Introduction to Chemical

Engineering Thermodynamics

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CHENG 211
Chapter 3:

Volumetric Properties of Pure

Fluids

Instructor:
Dr. Hayat Abdulla Yusuf

Modified from:
Dr. Mohammad Al- Aseeri & Dr. Shaker Haji

Dr. Hayat Abdulla Yusuf 1

Ref: the course’s textbook, by Smith J.M et al
Chapter 3 Objectives:

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Present a rule which relates the number of independent variables required
to fix the thermodynamic state of a system species and phases present ∙

Describe qualitatively the general nature of PVT behavior of pure substances

Provide a detailed treatment of the ideal-gas state ∙

Treat equations of state, which are mathematical formulations of the PVT

behavior of fluids
Introduce generalized correlations that allow prediction of the PVT behavior
of fluids for which experimental data are lacking
Dr. Hayat Abdulla Yusuf 2
Introduction and sec. 3.1

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3.1 The Phase Rule

Dr. Hayat Abdulla Yusuf 3

3.1 The Phase Rule

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• For multi-phase systems at equilibrium, the number of independent variables that
must be arbitrary fixed to establish its intensive state is given by the celebrated
phase rule of J. Willard Gibbs. It is presented here to non-reacting systems:

F  N  2
Where
•  is the number of phases,
• N is the number of chemical species
• F is the degree of freedom (D.F.).

Dr. Hayat Abdulla Yusuf 4

 3.1 The Phase Rule

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• The phase rule is concerned with the phases of the system.
• The intensive state (of each phase) of a system at equilibrium is established when
its T, P & the compositions of all phases are fixed.
• These are therefore phase-rule variables, but they are not all independent.

• The phase rule gives the number of variables from this set which must be arbitrary
specified to fix all remaining phase-rule variables, and thus the intensive state of
the system.
Dr. Hayat Abdulla Yusuf 5
 3.1 The Phase Rule

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• A phase is a homogeneous region of matter. It needs not be continuous.

• Note that,
• An abrupt change in properties always occurs at the boundary b/n phases.
• Various phases can coexist, but they must be in equilibrium for the phase rule to
apply.
• Example: Saturated aqueous salt solution at its boiling point with excess salt
crystals present, for this system DF =?
• The phase-rule variables are intensive properties, independent of the extent of
the system and of the individual phases.
Dr. Hayat Abdulla Yusuf 6
 3.1 The Phase Rule

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Note that,

• The phase rule gives the same information for a large system as for a small one
and for different relative amounts of phases.

• Moreover, only individual-phase compositions are phase rule variables; overall or

total compositions are not phased variables when more than one phase is present.

• The minimum number of degrees of freedom (D.F.) for any system is zero. When
F=0, the system is invariant. Dr. Hayat Abdulla Yusuf 7
 Example

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• Use the Gibbs Phase Rule to determine the number of the intensive
properties that can be defined for a saturated liquid-vapor water mixture.
Are all the phase-rule variables (T, P, & the compositions of all phases)
fixed when the T is given?

Dr. Hayat Abdulla Yusuf 8

 Example 3.1_Modified

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How many DOF has each of the following systems

a) Liquid water in equilibrium with its vapor

b) Liquid water in equilibrium with a mixture of water vapor and nitrogen
c) A liquid solution of alcohol in water in equilibrium with its vapor

Dr. Hayat Abdulla Yusuf 9

Sec. 3.2

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PVT Behavior of
Pure Substances

Dr. Hayat Abdulla Yusuf 10

3.2 P V T Behavior of Pure Substances

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Isothermal Supercritical
change

Isobaric change

Dr. Hayat Abdulla Yusuf 11

3.2 PVT Behavior of Pure Substances
(PVT Diagrams)

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Dr. Hayat Abdulla Yusuf 12
 Single-Phase Regions

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• For single phase regions analytically, we can write:
f(P,V,T)=0
• Such a relation is known as PVT equation of state, which relates P, V & T for
a pure homogeneous fluid in equilibrium states.

• The ideal-gas equation of state, PV=RT, has approximate validity for the low-
pressure gas region.

Dr. Hayat Abdulla Yusuf 13

Single-Phase Regions

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• An equation of state may be solved for any one of the three quantities P, V, or T as a
function of the other two.

• For example, if V is considered a function of T & P, then

V  V  P ,T 
• and  V   V 
dV    dT    dP
 T  P  P T
1  V 
• where,  Volume expansivit y
V  T  P
1  V 
  Isothermal com pressibility
V  P T
14
Dr. Hayat Abdulla Yusuf
Single-Phase Regions

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• In combination,
dV
  dT   dP
V
• For the liquid phase, both  &  are small.

• Note:
• No real fluid is truly incompressible, but this assumption gives good
approximations.

• No equation of state exists for an incompressible fluid, because V is independent of

T & P.
Dr. Hayat Abdulla Yusuf 15
Single-Phase Regions

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1  V 
   Volume expansivit y
V  T  P

1  V 
    Isothermal com pressibility
V  P T

• Note:

• For liquids  is almost always positive & is necessarily positive.

• For conditions far from critical point  &  are weak functions of T & P. Thus, on integration of
dV
  dT   dP
V
• we get V
ln 2   T 2  T 1     P2  P1 
V1
Dr. Hayat Abdulla Yusuf 16
Summary

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For Single-Phase Region:

1  V 
   Volume expansivit y
V  T  P

1  V 
    Isothermal com pressibility
V  P T

dV
 dT  dP
V
V2
ln   T 2  T 1     P 2  P 1 
V1 17
Dr. Hayat Abdulla Yusuf
 Example 3.2

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For liquid acetone at 20oC and 1 bar,

•  = 1.487x10-3 oC-1, = 62x10-6 bar-1, V = 1.287 cm3 g-1

• For acetone, find:

 P 
a) The value of  at 20oC and 1 bar.
 T V
b) The pressure generated by heating at constant V from 20oC and 1 bar to 30oC.
c) The change in volume for a change from 20oC and 1 bar to 0oC and 10 bar.
Dr. Hayat Abdulla Yusuf 18
Sec. 3.3

