Chapter 2

Engineering Equations of State

for PvT properties

Equation of state

equation that relates measured variables

by fitting experimental data
mathematically: f(P,v,T) = 0
EOS can be precise in

P: P = f(T,v)
in v: v = f(T,P)
in z: z = Pv/RT = f(T,v)
in z: z = Pv/RT = f(T,P)
2

Ideal gas equation

Most common EOS: ideal gas model

P = RT/ v
Relates P, T and v
Derived directly from the kinetic theory of gases
Assumptions:

Molecules occupy no volume

Molecules exert no intermolecular forces

Generalization to non-ideality

Generalizing intermolecular interactions to

non-ideal behavior
Principle of corresponding state

The dimensionless potential energy is the same

for all species
Scale potential energy to the energy parameter
Example: critical point - a state determined by
intermolecular interaction characteristics of a
given species
Tr = T/Tc

Principle of corresponding
states

Two-parameter corresponding states

Three-parameter corresponding states

Two-parameter corresponding
states

says that all fluids when compared at the

same reduced temperature (Tr) and
reduced pressure (Pr), have approximately
the same compressibility factor, Z and all
deviate from ideal gas behavior to about the
same degree

Statement is based on non-polar species

6

Figure 3.1 Dashed lines are for methane, solid lines are for pentane.
The figure demonstrates that critical pressure and temperature alone
are insufficient to accurately represent the PvT behavior.

Three-parameter
corresponding states

However, different classes of molecules have

different intermolecular interactions (e.g.
polar vs. non-polar) and behaves differently
Therefore, additional parameter introduced:

Pitzer acentric factor,

characterizes how non-spherical a molecule is
is a way to class molecules according to
different characteristics
8

Three-parameter
corresponding states

says that all fluids having the same value

of acentric factor, when compared at the
same Tr and Pr, have about the same value
of Z and all deviate from ideal gas behavior
to about the same degree

The acentric factor, is defined with reference to its

vapor pressure. specifies a vapor pressure at a
reduced temperature of 0.7.

1.0 log Prsat

T r 0 .7

Psat at reduced
T of 0.7

Figure 3.2
Reduced vapor
pressure plotted
as a function of
reduced
temperature.
10

Generalized Compressibility
Factor Charts

PvT behavior can be generalized in terms of Tc, Pc

and . The correlation for Z is

Z Z 0 Z 1
Accounts
for simple
molecules

Correction factor for

the nonsphericity of
a species

Tables (Appendix C of textbook) or charts (Figure

4.14 of textbook) summarized the values of Z0 and
Z1 at reduced temperature and pressure. can be
found from Appendix A of your textbook.
11

Figure 3.3: Generalized

charts for estimating the
compressibility factor. The
plot of Z0 represents the
behaviour of a fluid that
would have =0. The plot
of Z1 is a correction factor
for
a
hypothetical
compound with =1.

12

Example 1: Application of the

generalized charts

Estimate the specific volume for CO2 at 310K and (a) 8 bars (b) 75
bars by the compressibility factor charts and compare to the
experimental values of 70.58 cm3/g and 3.9 cm3/g respectively.
Solution: = 0.228, Pc= 73.76 bar, Tc= 304.2 K
(a) Tr= 310/304.2= 1.02
Pr= 8/73.82= 0.108
From the charts, Z0= 0.96, Z1= 0,
Z= 0.96 + 0.228(0)= 0.96
v= ZRT/P
= ZRuT/PM
= [0.96*83.14cm3bar/molK*310 K]/[8 bar*44g/mol]
= 70.29 cm3/g (within 0.4 % of the experimental value)

13

Cont. Example 1

(b)

Tr= 310/304.2= 1.02

Pr= 75/73.76= 1.02

Interpolate between the reduced temperatures of 1.0 and 1.05.

At Tr= 1.0, Z0= 0.22, Z1= -0.08, therefore,
Z= 0.22 + 0.228*(-0.08)= 0.202
At Tr= 1.05, Z0= 0.58, Z1= 0.03, therefore,
Z= 0.58 + 0.228*(0.03)= 0.587
Interpolating, Z= 0.202 + (0.587-0.202)*0.02/0.05= 0.356
v= ZRT/P
= ZRuT/PM
= [0.356*83.14cm3bar/molK*310 K]/[75 bar*44g/mol]
= 2.78 cm3/g (giving 29% error relative to the experimental value)
14

The Virial Equation of State

At low pressure, the equation of state can be written

as explicit in a power series with respect to the
density.

Z 1 B C 2 D 3 ...

Derived from first

principles using
statistical
mechanics

B, C, D Virial
coefficients temperature
dependent only

C = D == 0 at low pressures
15

The virial equation is often

referred as:
Z 1 BP / RT or Z 1 B
where B T B B RT / P
0

B Pr / Tr

B 0 0.083 0.422 / Tr1.6

1

4.2
r

B 0.139 0.172 / T

Subject to Tr 0.686 0.439 Pr

or Vr 2.0
16

The Virial Equation of State

for vapor only

low pressures
obsolete
never use the virial equation

17

Example 2: Virial equation

Estimate the specific volume for CO2 at 310K and (a) 8 bars (b) 75 bars by
the virial equation and compare to the experimental values of 70.58 cm3/g
and 3.9 cm3/g respectively.

