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

2
 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.

3
 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).

4
 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.
5
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.

6
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.

7
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.

8
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.

9
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?

10
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.

11
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

12
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.

13
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.

14
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.

15
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

16
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.

17
 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

19
 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 ([Link]/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

23
 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

24
 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

25
 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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 Adiabatic processes
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
 Adiabatic processes
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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 Adiabatic processes
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

32
 Adiabatic processes
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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 Irreversible processes
• Regardless of the path taken during the process, or the reversibility of the
process, the equations for 𝒊𝒈 , 𝒊𝒈 , 𝒊𝒈 , and 𝒊𝒈 remain valid.

• However, the equations used for Q and W will change depending on the process.
The work for an irreversible process is generally calculated in two steps:

1. Determine W for a mechanically reversible process that accomplishes the

same state change as the real, irreversible process of interest.

2. For work produced by the system, multiply by a mechanical efficiency factor.

For work done on the system, divide by a mechanical efficiency factor.

34
 Irreversible processes
Example 3.3: Air is compressed from an initial state of 1 bar and 298.15 K to a final
state of 3 bar and 298.15 K by three different mechanically reversible processes in a
closed system. The air has a molar volume of 0.02479 m3/mol in the initial state.

a) Heating at constant V, then cooling at

constant P
b) Isothermal compression
c) Adiabatic compression, then cooling at
constant V

Calculate the W, Q, ΔU, and ΔH of the air

for each process, given:

𝒊𝒈
𝑽 20.785 J/mol∙K
𝒊𝒈
𝑷 29.100 J/mol∙K
35
Image via Smith and Van Ness, 9th edition
 Virial equations of state
What happens when the ideal gas law no longer holds? (ie; )

One way to describe this deviation from ideal behaviour is using virial expansion.
For a non-ideal fluid, we want to develop an equation that can capture this across a
range of temperatures.

First, we introduce the compressibility factor Z:

3.32

→ For an ideal gas, Z = 1.

→ When repulsive forces between molecules dominate, Z > 1.
→ When attractive forces between molecules dominate, Z < 1.

36
 Virial equations of state
• Z is a dimensionless value
that can be thought of as a
measure of the deviation of
volume/density from ideal-
gas behaviour.

• As with our PVT variables,

we can plot PZT as a
surface.

• In this particular
representation, we are
mapping the compressibility
of CO2 as a function of
temperature and pressure.
37
Image via Smith and Van Ness, 9th edition
 Virial equations of state
To develop the virial equations, we express Z as a Taylor expansion in terms of V -1:

3.33
𝟐 𝟑

or in terms of P: 𝟐 𝟑 3.34

These parameters B, C, D and B’, C’, D’ are known as virial coefficients. B/B’ are
the second virial coefficients, C/C’ are the third virial coefficients, and so on.

Equating 3.33 and 3.34, and using 3.32 to simplify:

𝟐 𝟑
3.35a-c
𝟐 𝟑
38
 Applying the virial equations
• The virial equations of state are firmly based on statistical mechanics – the virial
coefficients have physical meanings (rather than just being empirical coefficients
that “make the equations work”.

→ The B term arises from interactions between pairs of molecules.

→ The C term arises from three-body interactions.

→ and so on, with higher order terms corresponding to higher order interactions.

• Higher order terms have smaller and smaller contributions to the ultimate value of
Z.

39
 Applying the virial equations
• Consider a plot of Z vs P for
methane.

• All isothermal lines originate at P =

0 and Z = 1 – why?

• At 350K and 500K, the slope is

much less steep – what does this
imply?

• For low pressures, each of these

isotherms is fairly linear and can be
approximated by a tangent at P = 0.

40
Image via Smith and Van Ness, 9th edition
 Applying the virial equations
How do we find the slope at P = 0? Differentiating eq. 3.34 for constant T gives:

𝝏𝒁
At P = 0, we get , and hence our tangent line in this linear region is
𝝏𝑷 𝑻
defined by:

3.36

This expression provides reasonable approximations at low pressures.