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Ideal Gas and Ideal-Gas State

Dr. Hayat Abdulla Yusuf 19

 Dr. Mohamed Al-Aseeri

3.3 The Ideal Gas_1

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For Ideal gas: Z 1 and then PV  RT

and U  U T  only
3.3.1 Implied Property Relations for an Ideal Gas

Since U  U T  then,
 U  d U T  C
CV     V T  o n ly
  T V dT
and for the enthalpy H  U  P V  U T  RT  H T  o n ly
Dr. Hayat Abdulla Yusuf 20
 3.3 The Ideal Gas_2

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 H  d H T  C
Then, CP    P T  o n ly
 T  P dT
And on differentiating

H  U  P V  U T  RT  H T 
we get dH dU
C P    R  CV  R
dT dT

This equation only imply that Cp & CV vary w/ T in such a way that their difference
is equal to R. Dr. Hayat Abdulla Yusuf 21
 Dr. Mohamed Al-Aseeri

3.3 The Ideal Gas_3

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For any change of state of an ideal gas one can write
dU  CV dT & U= C V d T alw ay s
d H  C pdT & H= C pdT alw ay s
U is function of T only (not V)
Note:
∆U is not equal to Q for these processes. (Why?)

The same discussion Is also true for H.

Dr. Hayat Abdulla Yusuf 22

 Dr. Mohamed Al-Aseeri

3.3.2 Equations for Process Calculations for Idea

Gases_1

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Work for a mechanically reversible closed-system process is
dW   PdV
And for ideal gas in any closed-system process is
d Q  dW  C V dT

On substitution for dW and solving for dQ yields

dQ  C V d T  Pd V
which is an equation for ideal gas in any mechanically reversible closed-
system process. 23
 Dr. Mohamed Al-Aseeri

3.3.2 Equations for Process Calculations for Idea

Gases_1

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dQ  C V d T  Pd V
This equation contains the variables P, V & T, only two are independent.
1) With P=RT/V, we can write
dV dV
dQ  C V dT  RT & dW   RT
V V
2) With V=RT/P & CV=CP-R,
dP dP
dQ  C P dT  RT & d W   RdT  RT
P P
3) With T=PV/R & CV=CP-R
CV CP
dQ  VdP  PdV & d W   PdV
R R 24
 Dr. Mohamed Al-Aseeri

1. Isothermal Process:

rights reserved.
U  H  0

rightsAllreserved.
V2 P2
Q  RT ln   RT ln

2008. All2022.
V1 P1

Copyright
V2 P2

© Copyright
W   RT ln  RT ln

©Textbook publisher’s
V1 P1
Q  W

V2 P2
Q  W  RT ln   RT ln  Const T 
V1 P1
Dr. Hayat Abdulla Yusuf 25
Dr. Mohamed Al-Aseeri

2. Isobaric Process:

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U   C V dT H   C P dT

Q   C P dT W   R T 2  T 1 

Q  H

Q  H   C P dT  Const P 
Dr. Hayat Abdulla Yusuf 26
Dr. Mohamed Al-Aseeri

3. Isochoric Process:

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U   C V dT H   C P dT

Q   C V dT W    PdV  0

Q  U

Q  U   C V dT  Const V 
Dr. Hayat Abdulla Yusuf 27
Dr. Mohamed Al-Aseeri

4. Adiabatic Process (constant heat capacities)_1:

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dQ  0
Thus,

R / CV
dV dT R dV T 2 V 1 
0  CV dT  RT     
V T CV V T1 V 2 
R /C P
dP T 2  P2 
0  C P dT  R T   
P T 1  P1 
C P / CV
CV CP P2  V 1 
0 VdP  [Link]   
R R Hayat Abdulla Yusuf
P1 V 2  28
 Dr. Mohamed Al-Aseeri
Modified by Dr. Hayat Abdulla

4. Adiabatic Process (constant heat capacities)_2:

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These equations can be expressed as

TV  1  const  (11− 𝛾)/𝛾


PV   const
TP  const
where CP
 (known as the specific heat ratio
CV
These equations are restricted in application to:
1. ideal gases
2. with constant heat capacities
3. undergoing mechanically reversible adiabatic expansion or compression (Isentropic).

When used for real gases it gives satisfactory approximations.

Dr. Hayat Abdulla Yusuf 29
Dr. Mohamed Al-Aseeri

4. Adiabatic Process (constant heat capacities)_2:

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For ideal gases, the work of any adiabatic closed-system is given by:

dW  dU  CV dT
For constant CV

W  U  C V T
because
C P CV  R R R
  1 or C V 
CV CV CV  1
R T
W  CV T 
whence  1
Dr. Hayat Abdulla Yusuf 30
Dr. Mohamed Al-Aseeri

4. Adiabatic Process (constant heat capacities)_3:

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Since
RT1  PV
1 1 & RT 2  PV
2 2
Then we can write
RT 2  RT1 PV
2 2  PV
W   1 1
 1  1
Because P,V & T are state functions, then

RT 2  RT1 PV  P1V 1
W   2 2  U  C V T
 1  1
Is always valid for adiabatic compression & expansion processes in a closed system
(reversible or not).
Dr. Hayat Abdulla Yusuf 31
 Dr. Mohamed Al-Aseeri

4. Adiabatic Process (constant heat capacities)_4:

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Because T2 & V2 are usually unknown, we can eliminate them by using


This yield, PV  const
   1      1  
RT1  P2  PV  P 
W     1  1 1  2   1
  1  P1     1  P1  
  

This equation is valid only for ideal gas w/ constant heat capacities in adiabatic,
mechanically reversible, closed-system processes. When used for real gases it gives
satisfactory approximations. Dr. Hayat Abdulla Yusuf 32
 4. Adiabatic Process (constant heat capacities)_5:

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Note:

  1.67 for monatomic gases (e.g., He)

  1.4 for diatomic gases (e.g., O2 )
  1.3 for polyatomic gases (e.g., CO2 )

Note:
The ratio g is less sensitive to temperature than CP & CV themselves.

