CHE 3473

Chemical Engineering Thermodynamics

Room A-235, SEC
M, W, F, 9:30-10:20 AM

Lecture 12
Corresponding State Theory

From the previous lecture

Law of Corresponding States

A. Corresponding States Principle (CSP)
The simple CSP was proposed by van der Waals, based on his EOS:
a
RT
a

2
P + 2 (V b ) = RT or P =

V
V

b
V

At the critical point

2

P
P
=0
= 0 and
2

V T ,C
V T ,C
Applying these conditions to the vdW EOS:
27 R 2TC2
9
a=
= RTCVC
64 PC
8

RTC
1
b=
= VC
8 PC
3

ZC

PCVC
3
=
=
RTC
8

Law of Corresponding States

Substitute for a and b in eq. (1):

9 RTCVC
1
P+
T
8V 2

RTC

V
8PC

= R

PRTC 9 R 2TC2VC
PV 9 RTCVC
+

=R
2
T
8 TV
8 PCT
64V PCT

Multiply eq. (2) by TC/PCVC

1
PrVr
+ 3
Tr
TrVr
where

P
Pr =
PC

1 Pr
1
8

2 =
3
3 Tr Vr Tr
Tr =

T
TC

V
Vr =
VC

Law of Corresponding States

Eq. (3) says:

Pr = f (Tr ,Vr )
PV
Z = f (Tr , Pr ) =
RT
PrVr PCVC 3 PrVr

=
=
Tr RTC 8 Tr
'

f and f are the same functions for all substances. This applies even if
vdW eqn. is not correct, as long as 2 parameters are sufficient.
The figure is from S.I Sandler, Chemical Engineering Thermodynamics, 2nd edn., Wiley, NY (1989)

General 2-Parameter EOS

If EOS is: P = f (T ,V ; a, b)
P
=0

V T ,C

At point C

2 P
=0

2
V T ,C

f (TC , VC ; a, b ) = 0
'

f = (TC , VC ; a, b ) = 0
''

Solve (2) and (3) for a and b in terms of Tc, Vc:

P= f

'''

(T , V ; TC ,VC )

or

Pr = f

'''

(Tr ,Vr )

General 2-Parameter EOS

In practice, ZC is constant for simple fluids,
but not for more complex ones:
Zc
Ar

0.290

Kr

0.291

Xe

0.290

N2

0.291

CH4

0.290

C(CH3)4

0.269

H2O

0.230

Conclusion: if a group of substances obey the same 2-parameter

EOS, then the simple corresponding states principle holds.

Law of Corresponding States

B. 3-Parameter Corresponding States, Pitzers Method
Simple CSP doesnt hold well for more complex fluids like water,
alcohols, higher MW hydrocarbons, etc. Pitzer examined
departures from simple CSP for many fluids, and sought to answer
the question: what is a good choice of a 3rd parameter in the eqn.

T P

Z = f
,
, X
TC PC

We want to choose X to be a sensitive measure of the departure

from simple CSP, but X also should be easy to measure. Pitzer
found that the temperature dependence of the vapor pressure was
sensitive to non-spherical intermolecular forces. Also vapor
pressure is easy to measure. He plotted:
1
Sat
log10 Pr
VS.
Tr

3-Parameter Corresponding States

1.43

log10 PrSat

1
Tr

-1.000

Simple Fluids
(Ar, Kr, Xe)

-1.000-

H2O

It turns out that for simple insert gases:

Sat
r

log10 P

= 1.000 at Tr=0.700 (1/Tr=1.43)

3-Parameter Corresponding States

For more complex fluids, e.g. H2O, at Tr=0.7, the log10PrSat lie below
the value for (Ar, Kr, Xe), so Pitzer defined the acentric factor by:

1.000 log10 (P

Sat
r
Tr = 0.7

CH4

0.008

n-C5H12

0.251

n-C8H18

0.394

CH3COOH

0.454

C6H6

0.212

EtOH

0.635

H2O

0.344

Simple fluids, Ar, Kr, Xe:

=0.