41
 Applying the virial equations
The two-term expansion can be written as either:

𝑷𝑽 𝑩𝑷 𝑷𝑽 𝑩
or 3.37
𝑹𝑻 𝑹𝑻 𝑹𝑻 𝑽

B is substance-dependent and is a function of temperature – experimental values

are available for many substances.

For pressures beyond the applicability of eq. 3.36 and 3.37, the three term virial
expansion can be used:

𝟐 3.38

Values for C are also substance-dependent functions of temperature. Higher order

virial terms are very rarely used.
42
 Applying the virial equations
Virial coefficients B and C for N2 as a function of temperature:

43
Image via Smith and Van Ness, 9th edition
 Applying the virial equations
Example 3.8: Reported values for the virial coefficients of isopropanol vapor at
200 °C are:

B = -388 cm3/mol
C = -26,000 cm6/mol2

Calculate V and Z for isopropanol at 200°C and 10 bar.

a) For the ideal-gas state

b) Using the 2-term virial expansion (eq. 3.36)

44
 Cubic equations of state
Cubic equations of state are simple, empirical equations capable of approximating
both liquid and vapour behaviour. The first practical cubic equation of state was
developed by van der Waals (vdW EOS).

3.39
𝟐

• Both a and b are positive constants, specific to each fluid.

𝒂
• The term accounts for attractive forces between molecules.
𝑽𝟐

• The term accounts for the finite size of molecules.

45
 Cubic equations of state
Behaviour of isotherms as predicted by
typical cubic EOS:

• For T > Tc, cubic EOS are nearly ideal and

monotonic.

• For T = Tc, there is an inflection at the

critical point

• For T < Tc, liquid and vapour regions are

well-described by the EOS, but the 2-
phase region is not.

46
Image via Smith and Van Ness, 9th edition
 General cubic equation of state
Over time, many tweaks and modifications have been made to the vdW EOS,
resulting to new equations of state. The first such example is the Redlich/Kwong
(RK) equation:

3.40

Further developments have taken the general form of:

3.41

For a given equation, and are the same for all substances, while and are
substance-dependent.
47
 General cubic equation of state
Parameters and can be determined by noting the inflection point at the
critical temperature, allowing us to impose the following mathematical conditions:

𝝏𝑷 𝝏𝟐 𝑷
3.42 and 3.43
𝝏𝑽 𝑻;𝒄𝒓 𝝏𝑽𝟐 𝑻;𝒄𝒓

Through differentiation of 3.41 and a whole bunch of algebra, we get:

𝑹𝑻𝑪 𝑹𝟐 𝑻𝟐𝑪
3.44 and 𝒄
𝑷𝑪 𝑷𝒄

a(T) can be extrapolated to other temperatures via:

different
things! 𝟐 𝟐
𝒓 𝑪
3.45
𝒄 48
 General cubic equation of state
In cubic equations of state defining b and a(T):

𝑹𝑻𝑪 𝜶(𝑻𝒓 ,𝝎)𝑹𝟐 𝑻𝟐𝑪

3.44 and 3.45
𝑷𝑪 𝑷𝒄

→ and are independent of substance, but specific to each equation of state.

→ 𝒓 is an empirical expression for each equation of state, with 𝒓 𝒄.

The quantity is a substance-specific parameter known as the acentric factor.

→ Given that we have Tc, Pc, and Vc at the critical point, it follows that there is also a
critical compressibility factor Zc. All these values are found in Appendix B in the
textbook for a variety of pure substances.

49
 General cubic equation of state
The values for 𝒓 , , , , and Zc are defined differently in different equations
of state.

EOS (year) 𝜶(𝑻𝒓 ) 𝝈 𝜺 𝜴 𝜳 ZC

van der Waals vdW 1 0 0 1/8 27/64 3/8
(1873)
Redlich/Kwong RK 𝑇
⁄ 1 0 0.08664 0.42748 1/3
(1949)
Soave/Redlich/Kwong SRK 𝛼 𝑇 ,𝜔 * 1 0 0.08664 0.42748 1/3
(1972)
Peng-Robinson PR 𝛼 𝑇 , 𝜔 ** 1+ 2 1− 2 0.07780 0.42748 0.30740
(1976)