Dr. Hayat Abdulla Yusuf 33

 5. Polytropic Process_1:

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Polytropic means “turning many ways”, and it suggests versatility.

Polytropic process is represented by the empirical equation:

PV  = Constant and where  =Constant

For ideal gas

TV  1  const TP  (1 − 𝛿)/𝛿
 1 
 const

Dr. Hayat Abdulla Yusuf 34

 Dr. Mohamed Al-Aseeri

5. Polytropic Process_2:

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For ideal gas and by using PV  = Constant we can write,

   1  
RT1  P2 
W     1
  1  P1  

And for constant heat capacities, the first law solved for Q

  1  
Q
     RT1  P2 
   1
  1   1  P1  
35
 Dr. Mohamed Al-Aseeri

5. Polytropic Process_3:

All rights reserved.

The processes described in this section correspond to the four paths shown

2022. reserved.
below for specific values of 

2008. All rights

© CopyrightCopyright
Isobaric process Paths of polytropic
processes characterized
Isochoric process

by specific values of 

©Textbook publisher’s
36
Dr. Hayat Abdulla Yusuf
 Example 3.3

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• An ideal gas undergoes the following sequence of mechanically reversible
processes in a closed system:
• From an initial state of 70oC and 1 bar, it is compressed adiabatically to 150oC.
• It is then cooled from 150 to 70oC at constant pressure.
• Finally, it is expanded isothermally to its original state.
• Calculate W, Q, ΔU, and Δ H for each of the three processes and for the entire
cycle.
• Take CV = (3/2)R and CP = (5/2)R.

Dr. Hayat Abdulla Yusuf 37

 Example 3.3

Dr. Hayat Abdulla Yusuf

38

©Textbook publisher’s Copyright 2022. All rights reserved.

 Dr. Mohamed Al-Aseeri

6. Irreversible Process:

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Note: All equations developed in this section have been derived for mechanically
reversible, closed system processes for ideal gases.

However, those equations which give property changes dU, dH, U & H
are valid for ideal gases regardless of the process.

Because they are state functions, they apply to reversible & irreversible
processes in both open & closed systems.
But for Q or W, unless it is equal to a property change, is subject to the
restrictions of derivation.
Dr. Hayat Abdulla Yusuf 39
 Dr. Mohamed Al-Aseeri

6. Irreversible Process:

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The work of an irreversible process is calculated by two steps:

1. Determine W for mechanically reversible process that accomplishes

same change of state as actual irreversible process.

2. This result is either multiplied by efficiency to give actual work done

by the process or divided by efficiency to get actual work applied to the
process.

Dr. Hayat Abdulla Yusuf 40

 Example 3.4

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• If the processes of example 3.3 are carried out irreversibly but so as to accomplish
exactly the same changes of state – the same changes in P, T, U, and H – then
different values Q and W result. Calculate Q and W if each step is carried out with
an efficiency of 80%.
Reversible process Ex 3.3 Reversible process Ex 3.4

Dr. Hayat Abdulla Yusuf 41

 Sec. 3.2

Virial Equations

Dr. Hayat Abdulla Yusuf

of State

42

©Textbook publisher’s Copyright 2022. All rights reserved.

Dr. Shaker Haji

3.2 Virial Equations of State

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In the isotherms region for gases & vapors, V decreases as P increases.
It is found that, PV for a given T  Constant.
PV = constant
120

100

Isotherm
80
P, atm

60

40

20

0
0 0.5 1 1.5 2 2.5
V, l/mol
Compare the two curves
Dr. Hayat Abdulla Yusuf 43
Dr. Mohamed Al-Aseeri

3.2 Virial Equations of State

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In the isotherms region for gases & vapors, V decreases as P increases.
It is found that, PV for a given T  Constant.
This suggests expressing PV for an isotherm by a power series in P:

where,
PV  a  bP  cP 2  ...
then,
b  aB , c  aC , etc.
where,
PV  a  1  B P  C P 2  ... 
a , B ,C ,etc., are constants for given T Abdulla
Dr. Hayat & chemical
Yusuf species 44
 Sec. 3.3

The Ideal Gas

Dr. Hayat Abdulla Yusuf

45

©Textbook publisher’s Copyright 2022. All rights reserved.

 Dr. Mohamed Al-Aseeri

Idea-Gas Temperature; Universal Gas Constant_1

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PV vs. P, shows that as P  0 the value of PV = constant for all gases, thus

 PV   a  f T 
*

This is the basis to establish an absolute temperature scale. The most common is the
definition of the Kelvin scale:

1. Makes (PV)* directly proportional to T, W/ R

as proportionality constant:

 PV 
*
 a  RT
2. Assigns T =273.16 K of triple point of water:
 PV t
*
 R  273.16K
Dr. Hayat Abdulla Yusuf 46
Dr. Mohamed Al-Aseeri

Idea-Gas Temperature; Universal Gas Constant_2

©Textbook publisher’s Copyright 2022. All rights reserved.

 PV 
*
 a  RT
 PV t
*
 R  273.16K , R : Universal gas const .

Divide the two equations by each other:

 PV   T / K  PV 
* *
or
T /K  273.16
 t 273.16K  PV t
* *
PV Dr. Hayat Abdulla Yusuf 47
 Dr. Mohamed Al-Aseeri

Idea-Gas Temperature; Universal Gas Constant_3

©Textbook publisher’s Copyright 2022. All rights reserved.

 PV 
*

T /K  273.16
 PV t
*

This equation establishes the Kelvin

temperature scale throughout the
temperature range for which (PV)* values
are experimentally accessible.
As P  0, molecules are separated by
infinite distances, their volumes become
negligible w.r.t Vt(g) & intermolecular
forces = zero.

Dr. Hayat Abdulla Yusuf 48

 Dr. Mohamed Al-Aseeri

Idea-Gas Temperature; Universal Gas Constant_4

©Textbook publisher’s Copyright 2022. All rights reserved.