Generalized Correlations of Pitzer

Z = Z (Tr , Pr , )
Expand Z about =0 in power of : Z=Z0+Z1
Where Z0=Z0(Tr, Pr)
Z1=Z1(Tr, Pr)
Z0, Z1 correlations are established using experimental
data for many fluids.
General Procedures:
Given T and P for substance of interest, calculate V and Z
(1) Look up Tc, Pc, , calculate Tr, Pr (App. B)
(2) Get Z0, Z1 at this Tr, Pr (App. E)
(3) Calculate from Z=Z0+Z1, V=Z(RT/P)

Example Problems
Problem #1
(a)Estimate the volume of 1kg of carbon monoxide at 71 bar and
147.4K. For carbon monoxide, Pc=34.99bar, Tc=132.9K, =0.048,
M=28.010kg/kmol.
(b) 560 g of dry ice (solid CO2) are introduced into an evacuated
2-liter container. The temperature rises, and CO2 vaporizes.
If the pressure in the tank is not to exceed 111bar, what should be
the maximum allowable temperature of the tank? For CO2,
Pc=73.83bar, Tc=304.2K, =0.024, M=44.010 kg/kmol.

Example Problems
Solution:
(a)
P
71
Pr =
=
= 2.0
PC
34.99

T
147.4
Tr =
=
= 1.1
TC 132.9

From App. E at p. 698, 699, we find: Z0=0.3953, Z1=0.0698

Z = Z 0 + Z 1 = 0.3953 + 0.048 0.0698 = 0.3987

nZRT 1 0.3987 8.314 147.4
3
3
V =
=
=
2.46

10
m
P
0.028 71 105

Example Problems
T
T
Tr =
=
TC
304.2
Using the equation V=nZ(RT/P), we have:
0.560
5
11110 0.002 =
8.314 Z T
0.044
ZT
209.8
ZTr =
=
= 0.69
ZT = 209.8
TC
304.2
Solve this by trial and error:

(b)

P
111
Pr =
=
= 1.5
PC
73.83

Find Z0 Find Z1

Z=Z0+Z1

Calculate ZTr, check with

0.1630

0.4619

0.5081

0.6605

0.1477

0.6640

0.7968

0.5959

0.1534

0.5996

0.6955

Given Pr

Guess Tr

1.5

1.1

0.4580

1.5

1.2

1.5

1.16

So, Tr=1.16, and

T = TrTC = 1.16 304.2 = 352.9 K

Example Problems
Problem #2
Calculate the work needed to compress isothermally 1 kg of
Isobutene from 100kPa and 300K (superheated vapor) to
saturated vapor conditions (V2=0.1449m3/kg). For the calculations
use the Soave-Redlich-Kwong cubic equation of state.
For isobutene: Pc=3647.7kPa, Tc=419.6K, R=0.148186kJ/(kg.K),
and =0.187.

Example Problems
Solution:
For isobutene: Pc=3647.7kPa, Tc=419.6K, R=0.148186kJ/(kg.K),and =0.187.
Then using the Soave-Redlich-Kwong EOS, the values of a and b are:
kJ m3
m3
a = 0.4531
b = 0.001477
kg
kg
At T=300K, the value of =0.9405. Since the initial state is a superheated vapor,
the specific volume of the initial state (100kPa, 300K) is given by the largest root
obtained by solving the cubic EOS:

V3

RT 2 V
ab
V +
a bRT Pb 2
=0
P
P
P

Solving this gives V1=0.4182m3/kg. In the final state, we know T2=T1, and
V2=0.1449m3/kg. To calculate the work, we can use the EOS and use it in the
definition of work:
V

vg ( v1 + b )
vg b a

W = P dV = RT ln

ln
= +43.41kJ

b
v1 ( vg + b )
v1 b
V