Solution: = 0.228, Pc= 73.82 MPa, Tc= 304.2 C

(a)
Tr= 310/304.2= 1.02
Pr= 8/73.82= 0.108
Check the applicability of virial equation
0.686 + (0.439*0.108)= 0.733<Tr
B0= 0.083 0.422/1.021.6= -0.326
B1= 0.139 0.172/1.024.2= -0.0193
Z= 1+[-0.326+(0.228*-0.0193]*0.108/1.02
Z= 0.965
v= ZRT/P
= ZRuT/PM
= [0.965*83.14cm3bar/molK*310 K]/[8 bar*44g/mol]
= 70.66 cm3/g (within 0.1 % of the experimental value)

18

Cont. Example 2
(b)

Tr= 310/304.2= 1.02

Pr= 75/73.82= 1.02

0.686 + (0.439*1.02)= 1.13>Tr

(virial equation not applicable)

19

Cubic equation of state

goes as a volume to the third power

hundreds of cubic EOS
provides reasonable values for both vapor
& liquid region
are approximates merely fit experimental
data

20

Cubic equation of state

Common Cubic EOS

Van der Waals EOS

Vapor only, low pressures

Redlich-Kwong EOS
Vapor only, moderate pressures

obsolete

Soave-Redlich-Kwong EOS
Vapor & saturated liquid, high pressures

Valuable in history
Nobody should use anymore

A very powerful equation used in industry

Peng-Robinson EOS
Vapor & saturated liquid, high pressures, HC industry std

Most commonly used in HC, better than SRK, a little more

complicated
21

Cubic equation of state

The general form of a cubic equation is

3 f1 (T , P ) 2 f 2 (T , P ) f 3 (T , P) 0

where fi(T,P) represents a function that can contain T,

P and fitting parameters

However, it is easier to solve cubic EOS in

3
2
the form of Z Z Z 0
22

Cubic equation of state

there are three roots for volume for fixed values of

T and P
meaning there are also 3 roots for Z
roots have different characteristics

Above critical point

1 positive real root
2 negative or imaginary numbers
Below critical point
3 real, positive roots
Lowest root liquid state
Highest root vapor state
Middle root throw out
23

van der Waals EOS

simplest form of the cubic EOS

P

RT
a
2
vb v

or

Z 1

b
a
1
a

1 b RT 1 b RT

Deviations due
to the repulsive
interactions

Deviations due
to the attractive
interactions

where
27 R 2Tc2
a
64 Pc

b 0.125 R

Tc
Pc
24

Redlich-Kwong EOS

The Redlich-Kwong EOS is given by

RT
a
P
1/ 2
b T ( b)
where
0.42728R 2Tc2.5
a
Pc
0.08664 RTc
b
Pc

25

Soave-Redlich Kuang EOS

is given by the equation:

RT
a
P

b ( b)
where

T
a a c 1 m 1
Tc

0.42747 R 2Tc2
ac
Pc

m 0.48508 1.55171 0.15613 2

0.08664 RTc
b
Pc

26

Soave-Redlich-Kwong EOS

written as a cubic polynomial:

Z 3 Z 2 Z 0
Where
-1
A B B2
-AB
A aP/(RT)2
B bP/RT
27

Example 3: SRK Equation

Use the SRK EOS to calculate for nButane at 500K and 30 bar
1. Z
2. v

28

29

30

Peng-Robinson EOS

is given by the equation

RT
a
P

b ( b) b( b)
where

T
a a c 1 m 1

0.45723553R 2Tc2
ac
Pc

m 0.37464 1.54226 0.26992 2

0.077796074RTc
b
Pc

31

Peng-Robinson EOS

written as a cubic polynomial:

Z 3 Z 2 Z 0
Where
B1
A 2B 3B2
B3 + B2 AB
A aP/(RT)2
B bP/RT
32

Figure 3.4 Comparison

of behavior of cubic in Z
for the PR-EOS at
several conditions.

P = Psat, T < Tc: The larger root of f(Z) is the vapor root. The
smallest root is the liquid root. The middle root corresponds to
a condition that violate thermodynamics stability.

P >> Psat, T < Tc: Compressed liquid, vapor root is less stable.

P << Psat, T < Tc: Superheated vapor, liquid root is less stable.

T > Tc: Supercritical fluid which can only have a single root.

33

17

The cubic equation can be solved by:

Iterative method such as the Newton-Raphson method
Analytical solution

1.

A summary of steps for iterative method:

Guess Zold=1 or Zold=0 and compute Fold(Zold)

2.

Compute dF/dZ

3.

Znew=Zold-F(Z)/(dF/dZ)

4.

If Z / Z new 1E 5 , print the value of Znew and stop

5.

Compute Fnew(Znew) and use this as Fold. Return to step 3

until step 4 terminates
An

initial guess of Z=0 converges on the smallest real root.

An initial guess of Z=1 converges on the largest real root.
At very high reduced pressures, an initial guess >1 may be required.

Example: Peng-Robinson
Equation

Use the Peng-Robinson EOS to

calculate for n-Butane at 500K and 30
bar
1. Z
2. v

35

Peng-Robinson EOS

Use the Peng-Robinson EOS to calculate for nButane at 500K and 30 bar

36

Example: Peng-Robinson
Equation

Estimate the specific volume for CO2 at 310K and (a) 8 bars (b) 75 bars by
the Peng-Robinson equation and compare to the experimental values of
70.58 cm3/g and 3.9 cm3/g respectively.
Solution: = 0.228, Pc= 73.82 MPa, Tc= 304.2 C
(a)
v= ZRT/P
= ZRuT/PM
= [0.961*83.14cm3bar/molK*310 K]/[8 bar*44g/mol]
= 70.36 cm3/g (within 0.3 % of the experimental value)

37