These conditions define an ideal-gas state, and

 PV 
*

T /K  273.16
 t
*
PV
establishes the “Idea-Gas Temperature Scale”

Dr. Hayat Abdulla Yusuf 49

 Dr. Mohamed Al-Aseeri

Two Forms of the Virial Equation

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The compressibility factor, Z, is defined by
PV
Z 
RT
With this definition & w/
 PV 
*
 a  RT
The virial equation becomes:
Z  1  B P  C P 2  ...
B C
An alternative expression is Z  1   2  ...
V V
Dr. Hayat Abdulla Yusuf 50
 Dr. Mohamed Al-Aseeri

Two Forms of the Virial Equation

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Z  1  B P  C P 2  ...
B C
Z  1   2  ...
V V
 
B , C ,etc . and B , C ,etc .
Both equations are known as virial expressions, where
are called virial coefficients, which for a given gas they are functions of T only.
The two types of coefficients are related as follows:

B C B2 D - 3BC  2B 3
B  , C , D 
 RT   RT 
2 3
RT
Dr. Hayat Abdulla Yusuf 51
Sec. 3.4

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Application of The Virial
Equations

Dr. Hayat Abdulla Yusuf 52

 3.4 Application of The Virial Equations_1

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The two forms of the virial equation are infinite series:

Z  1  B P  C P 2  ...
B C PV
Z  1   2  ... Z 
V V RT
In practice, two or three terms are sufficient to give good approximations to
the values of the series.
This is realized for gases & vapors at low & moderate pressures.

Dr. Hayat Abdulla Yusuf 53

Dr. Mohamed Al-Aseeri

3.4 Application of The Virial Equations_2

©Textbook publisher’s Copyright 2022. All rights reserved.

From this figure we can see that at P =0, z =1

Also we can see that the isotherms are nearly

straight lines at low pressures (i.e., P0).

Z  1  B P  C P 2  ...

Dr. Hayat Abdulla Yusuf Compressibility-factor graph for methane

54
Dr. Mohamed Al-Aseeri

3.4 Application of The Virial Equations_3

©Textbook publisher’s Copyright 2022. All rights reserved.

Z  1  B P  C P 2  ...
Differentiation of the above equation at a given temperature yields,
 Z 
   B   2C 
P  3 D P 2
 ...
 P T
from which,
 Z 
 P   B
 T ;P  0
Thus, the equation of the tangent line to the isotherms is

Z  1  BDr. Hayat
P Abdulla Yusuf 55
Dr. Mohamed Al-Aseeri

3.4 Application of The Virial Equations_4

©Textbook publisher’s Copyright 2022. All rights reserved.

A more common form of this equation results from substituting B   B RT
Z  1  B P
which yields,
PV B
Z  1 P
RT RT
This equation is often applied to vapors at T<Tcr up to P = Psat.
At higher T it provides a reasonable approximation for gases up to a P of
several bars, with P range increasing as the T increases
Dr. Hayat Abdulla Yusuf 56
 Dr. Mohamed Al-Aseeri

3.4 Application of The Virial Equations_5

©Textbook publisher’s Copyright 2022. All rights reserved.

B C
Z  1   2  ...
V V
The other equation as well may be truncated to two terms for application at low
pressure:
PV B
Z  1
RT V
But
PV B
Z  1 P
is more preferred. RT RT
Note:
B is substance & temperature dependent.
Dr. Hayat Abdulla Yusuf 57
Dr. Mohamed Al-Aseeri

3.4 Application of The Virial Equations_6

©Textbook publisher’s Copyright 2022. All rights reserved.

For pressure above the range of applicability (i.e., P>Psat) but below Pcr, the
virial equation truncated to three terms often provides excellent results.
Then the appropriate form is
PV B C
Z  1  2
RT V V

This equation can be solved directly for P, but it is cubic in V.

Solution for V is readily accomplished by an iterative scheme.

Note:B & C are substance & temperature dependent.
Dr. Hayat Abdulla Yusuf 58
Dr. Mohamed Al-Aseeri
Modified by Dr. Hayat Abdulla

3.4 Application of The Virial Equations_7

©Textbook publisher’s Copyright 2022. All rights reserved.

This figure illustrates the effect of T on virial coefficients B & C for N2.
B: increases monotonically w/ T.
C: -ve at low T, passes through a maximum at T near Tcr and then decreases
slowly as T increases.

Although numerical values are

different for other gases, the
trends are similar

59
 Dr. Mohamed Al-Aseeri

3.4 Application of The Virial Equations_8

©Textbook publisher’s Copyright 2022. All rights reserved.

A class of EOSs were developed based on the virial equations by
Benedict/Webb/Rubin and they are known as extended virial equations:

RT Bo RT  Ao  C o T 2 bRT  a
P   2

V V V3
a c    
 6  3 2  1  2  exp 2
V V T  V  V

where Ao, Bo, Co, a, b, c,  and  are all constant for a given fluid. This
equation is used in petroleum & natural-gas industries.
Dr. Hayat Abdulla Yusuf 60
 Example 3.8

©Textbook publisher’s Copyright 2022. All rights reserved.

Reported values for the virial coefficients of isopropanol vapor at 200oC are:
B = -388 cm3/mol C = -26,000 cm6/mol2
Calculate V for isopropanol at 200oC and 10 bar using by the ideal gas law and the
two virial equations truncated to three terms.
Note: R = 83.14 [Link]/mol.K, T = 473.15 K

PV B C
Z  1  2
RT V V
P  B C 
V i 1  1   2 
RT  Vi Vi  61
Dr. Hayat Abdulla Yusuf
 Example

©Textbook publisher’s Copyright 2022. All rights reserved.

For liquid acetone at 20oC and 1 bar,

•  = 1.487x10-3 oC-1, = 62x10-6 bar-1, V = 1.287 cm3 g-1

• For acetone, find:

 P 
a) The value of  at 20oC and 1 bar.
 T V
b) The pressure generated by heating at constant V from 20oC and 1 bar to 30oC.
c) The change in volume for a change from 20oC and 1 bar to 0oC and 10 bar.
Dr. Hayat Abdulla Yusuf 62
Sec. 3.5

©Textbook publisher’s Copyright 2022. All rights reserved.

