Chapter 8

Real Gases
Compression Factors
Real gases do not obey the perfect gas equation exactly. The
measure of the deviation from ideality of the behavior of a
real gas is expressed as the compression factor Z:
RT
PV
T P Z
m
) , (
(8.1)
Real Gases
Z
P
200 K
500 K
1000 K
200 K
1000 K
0 300 600 900
3
2
1
0
CH
4
Z
P
H
2
0 100 200 300
1.2
1
0.8
0
0
o
C

N
2
CH
4
Physical Chemistry
Real Gas Equations of State
( ) RT b V
V
a
P
m
m
=
|
|
.
|

\
|
+
2
2
m m
V
a
b V
RT
P

=
(8.2)
van der Waals equation
Ideal Gas Law/Perfect Gas Equation:

PV = nRT (1.18)*
RT PV
m
=
Real Gases
Physical Chemistry
Van der Waals Equation of State
RT b V
V
a
P
m
m
= + ) )( (
2
RT PV
m
=
Real Gases
Physical Chemistry
: to correct the effect of intermolecular attractive forces
on the gas pressure
2
m
/ a V
b: the volume excluded by intermolecular repulsive forces
Virial Equation of State
(

+ + + + =
3 2
) ( ) ( ) (
1
m m m
m
V
T D
V
T C
V
T B
RT PV
(8.4)
Redlich-Kwong Equation
2 / 1
) ( T b V V
a
b V
RT
P
m m m
+

=
(8.3)
Real Gases
Physical Chemistry
Real Gas Equations of State
The limited accuracy of the data allows evaluation of only
B(T) and sometimes C(T).
Virial Equation of State
] ) ( ' ) ( ' ) ( ' 1 [
3 2
+ + + + = P T D P T C P T B RT PV
m
(8.5)
2 2 2
) ' ' ( , ' T R C B C RT B B + = =
(8.6)
B
P
RT
V
m
+ =
(8.7)
low P
m m m m
m m
RTV
a
V b RTV
a
b V
V
Z
RT
PV

= =
/ 1
1
vdW gas
2
m m
V
a
b V
RT
P

=
(8.2)

RT
V
m
Real Gases
Physical Chemistry
(

+ + + + =
3 2
) ( ) ( ) (
1
m m m
m
V
T D
V
T C
V
T B
RT PV
(8.4)
Power series in 1/V
m
Power series in P

Gas Mixtures
2 2 1 1 2
2
2
2 / 1
2 1 2 1 1
2
1
) ( 2 b x b x b and a x a a x x a x a + = + + =
(8.10)
For a mixture of two gases, 1 and 2, use a two-parameter
equation,
(8.11)
tot
m
n
V
V
mean molar volume
Real Gases
Physical Chemistry
x
1
and x
2
: the mole fractions of the components
b: a weighted average of b
1
and b
2

a: related to intermolecular attractions
(a
1
a
2
)
1/2
: intermolecular interaction between gases 1 and 2

Isotherms of H
2
O
P
V
m

400
o
C
U
R
J
N
Y
374
o
C
300
o
C
200
o
C
H
2
O
L + V
L
V
L
G
H
T S
K
M
W
Condensation
T < 374
o
C
gas condenses to
liquid when P|
T = 300
o
C
R(vapor)S(satura
ted vapor), P|, V+
S(saturated
vapor)W(saturated
liquid), P, V+ +
W(saturated
liquid)Y(liquid),
P |, V+
Real Gases
Physical Chemistry
t/
A
D
C
0.00611
0.01
solid
gas
liquid
O
P

/

1
0

5

P
a

374.2
218 atm
H
2
O phase diagram: P T
99.974
1 atm
0.0024
I
R
S
Y
T
f
T
b
T
3
Real Gases
Physical Chemistry
400
o
C
Condensation
T > 374
o
C
No amount of
compression will
cause the
separation out of a
liquid phase in
equil. with the gas.
T = 374
o
C
Critical temperature T
c
Critical pressure P
c
Critical volume V
m,c
Critical constants
Isotherms of H
2
O
P
V
m

U
R
J
N
Y
374
o
C
300
o
C
200
o
C
H
2
O
L + V
L
V
L
G
H
T S
K
M
W
Real Gases
Physical Chemistry
Fig. 8.3
Critical constants
Critical T (T
c
), T
c
(CO
2
)=304.2 K
Critical P (P
c
), P
c
(CO
2
)=7.38 MPa
Critical molar V (V
m,c
), V
m,c
(CO
2
)=9410
-6
m
3
mol
-1

Isotherms of CO
2

{P}
{V
m,c
}
T
3

c
T
c

g
b
a
l
T
1
T
2

Real Gases
Physical Chemistry
Table 8.1 Critical Constants
Species T
c
/ K P
c
/ atm

V
m,c
/ cm
3
mol
-1
Ar 150.7 48.3 74.6
Ne 44.4 27.2 41.7

N
2
126.2 33.5 89.5
H
2
O 647.1 217.8 56.0
D
2
O 643.9 213.9 56.2

H
2
S 373.2 88.2 98.5
CO
2
304.2 72.88 94.0
HCl 324.6 82.0 81.0
CH
3
OH 512.5 80.8 117
Real Gases
Physical Chemistry
Fluid
There is a continuity between the gaseous and the liquid
states. In recognition of this continuity, the term fluid is used
to mean either a liquid or a gas.
An ordinary liquid can be viewed as a very dense gas. Only
when both phases are present in the system is there a clear-cut
distinction between liquid and gaseous states.
For a single-phase liquid system it is customary to define as a
liquid a fluid whose temperature is below T
c
and whose molar
volume is less than V
m,c
.
If these two conditions are not met, the liquid is called a gas.
So a further distinction between gas and vapor can be made,
but these two words are used interchangeably in this book.
Real Gases
Physical Chemistry
Supercritical fluid
A supercritical fluid is one whose T and P satisfy
A supercritical fiquid usually has liquidlike density but its
viscosity is much lower than typical for a liquid and diffusion
coefficients in it are much higher than in liquids.
T > T
c
and P > P
c

