PVT Behavior of Fluids and the Theorem of Corresponding States

Compressibility Factor
The volumetric PVT behavior of a material is often characterized by
the compressibility factor Z
PV
PV
Z

NRT RT
Typical values: ideal gas, Z = 1.0; liquids, Z ~ 0.01 to 0.2;
critical point, Zc ~ 0.27 to 0.29
Theorem of Corresponding States
This theorem suggests that values of thermodynamic properties of
different fluids can be compared when properties are normalized by
their values at the critical point
Z f Z c , Tr , Pr

PVT Behavior of Fluids and the Theorem of Corresponding States

Theorem of Corresponding States
The reduced temperature and
pressure are simply
Tr T Tc and Pr P Pc
If Zc is assumed to be a
constant for all materials
Z f Tr , Pr
Experimental observations
provide strong evidence to
support this approach
The relation above indicates that all fluids have the same reduced
volume Vr (as well as other properties) at a specified Tr and Pr
In Example 7.2 the principle of corresponding states was used to
relate the a and b constants of the van der Waals equation of state to
a fluids critical properties, specifically Tc and Pc

PVT Behavior of Fluids and the Theorem of Corresponding States

Generalized Coexistence Curve
The theorem of corresponding states can be used to obtain a
generalized phase diagram
Law of rectilinear diameters states that the average density in
the L-V region varies linearly over a wide temperature range below
the critical point
Zeno line the Z = 1.0 line on
the phase diagram
For states with Z > 1.0 (hard fluid),
repulsive forces dominate and
conversely, for states where
Z < 1.0 (soft fluid) attractive forces
are dominant

PVT Behavior of Fluids and the Theorem of Corresponding States

Acentric Factor
To improve the accuracy of property predictions, Pitzer and
coworkers introduced the acentric factor as a third correlating
parameter
Z Z 0 Tr , Pr Z 1 Tr , Pr
The acentric factor was developed
as a measure of the difference in
structure between the material of
interest and a spherically symmetric
gas such as argon
Therefore, the parameter is related
to a molecular property
The parameter is defined using the
reduced vapor pressure
log10 Pvp ,r T 0.7 1
r

PVTN Equations of State for Fluids

Overview
Although the corresponding states correlations are useful, the data
is displayed in charts and graphs are therefore cumbersome to use
A more useful means to express a fluids PVT behavior is through an
analytical expression (PVT equation of state)
Two general approaches
Statistical mechanical models based on rigorous theoretical
principles accounting for the interactions between molecules
(preferred by physicists and physical chemists)
Empirical expressions models formulated by determining
parameters in a mathematical expression through a fit to
experimental data (preferred by chemical engineers)

PVTN Equations of State for Fluids

Relating EOS Parameters to Experimental Data
Empirical models have parameters that must be determined to
calculate PVT data
A common way to determine these parameters is to relate the model
parameters to a fluids critical properties
By adopting this approach we are utilizing the theorem of
corresponding states
The critical point criteria for a single-component system require
P

0
Tc

and

2P

2
V

0
Tc

Recall Example 7.2, where these criteria were used to determine the
parameters for the van der Waals EOS

PVTN Equations of State for Fluids

Cubic Equations of State
Since the pioneering work of van der Waals, numerous
modifications of the original vdW EOS have been published
Most are pressure-explicit cubic forms, i.e.,
P f T ,V , N
van der Waals EOS
RT
a
P
2
V b V
27 R 2Tc2
a
64 Pc

and
Zc = 0.375

RTc
b
8 Pc

PVTN Equations of State for Fluids

Redlich-Kwong
RT
a
P

V b
T V V b
a R 2Tc2.5
a
Pc
b RTc
b
Pc

with

with

Zc = 0.333

a 9 2 1 0.42748
13

1
0.08664
3

13

Redlich-Kwong-Soave
The attractive term is made temperature dependent and the acentric
factor is introduced
2
a ac f , Tr ac 1 k 1 Tr
Zc = 0.333
with
k 0.48508 1.55171 0.15613 2

PVTN Equations of State for Fluids

Peng-Robinson
P

with

RT
a , Tr

V b V V b b V b

Zc = 0.307

a , Tr ac , Tr
0.45724 R 2Tc2
ac
Pc
, Tr 1 1 Tr

0.37464 1.54226 0.26992 2

b

0.07780 RTc
Pc

PVTN Equations of State for Fluids

Hard-Sphere Equation of State
A class of EOSs that incorporate knowledge of the specific
molecular interactions with additional fitted parameters
The repulsive term is theoretically based
The term bo below accounts for the excluded volume of a molecule
The attractive term is empirical
Here is one example of a hard-sphere EOS that uses the CarnahanStarling repulsive term and van der Waals attractive term
RT V 3 boV 2 bo2V bo3
a