3.5 Cubic Equations of
State

Dr. Hayat Abdulla Yusuf 63

 Dr. Mohamed Al-Aseeri Modified: Dr. Hayat Abdulla, Sem 1, 2014

3.5 Cubic Equations of State_1

©Textbook publisher’s Copyright 2022. All rights reserved.

Cubic equations are the simplest equations capable of representing both
liquid & vapor behavior.
The van der Waals EOS (The first practical Cubic EOS, 1873):

RT a
P   2
V b V

Where a & b are positive constants and substance dependent.

When a and b are zero, the ideal –gas equation is recovered

Dr. Hayat Abdulla Yusuf 64

 3.5 Cubic Equations of State_2

©Textbook publisher’s Copyright 2022. All rights reserved.

RT a
P   2
V b V
For water:
a = 5.5x106 cm6/mol2
b = 30.5 cm3/mol
Notice the unrealistic behavior of EOS in the two-
phase region

This figure is a schematic PV diagram for

water showing 3 isotherms plotted using
the van der Waals EOS.
Dr. Hayat Abdulla Yusuf 65
3.5 Cubic Equations of State_2

©Textbook publisher’s Copyright 2022. All rights reserved.

Nonequilibrium or metastable
states of superheated liquid and
subcooled vapor.

Dr. Hayat Abdulla Yusuf 66

 3.5 Cubic Equations of State_3

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Cubic EOS have 3 volume roots,
which at least 1 is real number (2
may be complex.)
Physically, meaningful values of
V are always real, positive, &
greater than constant b.

Dr. Hayat Abdulla Yusuf 67

 Modified: Dr. Hayat Abdulla, Sem 1, 2014

3.5 Cubic Equations of State_3

©Textbook publisher’s Copyright 2022. All rights reserved.

No. of real volume roots depends on the state (i.e. T & P ):
Root 2: Root 1 :
• For T > Tcr: One root.
liquid-like vapor-like
• For T = Tcr: One root, Root 3: No
except at Pc there are significance
three roots, all = Vc.
• For T < Tcr: P yields one
or three roots (depending
on P). But not all are
stable. The stable states
are only Vsat (liq) and Vsat
(vap)

68
Dr. Hayat Abdulla Yusuf
 A Generic Cubic Equation of State

©Textbook publisher’s Copyright 2022. All rights reserved.

RT a T 
P  
V  b V   b V   b 
where:
• for a give equation,  &  are pure numbers, the same for all substances.
• a(T) & b are substance-dependent parameters
• a(T) is T-dependent and is specific to each EOS

This Eq. reduces to van der Waals EOS when:

a(T) = a (Substance-dependent constant),  =  = 0.
Dr. Hayat Abdulla Yusuf 69
 Dr. Mohamed Al-Aseeri

Determination of Equation-of-State Parameters_1

©Textbook publisher’s Copyright 2022. All rights reserved.

The constants in an equation of state for a particular substance may be
evaluated by a fit to available PVT data.
For cubic EOS suitable estimates are usually found from values of critical
constants Tc & Pc.

RT a T 
P  
V  b V   b V   b 

Dr. Hayat Abdulla Yusuf 70

 Determination of Equation-of-State Parameters_2

©Textbook publisher’s Copyright 2022. All rights reserved.

Because the critical isotherm exhibits a horizontal inflection at the critical point, then
mathematically we can write

 P 
 V  0
 T ;cr
&
  2P 
 2 
0
 V T ;cr
Furthermore, the EOS may itself be written for the critical conditions. 71
Dr. Hayat Abdulla Yusuf
Dr. Hayat Abdulla,

Determination of Equation-of-State Parameters_3

©Textbook publisher’s Copyright 2022. All rights reserved.

Because V=Vc for each of the three roots at critical points: )3=0

3 2 2 3 (A)
Equation (3.41) written for (T=Tc, P=Pc) and expanded in polynomail form becomes:
(B)
From equations A and B:

Dr. Hayat Abdulla Yusuf 72

Dr. Hayat Abdulla

Determination of Equation-of-State Parameters_4

©Textbook publisher’s Copyright 2022. All rights reserved.

• Solving for Eq. (D) for a, combining result with Eq. (E), and
solving for b gives:

• Substituting for b in Eq. (c) allows solution for Vc which can then
be eliminated from the equations for a and b:

Dr. Hayat Abdulla Yusuf 73

Determination of Equation-of-State Parameters_5

©Textbook publisher’s Copyright 2022. All rights reserved.

For the van der Waals EOS the parameters are
evaluated to be:
27 R 2Tc 2 1 RTc 3 RTc
a b V c 
64 Pc 8 Pc 8 Pc
Substituting for Vc in the equation for critical compressibility factor
reduces it to
PV 3
Zc  c c

RTc 8

Dr. Hayat Abdulla Yusuf 74

Determination of Equation-of-State Parameters_6

©Textbook publisher’s Copyright 2022. All rights reserved.

RT a T 
P   (3.42)
V  b V   b V   b 
A similar procedure can be applied to the generic cubic EOS yields
the following expressions for the parameters:
 T r  R 2Tc 2
a T    (3.45)
Pc
RTc
b  (3.42)
Pc
where  &  are pure numbers, independent of substance &
determined from values assigned for  &  .
Dr. Hayat Abdulla Yusuf 75
 Determination of Equation-of-State Parameters_7

©Textbook publisher’s Copyright 2022. All rights reserved.

How can I write a particular EOS? RT a T 
P  
Example: Write down Redlich/Kwong (RK) EOS? V  b V   b V   b 
 T r  R 2Tc 2
a T   
Pc
RTc
b 
Pc

76
Determination of Equation-of-State Parameters_8

©Textbook publisher’s Copyright 2022. All rights reserved.

The modern development of cubic EOS was initiated in 1949 by
publication of the Redlich/Kwong EOS:
RT a T 
P  
V  b V V  b 
R 2Tc 2
where a T   (0.42748) 1/ 2
T r Pc

RTc
b  (0.08664)
Pc
Dr. Hayat Abdulla Yusuf 77
 Determination of Equation-of-State Parameters_9

©Textbook publisher’s Copyright 2022. All rights reserved.

