valid at low
pressures and high temperatures. Usually a good approximation at ambient
conditions – for higher pressures and lower temperatures, its predictions fail.

• Key assumptions:
→ Molecules in the gas have no volume (treated as point-like particles)
→ No interactions between molecules

• Ideal-gas state: a hypothetical state in which a gas perfectly obeys the ideal gas
law.

• In the ideal-gas state, there is no pressure dependency, only temperature – why?

• The ideal gas law was discovered experimentally, but can be derived from first
principles using the assumptions above (alvarofeito.com/articles/ideal-gas/) 21
 Ideal gas and ideal-gas state

This state is defined by two equations:

𝒊𝒈
Equation of state: 3.7

𝒊𝒈 3.8
Internal energy:

For real gases, this law does not hold, as U = U (T, P). So then why bother with it in
the first place? For real gases (more on this in chapter 6), we can perform
calculations in three steps:

1. Evaluate property changes for transforming real-gas state into ideal-gas

state.
2. Calculate property changes in the ideal state.
3. Evaluate property changes for transformation of ideal-gas state back into
real-gas state.
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 Ideal gas and ideal-gas state
Recall from chapter 2:

For constant volume and constant pressure, we define the heat capacity CV and CP
(respectively) as:

𝝏𝑼 𝝏𝑯
𝑽 𝝏𝑻 𝑽 𝑷 𝝏𝑻 𝑷

𝑽 𝑷

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 Ideal gas and ideal-gas state
Using these definitions with 3.7 and 3.8 yields:

𝒊𝒈 𝒊𝒈
𝒊𝒈 𝒊𝒈
3.9 𝒗 𝒗
𝑽 𝑽

Enthalpy in the ideal-gas state:

3.10 𝒊𝒈 𝒊𝒈 𝒊𝒈 𝒊𝒈 𝒊𝒈

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 Ideal gas and ideal-gas state
Cp is also a function of temperature only in the ideal-gas state:

𝒊𝒈 𝒊𝒈
𝒊𝒈 𝒊𝒈
3.11 𝒑 𝑷
𝑷 𝑷

We find a relation between the two heat capacity values:

𝒊𝒈 𝒊𝒈
𝒊𝒈 𝒊𝒈
3.12 𝒑 𝑽

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 Ideal gas and ideal-gas state
From equations 3.9 and 3.11, we obtain:

𝒊𝒈 𝒊𝒈
3.13a 𝑽
𝒊𝒈 𝒊𝒈
3.13b 𝑽

3.14a 𝒊𝒈 𝒊𝒈
𝑷
𝒊𝒈
3.14b 𝒊𝒈
𝑷

As usual, since U and H are state functions, ΔU and ΔH depend only on the initial
and final states, and not the path taken between them.

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 Process calculations for the ideal-gas state
For a closed system, mechanically reversible process:
𝒊𝒈 𝒊𝒈
𝑽

𝒊𝒈 𝒊𝒈
Rearranging: 𝑽 3.15

𝒊𝒈 𝒅𝑽𝒊𝒈
Using : 𝑽
3.16
𝑽𝒊𝒈

𝒅𝑽𝒊𝒈
3.17
𝑽𝒊𝒈

And then using and with 3.12:

𝒊𝒈 𝒅𝑷 𝒅𝑷
𝑷 𝑷 𝑷
3.18 3.19 27
 Process calculations for the ideal-gas state
For an isothermal process (constant T), 3.13b and 3.19 yield:

𝒊𝒈 𝒊𝒈 (remember that dT = 0)

Because U = Q + W = 0, integrating equations 3.16 – 3.19 gives:

𝒊𝒈
𝟐 𝟏
𝒊𝒈
𝟐
𝟏
𝒊𝒈
𝟏 𝟐
𝒊𝒈
𝟏
𝟐

Thus we have:
𝒊𝒈
𝟐 𝟏
𝒊𝒈 3.20
𝟐
𝟏 28
 Process calculations for the ideal-gas state
For an isobaric process (constant P), 3.13b and 3.19 yield:

𝒊𝒈 𝒊𝒈
𝑽 𝟐 𝟏 (remember that dP = 0)

Using equations 3.14b and 3.18 gives:

𝒊𝒈 𝒊𝒈 3.21
𝑷

For an isochoric process (constant V), 3.13b and 3.16 yield: (remember that dV = 0
and W = 0)

𝒊𝒈 𝒊𝒈
𝑽 3.22

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 Process calculations for the ideal-gas state
An adiabatic process is one for which no heat is transferred between the system
and the surroundings (ie; dQ = 0). Setting equation 3.16 equal to 0 and integrating
gives:
𝑹
𝒊𝒈 𝒊𝒈 𝒊𝒈
𝑪𝑽
𝟐 𝟏
𝒊𝒈 𝒊𝒈 𝒊𝒈
𝟏
𝑽 𝟐

Alternatively, setting equation 3.18 equal to 0 and integrating gives:

𝑹
𝒊𝒈
𝟐 𝟐 𝑪𝑷
𝒊𝒈
𝟏 𝟏
𝑷

Equating the two, we get:

𝒊𝒈
𝑪𝑷
𝒊𝒈 𝒊𝒈
𝑪𝑽
𝟐 𝟏
𝒊𝒈
𝟏
𝟐 30
 Process calculations for the ideal-gas state
We can rewrite the previous equations as:

𝒊𝒈 𝜸 𝟏 3.23a
𝟏 𝜸⁄ 𝜸
3.23b
𝒊𝒈 𝜸 3.23c

𝒊𝒈
𝑪𝑷
By definition: 𝒊𝒈
3.24
𝑪𝑽

With this definition and 3.12:

𝑹 𝑹 𝜸 𝟏
𝒊𝒈 and 𝒊𝒈
𝑪𝑽 𝑪𝑷 𝜸

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 Process calculations for the ideal-gas state
For ΔU and ΔH, equations 3.13b and 3.14b remain valid.

For an adiabatic process (dQ = 0) in a closed system, equation 3.13a becomes:

𝒊𝒈
𝑽

𝒊𝒈 𝒊𝒈 𝒊𝒈 𝑹𝜟𝑻 3.25
For constant 𝑽 : 𝑽 𝜸 𝟏

Using the ideal gas equation of state:

𝒊𝒈 𝒊𝒈
𝟐 𝟏 𝟐 𝟐 𝟏 𝟏
3.26

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 Process calculations for the ideal-gas state
For a compression/expansion processes, we typically only know the initial state and
the final pressure (ie: V2 is unknown). We can rewrite 3.26 accordingly using 3.23c:

𝒊𝒈 𝜸 𝟏⁄𝜸 𝜸 𝟏 ⁄𝜸
𝟏 𝟏 𝟐 𝟏 𝟐
3.27
𝟏 𝟏

When applied to real gases, equations 3.23 through 3.27 tend to give satisfactory
explanations for reversible, closed adiabatic processes.

• For monatomic gases, = 1.67

• For diatomic gases, = 1.4
• For simple molecules, = 1.3

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Next lecture: Virial and cubic equations of state

Reading: Chapter 3

Practice problems: to be posted

Check out:
• https://alvarofeito.com/articles/ideal-gas/ (first principles derivation of
the ideal gas law)

• https://youtu.be/eyn7MusdQ9g?si=Ny0u8NeZR_cwPO2U (first 14
minutes give an approachable explanation of phase transitions and
supercritical state)

• https://www.youtube.com/watch?v=cXcF8Z1zD7M&list=PLpwExhz092
Aq5zSWEB_ISZxi_Nff9V5yd&index=6 (PV diagram explainer)
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