V2
V
V bo 3

3
bo
6

molecular diameter

PVTN Equations of State for Fluids

Virial-Type Equation of State
An important EOS class that has a rigorous basis in molecular
theory (may be derived from statistical mechanics)
The compressibility is expressed as a polynomial in volume
PV
B C
Z
1 2 1 B C 2
RT
V V
Or as a polynomial expansion in pressure
Z 1 BP C P 2 DP 3
Where
B

B
RT

C B2
C
RT 2

D 3BC 2 B 3
D
RT 3

The coefficients B, C, D, are termed the second, third, fourth,

virial coefficients

PVTN Equations of State for Fluids

Method of Abbott
The virial equation is truncated after the second virial coefficient
term and the pressure is obtained
PV
BP
RT
Z
1
P
RT
RT
V B
The second virial coefficient is expressed in terms of two functions
of temperature B(0) and B(1) as well as the acentric factor
RTc 0
B B 1
B
Pc

Where
B

0.422
0.083 1.6
Tr

and

0.172
0.139 4.2
Tr

PVTN Equations of State for Fluids

Benedict-Webb-Rubin EOS
Another example of a virial-type EOS
Has eight parameters
Frequently used for modeling the PVT behavior of light
hydrocarbons and gases in petroleum and natural gas applications
Co 1 bRT a
RT
P
Bo RT Ao 2 2

3
V
T V
V
a c1 V 2
2

exp

V
6
3 2
V
V T

Evaluating Changes in Properties Using Departure Functions

Overview
We now develop methods for determining changes in derived
thermodynamic properties of a pure substance
Because properties are state functions, we can choose any
convenient path to calculate the change in the property of interest
(e.g., H, S, U, A, or G)
To perform the calculation, we must generally have access to two
constitutive relationships
1. A PVT or PVTN equation of state (EOS)
2. An ideal-gas state heat capacity equation

Evaluating Changes in Properties Using Departure Functions

Convenient Path
To calculate property changes between two well-defined states
(T1,P1,V1) and (T2,P2,V2) we use the following three-step process
1. Isothermal expansion at T1 from P = P1 to 0 (or V = V1 to
2. Isobaric (or isochoric) heating from T1 to T2 in an attenuated
ideal gas state [P = 0 (or V = )]
3. Isothermal compression at T2 from P = 0 to P2
(or from V = to V2)

Evaluating Changes in Properties Using Departure Functions

Convenient Path
The total property change between states 1 and 2, B (where B is
one of H, S, U, A, or G), is the sum over these three steps
B B T2 , P2 ,V2 B T1 , P1 ,V1

B T1 , P 0,V B T1 , P1 ,V1

B T2 , P 0,V B T1 , P 0,V
B T2 , P2 ,V2 B T2 , P 0,V

step (1)
step (2)
step (3)

Step (2) occurs entirely within the ideal-gas state

Recall that only 2 of the 3 intensive variables T, P, and V are
independent
We select T as one independent variable and choose P or V based on
the PVT EOS we have
If we have a pressure-explicit EOS (P = f (T,V)), we choose V
If we have a volume-explicit EOS (V = f (T,P)), we choose P

Evaluating Changes in Properties Using Departure Functions

Example 8.3
Develop expressions for S between states 1 and 2 assuming you
have analytic forms for (1) a volume-explicit EOS and (2) a pressureexplicit EOS and C po T a bT cT 2 dT 3
Summary
Volume-explicit EOS
S

P2

V
T

T2

C po T

T1

P1
T
0

R

P
P

Pressure-explicit EOS
dP

T T2

P
S

T
V2

R

P
P

V1
T

dP
T T1

T1

dV
T T2

Cvo T
V2
dT R ln
T
V1

P2
dT R ln
P1

T2

R

V

R

V

dV
T T1

Evaluating Changes in Properties Using Departure Functions

Departure (Residual) Functions
A departure function is the difference between the property of
interest in its real state at a specified T, P, and V and in an idealgas state at the same temperature T and pressure P
There are two equivalent forms of the departure function
B T , P B ideal gas T , P B T , P B o T , P

B T ,V B ideal gas T ,V o B T ,V B o T ,V o
B is any derived property (H, S, U, A, or G) and Vo = RT / P(T,V)

Evaluating Changes in Properties Using Departure Functions

Residual Entropy
Based on Example 8.3, the residual entropy is defined as
V
S T , P S T , P

0
T
o

R
dP
P
P

Evaluating Changes in Properties Using Departure Functions

Residual Helmholtz Energy
When working with pressure-explicit EOSs, the departure function
for the Hemlholtz energy is particularly useful
The differential expression for A is
dA SdT PdV
Integrating at constant T between A(T,V) and A(T,) gives
V