PV 3
For van der Waals EOS: Z c  c c 
RTc 8
Note that different values of this parameter can be found for different EOS.

78
 Determination of Equation-of-State Parameters_10

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Generally the values of Zc obtained do not agree with the experimental ones.
It was found that each chemical species has its own Zc and that experimental
Zc are smaller than the values illustrated in Table 3.1.

79
Dr. Hayat Abdulla Yusuf
Dr. Mohamed Al-Aseeri

Theorem of Corresponding States; Acentric Factor_1

©Textbook publisher’s Copyright 2022. All rights reserved.

Experiments shows that Z for different fluids exhibit similar behavior when correlated as
function of Tr & Pr.

T P
Tr  & Pr 
Tc Pc
This provide the basis for the simplest form of the theorem of corresponding states:
All fluids, when compared at the same reduced T & reduced P, have approximately the
same compressibility factor & deviate from ideal-gas behavior to about the same degree.

This is called two-parameter theorem of corresponding states (require use of Tc & Pc)

Although it is very nearly exact for the simple fluids (Ar, Kr, Xe) systematic deviations are
observed for more complex fluids.
Dr. Hayat Abdulla Yusuf 80
 Theorem of Corresponding States; Acentric Factor_2

©Textbook publisher’s Copyright 2022. All rights reserved.

To improve the results we introduced a third corresponding-states
parameter, that is related to molecular structure: the acentric factor ().
d log Prsat
Pitzer and coworkers: S
d (1/ T r )
i  log  Prsat  SF  log  Prsat  i at T r = 0.7

SF : Simple Fluid

  1.0  log  Prsat T  0.7

r

81
Theorem of Corresponding States; Acentric Factor_3

©Textbook publisher’s Copyright 2022. All rights reserved.

This is the basic premise of the following three-parameter theorem of
corresponding states:

All fluids having the same value of , when compared at the same Tr & Pr, have
about the same value of Z, and all deviate from ideal-gas behavior to about the
same degree.

Dr. Hayat Abdulla Yusuf 82

Dr. Hayat Abdulla

RT a T 
Roots of the Generic Cubic EOS P  
V  b V   b V   b 

©Textbook publisher’s Copyright 2022. All rights reserved.

Vapor & Vapor-Like Roots of the Generic Cubic EOS
For vapor or vapor-like volume, the Generic Cubic EOS will become
RT a T  V b
Eqn. (3.49):
Eqn. (3.42) multiplied
V  b 
P P V   b V   b  through by (V-b)/RT

Initial guess: V = RT /P
Liquid & Liquid-Like Roots of the Generic EOS
For liquid or liquid-like volume, the Generic Cubic EOS will become
Eqn. (3.49) solved for the
 RT  bP VP 
V  b  V  b V  b  
V in the numerator of the

 a   
T
final fraction
83
Dr. Hayat Abdulla Yusuf Initial guess: V = b
 Example 3.9

©Textbook publisher’s Copyright 2022. All rights reserved.

• Given that the Pvap of n-butane at 350 K is 9.4573 bar, find the molar volumes of
saturated-vapor and saturated-liquid n-butane at these conditions as given by
Redlich/Kwong EOS.
Recall Eqn. (3.45)  T r  R 2Tc2 RTc
a T    (3.45) b 
and Eqn. (3.46): Pc Pc
R Tc 2 2
a T   (0.42748) 1 / 2  15,502,894.43 bar.(cm 3 /mol)2
T r Pc
RTc
b  (0.08664)  80.67 cm 3 /mol
Pc
 1 ,  =0 b  80.67 cm 3 /mol   1 ,  = 0, P  9.4573 bar
T  350 K, R  83.14...
84
Dr. Hayat Abdulla Yusuf
 Cont. Example 3.9

©Textbook publisher’s Copyright 2022. All rights reserved.

1) Find V v RT a T  V b
V  b 
P P V   b V   b 
RT a T  V i  b
V i 1  b  RT
P P V i V i  b  V0   3, 076.9 cm 3 /mol
P
V  2, 555.3 cm /mol
v 3

2) Find V l
 RT  bP VP 
V  b  V   b V   b   
 a T  
 RT  bP V i P 
V i 1  b V i V i  b    V 0  b  80.67 cm /mol
3

 a T  
V l
 133.3 cm 3 /mol
85
Dr. Hayat Abdulla Yusuf
Cont. Example 3.9

©Textbook publisher’s Copyright 2022. All rights reserved.

PV diagram for n-butane at
T=350 K as described by RK
EOS, Example 3.9

86
Cont. Example 3.9

©Textbook publisher’s Copyright 2022. All rights reserved.

• The Soave/Redlich/Kwong and the Peng/Robinson equations were developed specifically
for vapor/liquid equilibrium calculations.

Method 2: Using the compressibility

factor calculation , refer to Page 98-99
Dr. Hayat Abdulla Yusuf 87
 Roots of the Generic Cubic Equation of State:
Alternative approach

©Textbook publisher’s Copyright 2022. All rights reserved.

Vapor & Vapor-Like Roots of the Generic Cubic Equation of State

Liquid & Liquid-Like Roots of the Generic Cubic Equation of State

Dr. Hayat Abdulla Yusuf 88

Sec. 3.6

©Textbook publisher’s Copyright 2022. All rights reserved.

Generalized Correlations For Gases

Dr. Hayat Abdulla Yusuf 89

 3.6 Generalized Correlations For Gases

©Textbook publisher’s Copyright 2022. All rights reserved.

Pitzer Correlations for the Compressibility factor

Z  Z 0  Z 1 T&P
Where Z0 & Z1 are functions of both Tr & Pr dependent
Lee & Kesler developed a correlation for Z0 & Z1 as f (Tr ,Pr ) and the data is
presented in forms of tables (App. E.1-E.4)

The Lee/Kesler correlation provides reliable results for gases which are non or only
slightly polar.
(e.g. He, Ne, Kr, Xe, H2, N2, O2, CO2, CH4, & C2H4)
Dr. Hayat Abdulla Yusuf 90
Dr. Hayat Abdulla Yusuf
Sample of Appendix E.1-E.4

91

©Textbook publisher’s Copyright 2022. All rights reserved.