/
* 𝛼 𝑇 ; 𝜔 = 1 + 0.480 + 1.574𝜔 − 0.176𝜔 1−𝑇

/
** 𝛼 𝑇 ; 𝜔 = 1 + 0.37464 + 1.54226𝜔 − 0.26992𝜔 1−𝑇

50
 General cubic equation of state
To further simplify, we define two additional dimensionless quantities:

𝒃𝑷 𝒂(𝑻)
3.46 and 3.47
𝑹𝑻 𝒃𝑹𝑻

Substituting these into 3.41 and rewriting in terms of Z leads to:

3.48

The roots of this cubic equation can be determined through iterative procedures,
starting at Z = 1 to find a value that converges for Z yielding 𝒊𝒈 .

Equation 3.48 is useful for solving for the vapour-like root (ie; the root along the
saturated vapour line).
51
 General cubic equation of state
Another form of eq 3.48 is suited for solving for the liquid root (ie; root along the
saturated liquid line):

3.49

The roots of this cubic equation can be determined through iterative procedures,
starting with to find a value that converges for Z yielding 𝒊𝒈 .

Combining 3.46 and 3.47 with equations 3.44 and 3.45 yields:

𝑷𝒓 𝜳𝜶(𝑻𝒓 ,𝝎)
3.50 and 3.51
𝑻𝒓 𝜴𝑻𝒓

where the reduced temperature 𝒓 𝒄 and the reduced pressure 𝒓 𝒄

52
 General cubic equation of state
Example 3.9: Given that the vapor pressure of n-butane at 350 K is 9.4573 bar, find
the molar volumes of (a) saturated-vapor and (b) saturated-liquid n-butane at these
conditions as given by the Redlich/Kwong equation.

How do we approach a problem like this?

53
 General cubic equation of state
• From Appendix B in the textbook, we find values for Tc and Pc for n-butane.
• Knowing that we are using the RK EOS, we can find our values for 𝒓 , , ,
, and Zc.

𝑇 = .
= 0.8233

.
𝑃 = .
= 0.2491

⁄
⁄
𝑞= = 𝑇 = 6.6048

( . )( . )
𝛽 = 𝛺 = .
= 0.026214

54
 General cubic equation of state
• Use 3.48 to find the root along the saturated vapour line.
• Since and in this model, 3.48 is simplified.

Next step is to solve this by iteration – what does that mean?

55
 General cubic equation of state
• Iteration can be easily set up in software of your choice.
• After sufficient iterations, Z will converge to the solution.

56
 General cubic equation of state
• Similar approach is used for finding the zero along the saturated liquid line.

57
 Generalized correlations
The dimensionless coordinates Tr and Pr (reduced temperature and pressure)
provide the basis for the two-parameter theorem of corresponding states:

All fluids, when compared at the same reduced temperature and reduced pressure,
have approximately the same compressibility factor, and all deviate from ideal-gas
state behaviour to about the same degree.

𝒓 𝒓

We can determine PVT values when we know the values of Tr, Pr and the acentric
factor , which was introduced by Pitzer. For simple fluids (such as Ar, Xe, Kr) we
can use Tr and Pr , but more complex fluids require the use of as well.

58
 Generalized correlations
The acentric factor of a fluid is defined
in reference to its vapour pressure
when evaluated at Tr = 0.7.

𝒔𝒂𝒕
3.52 𝟏𝟎 𝒓 𝑻𝒓 𝟎.𝟕

All fluids with the same acentric factor

value, when compared at the same
reduced temperature and reduced
pressure, have approximately the
same compressibility factor, and all
deviate from the ideal gas behaviour to
approximately the same degree.

59
Image via Smith and Van Ness, 9th edition
 Pitzer correlations
Pitzer general correlation for gases – the compressibility factor Z:

𝟎 𝟏 3.53

• For simple fluids, and 𝟎.

• Values for 𝟎 and 𝟏 are available in the Lee/Kesler tables (Appendix D in your
textbook).
• Reliable for non-polar and slightly polar gases.
• Double linear interpolation (illustrated in Appendix E) is required when using
these tables to determine 𝟎 and 𝟏 .