A T ,V A T , PdV

To obtain the departure function, we must also account for the

change from V to V = Vo, which occurs in the ideal-gas state
A T , A T ,V
o

PdV
ideal gas

To avoid a singularity we also add and subtract

V RT
V dV

Evaluating Changes in Properties Using Departure Functions

Residual Helmholtz Energy
The final result is
A T , V Ao T , V o

o
RT
V

P dV RT ln

V
V

Residual Entropy
The entropy is obtained by differentiating A with respect to T
A

S T ,V S o T ,V o

RT
Vo
P V dV R ln V
V

Evaluating Changes in Properties Using Departure Functions

Other Departure Functions
Now that A and S are known, other departure functions can be
obtained through simple algebra
U T , V U o T , V o A Ao T S S o

H T ,V H o T ,V o U U o PV RT

G T , V G o T ,V o H H o T S S o
General Result
To determine the change in a thermodynamic property between two
states, we evaluate two isothermal departure functions (at T1 and T2)
and a temperature change contribution in the ideal gas state
B T2 ,V2 B T1 ,V1 B T2 ,V2 B o T2 ,V2o
departure function at T1
B T1 ,V1 B o T1 ,V1o

B o T2 ,V2o B o T1 ,V1o

departure function at T2
ideal-gas isotherm

Evaluating Changes in Properties Using Departure Functions

Departure Functions for Volume-Explicit PVT EOSs
When volume-explicit PVT EOSs are available the following
isothermal departure functions should be used
G T , P G T , P RT
o

H T , P H T , P RT
o

S T , P S T , P RT
o

dP
Z 1
P
P

dP
P P

P
dP
dP
R Z 1
0
P
P P

Evaluating Changes in Properties Using Departure Functions

Useful Ideal-Gas Property Relationships
Internal Energy:
U T2 ,V
o

o
2

U T1 ,V
o

o
1

U T2 , P2 U T1 , P1 Cvo dT

H T2 , P2 H T1 , P1 C op dT

T2

T1

Enthalpy:
H T2 ,V
o

o
2

H T1 ,V
o

o
1

T1

Entropy:
S o T2 ,V2o S o T1 ,V1o

T2

T1

S T2 , P2 S T1 , P1
o

T2

T2

T1

Cvo
V2o
dT R ln o
T
V1

C po

P2
dT R ln
T
P1

Evaluating Changes in Properties Using Departure Functions

Heat Capacity Departure Functions (Pressure-Explicit PVT EOS)
The heat capacities are related to differentials of the entropy with
temperature, for example Cv is defined as
Cv S

T T V
Evaluating the derivative yields
2
V P
Cv T ,V Cvo T ,V o T
dV
T 2

V
The constant pressure heat capacity departure function requires a bit
more work to obtain
2
2

T
V P

V
o
o
C p T ,V C p T ,V T
dV T
R
T 2
P V T

V
Often times it is more convenient to obtain Cp Cpo by first
determining Cv Cvo and then using an expression that relates Cv
and C that will be introduced below

Evaluating Changes in Properties Using Departure Functions

Heat Capacity Departure Functions (Volume-Explicit PVT EOS)
With a volume-explicit PVT EOS the constant pressure heat
capacity departure function is relatively straightforward to obtain
Cp
T

Evaluating the derivative yields

C p T , P C po T , P T

2V
T 2 dP

Evaluating Changes in Properties Using Departure Functions

General Relationships Between Cv and Cp
Using the formalism introduced in Chapter 5 one can obtain the
following relationship between Cv and Cp
TV 2p
C p Cv
T
The above expression is completely general and therefore can be
used to relate heat capacities for real or ideal gases as well as for
liquids and solids
Recalling the definitions of T and p, the expression above can
equivalently be written as
P T V2
C p Cv T
P V T

Compressibility and Heat Capacity of Solids

Incompressible Substances
Most solids and many liquids far below their critical temperatures
have very low compressibilities
In these situations one can assume perfectly or nearly
incompressible behavior as a first-order approximation
An incompressible substance is defined as having a constant
volume (V = constant) independent of T and P
From this definition, it follows that p = T = 0 for an
incompressible substance
For a nearly incompressible substance the following expressions are
appropriate (for a perfectly incompressible substance, the
approximation becomes a true equality)
C p Cv
dS

Cv
dT
T

dU Cv dT
dH C p dT VdP Cv dT VdP

Derived Property Representations

Overview
Before the infusion of computers, charts or tubular data were used
widely for engineering problem solving
Although computer-generated representations of thermodynamic
properties are preferred, many graphical forms of data are still used
in engineering practice
The temperature-entropy (T-S) diagram for water is a good example