3.6 Generalized Correlations For Gases

©Textbook publisher’s Copyright 2022. All rights reserved.

Pitzer Correlations for the Second Virial Coefficient

The tabular nature of Z0 & Z1 is a disadvantage.

The simplest form of virial equation is, however, valid for low to moderate pressures:

BP ˆ Pr ˆ BPc
Z 1 1 B B
RT Tr RTc
B̂  B 0   B 1 T dependent
0.422 0.172
B 0  0.083  B 1  0.139 
T r1.6 Dr. Hayat Abdulla Yusuf T r4.2 92
 3.6 Generalized Correlations For Gases

©Textbook publisher’s Copyright 2022. All rights reserved.

Pitzer Correlations for the Third Virial Coefficient
B C
Z 1  2
V V
Pr  Pr 
2
RHS Eq: T, P, & Z
Z 1 Bˆ ˆ
C   dependent
Tr Z T Z
 r 
2
BPc CP
Bˆ  & Cˆ  2 c 2 Cˆ  C 0   C 1
RT c R Tc

93
 Conditions of Approximate Validity of the Ideal-Gas
EOS

©Textbook publisher’s Copyright 2022. All rights reserved.

When the ideal-gas EOS may be used as a
reasonable approximation to reality?

Region where Z0 lies b/n 0.98 &

1.02 the ideal-gas approximation
is reasonable.

94
Dr. Hayat Abdulla Yusuf
Conditions of Approximate Validity of the Ideal-Gas
EOS

©Textbook publisher’s Copyright 2022. All rights reserved.

Source: Gour-Jen Su, “Modified Law of
Corresponding States,” Ind. Eng. Chem.
(international ed.) 38 (1946), p.803

95
Dr. Hayat Abdulla Yusuf
Conditions of Approximate Validity of the Ideal-Gas
EOS

©Textbook publisher’s Copyright 2022. All rights reserved.

Very rough guideline:

Pr < 0.001 any Tr

Pr < 0.01, Tr > 0.5
Pr < 0. 1, Tr > 1
Pr < 1.0, Tr > 2
Pr < 3.0, Tr > 3
Dr. Hayat Abdulla Yusuf 96
 Example 3.11_Modified

©Textbook publisher’s Copyright 2022. All rights reserved.

• What pressure is generated when 1 lb-mol of methane is stored in a volume of 2 ft3
at 122oF? Base calculations on each of the following
9th edition’s problem is in SI units:
a) The ideal-gas EOS 500 mol, 0.06 m3, and 50 oC

b) The Redlich/Kwong EOS.

c) A generalized correlation:
1. The simplest form of the virial equation with the Pitzer correlation.
2. Pitzer’s compressibility factor correlation

Dr. Hayat Abdulla Yusuf 97

 Cont. Example 3.11

©Textbook publisher’s Copyright 2022. All rights reserved.

Solution
V = 2 ft3, T = 122oF + 459.67 = 581.67oR, R = 0.7302 ft3 atm/(lb-mol R) w=
0.012, Tc = 343.1 R, Pc = 45.4 atm, Tr = 1.695, P = ?
RT
Ideal gas EOS: P   212.4 atm Pexperimental  185 atm
V a T 
RT
RK EOS: P    187.49 atm
V  b V V  b 
Second Virial EOS:
BP P
a (T )  453.94 atm(ft 3 / lb-mol) 2 , b  0.4781 ft 3 / lb-mol Z 1  1  Bˆ r
BPc RT Tr
Bˆ  , B̂  B 0   B 1   0.012 (Table B.1)
RTc
0.422 0.172 Bˆ  0.09696
B 0  0.083  1.6 =  0.09840 B 1  0.139  4.2
 0.12025
Tr Tr
𝑃𝑉 Dr. Hayat𝐵Abdulla Yusuf
B  0.53502 ft 3 /lb-mol =1+ =155.56 atm Or 𝑃 = = 𝟏𝟔𝟕. 𝟓 𝒂𝒕𝒎 98
𝑅𝑇 𝑉
 Cont. Example 3.11

©Textbook publisher’s Copyright 2022. All rights reserved.

• Solution
V = 2 ft3, T = 122oF + 459.67 = 581.67oR, R = 0.7302 ft3 atm/(lb-mol R) w = 0.012, Tc
= 343.1 R,Pc = 45.4 atm, Tr = 1.695, P = ?
• c) Pitzer’s Z-Correlation: Z  Z 0  Z 1 Z0 & Z1 = f(Tr ,Pr )
RT
• Initial guess P   212.4 atm Pr  4.6784
V
Pr  4.6784, T r  1.70  Z 0  0.8956, Z 1  0.2710

Z  0.8988, P  Z (RT /V )  (0.8988)(212.4)  190.91 atm Pr  4.2051

Pr  4.2051, T r  1.70  Z 0  0.8914, Z 1  0.2596
Z  0.8946, P  Z (RT /V )  (0.8946)(212.4)  190.00 atm Pr  4.1851
Pr  4.1851, T r  1.70  Z 0  0.8913, Z 1  0.2591
Z  0.8944, P  Z ( RT /V )  (0.8944)(212.4)  189.97 atm 99
Sec. 3.7

©Textbook publisher’s Copyright 2022. All rights reserved.

Generalized Correlations For Liquids

Dr. Hayat Abdulla Yusuf 100

Dr. Mohamed Al-Aseeri
Modified by Dr. Hayat Abdulla

3.7 Generalized Correlations For Liquids_1

©Textbook publisher’s Copyright 2022. All rights reserved.

Although the molar volume of liquids can be calculated by cubic EOS, the results
are often not of high accuracy.
Lee/Kesler correlation includes data for subcooled liquids too (non or slightly
polar fluids)
Generalized equations are available for the estimation of molar volumes of
saturated liquids. The simplest equation is proposed by Rackett

1T r 2 / 7
V sat
V c Z c
An alternative form is
Pr 1 1Tr 2 / 7 
Z sat  Zc
Tr 101
Dr. Hayat Abdulla Yusuf
 Dr. Mohamed Al-Aseeri
Modified by Dr. Hayat Abdulla

3.7 Generalized Correlations For Liquids_2

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Lydersen, Greenkorn, and Hougen developed a two-parameter corresponding-
states correlation for estimation of liquid volumes.