60
 Pitzer correlations
Pitzer general correlation for gases – the second virial coefficient B. Based on eq.
3.36:

𝑪 𝒓 𝒓
3.57
𝑪 𝒓 𝒓

Pitzer and collaborators proposed the following correlations for :

𝑩𝑷𝑪 𝟎 𝟏
3.58 and 3.59
𝑹𝑻𝑪

Equations 3.57 and 3.59 together become:

𝟎 𝒓 𝟏 𝒓
𝒓 𝒓 61
 Pitzer correlations
Comparing this expression with equation 3.53, we find that:

𝟎 𝟎 𝑷𝒓 𝟏 𝟏 𝑷𝒓
3.60 and
𝑻𝒓 𝑻𝒓

𝟎 𝟏
The second virial coefficients are functions of T only – likewise, and are
functions of T only. They are defined by the Abbott equations:

3.61 𝟎
𝟏.𝟔
𝒓

3.62 𝟏
𝟒.𝟐
𝒓

62
 Pitzer correlations
• Above the dashed line, the Pitzer
correlations for B (line) differ by <
2% from the tabular Lee-Kesler
correlations for Z (points).

• As a general rule, below the critical

point, for most species, Eqns. 3.59-
3.62 are reasonable approximations
for pressures up to the vapour
pressure of a given species.

• Valid at low to moderate pressures.

63
Image via Smith and Van Ness, 9th edition
 Pitzer correlations
Pitzer correlations are available for the third virial coefficient C. Equation 3.38 can
be rewritten in the reduced form:
𝟐
𝒓 𝒓
3.63
𝒓 𝒓

𝑪𝑷𝟐𝑪
3.64 and 𝟎 𝟏 3.65
𝑹𝟐 𝑻𝟐𝑪

𝟎
𝟏𝟎.𝟓 3.66
𝒓 𝒓
𝟏
𝟐.𝟕 𝟏𝟎.𝟓 3.67
𝒓 𝒓

Because 3.63 is cubic, Z must be determined via iteration – again, we can start by
setting Z equal to 1 on the right side of the equation.
64
 Pitzer correlations
• When Z or Z0 are between 0.98-
1.02, the ideal-gas state provides a
reasonable approximation.

• This corresponds to the area under

the solid lines in this plot of Pr vs. Tr

• Z0 tends to be the most dominant

term in eq. 3.53

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Image via Smith and Van Ness, 9th edition
 Generalized correlations for liquids
Molar volumes of liquids can be calculated using generalized cubic equations of
state, but the results are often inaccurate.

The Lee/Kesler correlations (found in Appendix D) include data for liquids, but
these are most suitable for nonpolar and slightly polar liquids.

The simplest generalized equations for estimating the molar volumes of saturated
liquids are those proposed by Rackett:

𝒔𝒂𝒕 (𝟏 𝑻𝒓 )𝟐/𝟕
𝒄 𝒄 3.68

𝒔𝒂𝒕 𝒓 [𝟏 (𝟏 𝑻𝒓 )𝟐/𝟕 ] 3.69

𝒄
𝒓

66
 Subcooled liquid volumes
Lyderson, Greenkorn, and Hougen
developed a two-parameter
corresponding-states correlation for
estimating liquid volumes, providing a
correlation for reduced density 𝒓 as a
function of 𝒓 and 𝒓 . By definition: 3.68

𝒄
3.70 𝒓 𝒓
𝟏
𝒄

This generalized correlation is shown in the plot above; it can alternately be

expressed as 3.71. In situations where V1, T1, and P1 are known, 𝒓𝟏 and 𝒓𝟐 can
be found from the plot and used to solve for unknown V2.

𝒓𝟏
3.71 𝟐 𝟏
Image via Smith and Van Ness, 9th edition
𝒓𝟐 67
Next lecture: Chapter 4

Reading: Chapter 4

Practice problems:

Chapter 3: Examples 3.4, 3.7, 3.8, 3.10, 3.13.

Practice problems 3.4, 3.9, 3.11, 3.16, 3.19, 3.20, 3.24,
3.28, 3.36, 3.42, 3.45, 3.54, 3.55, 3.65, 3.67

68