Real Gases
Physical Chemistry
Supercritical fluid
-60 -40 -20 0 20 40 60 80 100
B
5
10
15
20
25
30
35
-56.6
t c=31.06

t/
o
C
gas
liquid
solid
100
200
300
400
500
600
700
800
900 1000 1100 1200
p /MPa
P c
=7.38MPa
A
0.518MPa
Supercritical
CO
2
is used
commercially
as a solvent to
decaffeinate
coffee.
Real Gases
Physical Chemistry
CO
2
Critical data and equations of state
Differentiating the van der Waals equation (8.2)
3 2
2
) (
m m
T
m
V
a
b V
RT
V
P
+

=
|
|
.
|

\
|
c
c
and
0 =
|
|
.
|

\
|
c
c
T
m
V
P
0
2
2
=
|
|
.
|

\
|
c
c
T
m
V
P
At the critical point:
(8.12)
2
m m
V
a
b V
RT
P

=
4 3 2
2
6
) (
2
m m
T
m
V
a
b V
RT
V
P

=
|
|
.
|

\
|
c
c
Application of the conditions (8.12) gives
3
,
2
,
2
) (
c m c m
c
V
a
b V
RT
=

and
4
,
3
,
3
) (
c m c m
c
V
a
b V
RT
=

(8.13)
Real Gases
Physical Chemistry
Critical data and equations of state
Division of the first equation in (8.13) by the second yields
2
, , c m c m
c
c
V
a
b V
RT
P

=
From van der Waals equation:
(8.14)
4
,
3
,
3
,
2
,
3
2
) (
) (
c m
c m
c m
c
c m
c
V
a
V
a
b V
RT
b V
RT
=

Use of (8.15) in the first equation in (8.13) gives

3
2
,
,
c m
c m
V
b V =
and
3 2
27
2
4 b
a
b
RT
c
=
(8.16)
b V
c m
3
,
=
(8.15)
Rb
a
T
c
27
8
=
Real Gases
Physical Chemistry
Critical data and equations of state
2
, , c m c m
c
c
V
a
b V
RT
P

=
Substitution of (8.15) and (8.16) into (8.14)
(8.14)
gives
2 2
27 9 2
27 / 8
b
a
b
a
b
b a
P
c
= =
(8.16)
b V
c m
3
,
=
(8.15)
Rb
a
T
c
27
8
=
(8.17)
Real Gases
Physical Chemistry
Critical data and equations of state
Substitution of (8.15) and (8.16) into (8.14)
Three equations for two parameters, a and b
2
27b
a
P
c
=
(8.16)
b V
c m
3
,
=
(8.15)
Rb
a
T
c
27
8
=
(8.17)
c
c
P
T R
a
64
27
2 2
=
(8.18)
c
c
P
RT
b
8
=
vdW gas
Real Gases
Physical Chemistry
Critical data and equations of state
Combination of (8.15) to (8.17)
2
27b
a
P
c
=
(8.16)
b V
c m
3
,
=
(8.15)
Rb
a
T
c
27
8
=
(8.17)
375 . 0
8
3
,
= =
c
c m c
c
RT
V P
Z
(8.19)
Real Gases
Physical Chemistry
Predicts the compressibility factor at the critical point
Van der waals equation
Critical data and equations of state
375 . 0
8
3
,
= =
c
c m c
c
RT
V P
Z
(8.19)
1
,
=
c
c m c
RT
V P
ideal gas
c
c
c
c
P
RT
P
RT
b 08664 . 0
3
) 1 2 (
3 / 1
=

=
(8.20)
c
c
c
c
P
T R
P
T R
a
2 / 5 2
3 / 1
2 / 5 2
42748 . 0
) 1 2 ( 9
=

=
(8.21)
333 . 0
3
1
,
= =
c
c m c
c
RT
V P
Z
(8.22)
R-K equation
Real Gases
Physical Chemistry
Van der waals equation
Selected equations of state
Equation Critical constants
Perfect gas
van der
Waals
Berthelot
m
V
RT
P =
2
m m
V
a
b V
RT
P

=
2
m m
TV
a
b V
RT
P

=
2
27b
a
2 / 1
3
3
2
12
1
|
|
.
|

\
|
b
aR
bR
a
27
8
2 / 1
3
2
3
2
|
.
|

\
|
bR
a
b 3
b 3
c
V
c
T
c
P
Real Gases
Physical Chemistry
Selected equations of state
Equation Critical constants
Perfect gas
R-K
virial
m
V
RT
P =
2 / 1
) ( T b V V
a
b V
RT
P
m m m
+

=
|
|
.
|

\
|
+ + + =
2
) ( ) (
1
m m m
V
T C
V
T B
V
RT
P
c
V
c
T
c
P
Real Gases
Physical Chemistry
The law of corresponding states
The critical constants are characteristic properties of gases
The reduced variables of a gas by dividing the actual variable
by the corresponding constant.
The observation that the real gases at the same reduced
volume and reduced temperature exert the same reduced
pressure is called the law (principle) of corresponding
states.
,
c
r
P
P
P ,
,c m
m
r
V
V
V ,
c
r
T
T
T
(8.27)
reduced
pressure
reduced
volume
reduced
temperature
) , (
r r r
T P f V =
(8.28)
Real Gases
Physical Chemistry