CHAPTER 2

EQUATION
OF STATE

EQUATION OF STATE
An equation of state
between state variables

is

relation

It
is
a
thermodynamic
equation
describing the state of matter under a
given set of physical conditions.
It is a constitutive equation which
provides a mathematical relationship
between two or more state functions
associated with the matter, such as its
temperature,
pressure,
volume,
or
internal energy.
Equations

of

state

are

useful

in

CLASSICAL IDEAL GAS LAW

PV = RT
Assumpti
on:
1) the gas consists of a large number of
molecules, which are in random motion
and obey Newton's laws of motion;
2) the volume of the molecules is
negligibly small compared to the volume
occupied by the gas; and
3) no forces act on the molecules except
during elastic collisions of negligible

CUBIC EQUATIONS OF STATE

Van der Waals equation of state
RedlichKwong equation of state

Soave modification of RedlichKwon

PengRobinson equation of state

VAN DER WAALS EQUATION OF STATE

The van der Waals equation may be
considered as the ideal gas law,
improved due to two independent
reasons:
Molecules are thought as particles with
volume, not material points. Thus V
cannot be too little, less than some
constant. So we get (V b) instead of V.
We consider molecules attracting
others within a distance of several
molecules' radii affects pressure

 P a V b RT

2
V

where V is molar volume

The substance-specific constants a and
b can be calculated from the critical
properties Pc, Tc, and Vc as
27R2 Tc2 27R2 Tc2
a

64 Pc
64 Pc
1 RTc 1 RTc
b

8 Pc 8 Pc

Cubic form of vdW eos

RT a
P
2
V b V
RT 2 a
ab

V b V V 0
P
P

P
3

Z3 B 1 Z2 A Z AB 0
aP 27Pr
A 2 2
R T 64Tr2
bP 1 Rr
B

RT 8 Tr

Principle of Corresponding States (PCS)

The principle of Corresponding States
(PCS) was stated by van der Waals and
reads: Substances behave alike at the
same reduced states. Substances at same
reduced states are at corresponding
states.
Reduced properties provide a measure of
the departure of the conditions of the
T
substance
from its Pown critical conditions
V
Tr
Pr
Vr
and are
Tc defined asPfollows
V
c
c

 The PCS says that all gases behave

alike at the same reduced conditions.
That is, if two gases have the same
relative departure from criticality
(i.e., they are at the same reduced
conditions), the corresponding state
principle demands that they behave
alike.
In this case, the two conditions
correspond to one another, and we
are to expect those gases to have the
same properties.

educed form of vdW EOS:

3
Pr 2 3Vr 1 8Tr
Vr

This equation is universal.

It does not care about which fluids we are
talking about.
Just give it the reduced conditions Pr, Tr
and it will give you back Vr regardless
of the fluid.
As long as two gases are at
corresponding states (same reduced
conditions), it does not matter what

The compressibility factor at the critical

point, which is defined as
PcVc
Zc
RTc
Zc is predicted to be a constant
independent of substance by many
equations of state; the Van der
Waals equation e.g. predicts a value of
0.375

Zc of various substances
Substance
H2O

Ne
N2

Value
0.23
0.30
0.30
0.29
0.29

Ar

0.29

He
H2

Application of
PCS

StandingKatz
Compressibili
ty Factor
Chart

REDLICH-KWONG EOS
RT
a
P

V b V V b
R2 Tc2
a 0.42748
Pc

1 2
Tr

RTc
b 0.08662
Pc
The RedlichKwong equation is adequate for
calculation of gas phase properties when:

P T

Pc 2Tc

Cubic form of RK eos

RT
a
P

V b V V b
Z3 Z2 A B B2 Z AB 0
aP
Pr
A 2 2 0.427482
RT
Tr
bP
Pr
B
0.08662
RT
Tr

SOAVE-REDLICH-KWONG EOS
RT
a
P

V b V V b
R2 Tc2
a 0.42748
Pc

RTc
b 0.08662
Pc

1 0.48508
1.55171
0.15613
1 T
2

ForH2 : 1.202exp 0.30288

Tr

0.5
r

Cubic form of SRK eos

RT
a
P

V b V V b
Z3 Z2 A B B2 Z AB 0
aP
Pr
A 2 2 0.427482
RT
Tr
bP
Pr
B
0.08662
RT
Tr

PENG-ROBINSON EOS
RT
a
P
2
V b V 2bV b2
R2 Tc2
a 0.45724
Pc
RTc
b 0.07780
Pc
1 0.37464
1.54226
0.2699

1 T
0.5
r

Cubic form of PR eos

RT
a
P
2
V b V 2bV b2
Z3 1 B Z2 A 2B 3B2 Z AB B2 B3 0
aP
Pr
A 2 2 0.457242
RT
Tr
bP
Pr
B
0.07780
RT
Tr

SOLVING CUBIC EQUATION

Z c2Z c1 Z c0 0
3

eos

c2

c1

c0

vdW
RK
SRK
PR

B1
1
1
B1

A
A B B2
A B B2
A 2B 3B2

AB
AB
AB
AB B2
B3

Z3 c2Z2 c1 Z c0 0
Calculate:
2
1

c
K c2
27
1
L 2c32 9c2c1 27c0
22
K3 L2
D
27 4
L

M D
2

(determinant)
13

N D
2

13

ase 1: D > 0
1 real root and 2 imaginary roots
c2
Z1 M N
3

se 2: D = 0

three real roots and at least two are equal

c2
Z1 M N
3
1
c2
Z2 Z3 M N
2
3

Case 3: D < 0
three, distinct, real roots

Zi 2

Where

K
c2
120
cos
k
3
3

k = 0 for i = 1
k = 1 for i = 2
k = 2 for i = 3

L 4

cos

27

The minus sign applies when B > 0,

The plus sign applies when B < 0.

NON CUBIC EQUATIONS OF STATE

VIRIAL EOS
B C D
Z 1 2 3 ...
V V V
PV
Z
1 B'P C'P2
RT
B
B
'
RT

C B
C'
RT 2

D 3BC 2B3
D'
3
RT

DIETERICI EOS

a RTV

P V b RTe

a
Tc
4Rb

a
Pc 2 2
4b e

Vc 2b

MIXTURE
For mixtures, we apply the same
equation, but we impose certain mixing
rules to obtain a and b, which are
functions of the properties of the pure
components.
We create a new pseudo pure
substance
a m that
ij the average
yiyj ahas
i j of the mixture.
properties
a ij 1 kij a i a j
bm yibi
i