The molar reduced density r is defined as

 Vc
r   , c   at critical point
c V

Dr. Hayat Abdulla Yusuf 102

Dr. Mohamed Al-Aseeri
Modified by Dr. Hayat Abdulla

3.7 Generalized Correlations For Liquids_3

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Method 1: no experimental data Method 2: experimental point
needed needed (V1)
 Vc V 2 r 1
r   
c V Dr. Hayat Abdulla Yusuf
V 1 r 2 103
 Example 3.14

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• Part 1: For ammonia at 310 K, estimate the molar volume of the saturated liquid.
• Part 2: Also estimate the volume of liquid ammonia at 100 bar, using:
a) The generalized density correlation chart for liquids
b) The chart and the experimental value of 29.14 cm3/mol for saturated liquid at 310 K.
c) Lee/Kesler correlation for Z0 & Z1.

• Solution
Table B.1: Tc = 405.7 K, Pc = 112.8 bar, Vc = 72.5 cm3/mol , Zc = 0.242, Tr = 0.7641

• Part 1:
V sat
 28.33 cm 3 /mol
V c Z c  2/ 7
sat 1T r
V 3
(V exp = 29.14 cm /mol) 104
Cont. Example 3.14

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At T = 310 K, P = 100 bar, Find V for liquid ammonia using:
a) The generalized density correlation chart for liquids
Solution Part 2
Tc = 405.7 K, Pc = 112.8 bar, Vc = 72.5 cm3/mol , Zc = 0.242 Tr = 0.764, Pr = 0.887.

From the chart @ Tr , Pr

→ ρr = 2.38
Vc
V   30.45 cm 3 /mol
r
3
(V exp = 28.6 cm /mol)

105
 Cont. Example 3.14

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• At T = 310 K, P = 100 bar, Find V for liquid ammonia using:
a) The generalized density correlation chart for liquids
b) The chart and the experimental value of 29.14 cm3/mol for saturated liquid at 310 K.
c) Lee/Kesler correlation for Z0 & Z1.
• Solution Part 2
Tc = 405.7 K, Pc = 112.8 bar, Vc = 72.5 cm3/mol , Zc = 0.242
Tr = 0.764, Pr = 0.887 V
V  c  30.45 cm 3 /mol (V exp = 28.6 cm 3 /mol)
a) Tr , Pr → rr = 2.38 r
V 2 r 1
 V  28.65 cm 3 /mol
V 1 r 2
b) V1 = 29.14, ρr1 = 2.34 ρr2 = 2.38
• c) V = ZRT/P = 33.87 cm3/mol Dr. Hayat Abdulla Yusuf 106
Dr. Hayat Abdulla
Yusuf

Cont. Example 3.14

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Lee-Kesler Correlation
Detail:

107
Dr. Hayat Abdulla Yusuf

Cont. Example 3.14

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Lee-Kesler
correlation Details:

108
Dr. Hayat Abdulla
Yusuf

Cont. Example 3.14

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• Lee-Kesler Correlation detail:

109
Dr. Hayat Abdulla

Appendix F: Single linear interpolation

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Dr. Hayat Abdulla Yusuf 110
Dr. Hayat Abdulla

Appendix F: Double linear interpolation

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111
 Dr. Hayat Abdulla

SYNOPSIS

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After thorough study of this chapter, including multiple readings and working through example and end-of-
chapter problems, one should be able to:
• State and apply the phase rule for nonreacting systems
• Interpret PT and PV diagrams for a pure substance, identifying the solid, liquid, gas, and fluid regions; the
fusion (melting), sublimation, and vaporization curves; and the critical and triple points
• Draw isotherms on a PV diagram for temperatures above and below the critical temperature
• Define isothermal compressibility and volume expansivity and use them in calculations for liquids and solids
• Make use of the facts that for the ideal-gas state Uig and Hig depend only on T (not on P and Vig), and that
C P ig = C V ig + R
• Compute heat and work requirements and property changes for mechanically reversible isothermal,
isobaric, isochoric, and adiabatic processes in the ideal-gas state
• Define and use the compressibility factor Z
• Intelligently select an appropriate equation of state or generalized correlation for application in a given
situation, as indicated by the following chart: 112
 Dr. Hayat Abdulla

SYNOPSIS

113

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 Dr. Hayat Abdulla

SYNOPSIS

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After thorough study of this chapter, including multiple readings and working through example and end-of-
chapter problems, one should be able to:
• Apply the two-term virial equation of state, written in terms of pressure or molar density.
• Relate the second and third virial coefficients to the slope and curvature of a plot of the compressibility factor versus
molar density
• Write the van der Waals and generic cubic equations of state, and explain how the equation-of-state parameters are
related to critical properties
• Compute parameters for the Redlich/Kwong, Soave/Redlich/Kwong, and Peng/Robinson equations of state from
critical properties
• Solve any of the cubic equations of state, where appropriate, for the vapor or vapor-likeand/or liquid or liquid-like
molar volumes at given T and P
• Apply the Lee/Kesler correlation by interpolation in the tables of Appendix D
• Determine whether the Pitzer correlation for the second virial coefficient is applicable for given T and P, and use it if
appropriate
• Estimate liquid-phase molar volumes by generalized correlations 114
Homework Problems

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7th 9th
edn edn
3.1 3.6
3.3
3.8 3.17
3.9 3.19 7th 9th
edn edn
3.10 3.21
3.46 3.61
3.11 3.22
3.50 3.68
3.22 3.32
3.51 3.69
3.24 3.35
3.58 3.76
3.30 3.42
3.61 3.79
3.32 This Photo by Unknown Author is licensed under CC BY-SA-NC
3.64
3.33 3.45
3.73 3.90
3.34
3.35 3.50
3.38 3.53
3.41 3.56
3.45 3.60

115
Dr. Hayat Abdulla Yusuf