CHE 3473

Chemical Engineering Thermodynamics

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

Lecture 10
Virial Equation of State

Virial Equation of State

Virial Equation of State
PV
B(T ) C (T )
= 1+
+ 2 + ...

RT
V
V

The third Virial coefficient

The second Virial coefficient

Benedict-Webb-Rubin (BWR) EOS

Used mainly for light hyrdocarbons, natural gas
See SVNA page 89
* Characteristics
High accuracy for this restricted group of molecules
Cumbersome (8 adjustable parameters)
The meaning is not very clear for mixtures.

Virial Equation of State

As 0, gases become ideal. Expand Z

PV
=1
RT

Idea: for real gas in a Taylor series about =0, at constant T.

Review: Taylor series
=

& ' ())

& ''())
& '''())
2
+ +! (x-a) + -! (x-a) + .! (x-a)3 +
=

:()
=9
( ):
!
:>?

= 0 = 1 + + + + ,
1! 2! 3!

< <

Virial Equation of State

=

Virial Equation of State

As 0, gases become ideal. Expand Z

PV
=1
RT

for real gas in a Taylor series about =0, at constant T

Z =Z

=0

Z
+

1 2Z

+
2
2

T , =0

Z = 1 + B + C 2 + D 3 +

or

2 +
T , =0

=1/V,
unit mass

(Virial EOS, Onnes, Leiden,1901)

PV
= Z = 1 + B'P + C 'P2 +
RT
B
C
= 1+ + 2 +
V V

(1)
(2)

Virial Equation of State

From (2): P =

RT
B
C
[1 + + 2 + ]
V
V V

Substitute for P in (1):

PV
B ' RT
B ' BRT
1
C ' ( RT ) 2
1
= 1+
+
+ o( 3 ) +
+ o( 3 )
2
2
RT
V
V
V
V
V
B ' RT
B ' BRT + C ' ( RT ) 2
= 1+
+
+
2
V
V
B ' RT = B

B
B =
RT
'

2
C

B
C' =
(RT ) 2

Virial Equation of State

Second virial coefficient

Third virial coefficient

Fourth virial coefficient

Z
B

=0

1 2Z
C
2 2

=0

1 3Z
D
3! 3

=0

Molecular theory (statistical thermodynamics) shows that:

B gives contribution to Z from 2 molecule (pair) interaction
C2 gives contribution to Z from 3 molecule (triple) interaction
D3 gives contribution to Z from 4 molecule interaction etc.

Virial Equation of State

Pressure Series: alternatively, we could expand Z in power of P

Z = 1 + B' P + C ' P 2 + D' P3 +

B, C, D are related to B, C, D,
B
Z
B =
=

RT P T , P =0
'

2
2

B
1

Z
'
C =
=
2
( RT )
2 P 2
3
D

3
BC
+
2
B
D' =
(RT )3

T , P = 0

(Otto, Berlin,1920s)

Virial Equation of State

Notes:
(1)The series usually converges faster than the P series;
(2)B, C, depend on T (and on composition for mixtures);
(3)To find B, C from experimental data, plot
PV

V
1 VS. 1
RT

PV

V
1
RT

The slope=C
B

1
=
V

Virial Equation of State

(4) B, C, D, 0 , as T
(5) Virial EOS is especially useful for mixtures since we have
exact mixing rules from statistical mechanics. (We know how B,
C, D,depend on composition x1, x2, x3,)
(6) The virial expansion can be rigorously derived from statistical
mechanics. This gives exact relations of B, C, D, in terms of
Intermolecular forces. The benefits are:
(a) Easy to get accurate correlations (corresponding states)
for B,C,, so that we can predict coefficients.
(b) Know exact mixing rules
(7) Virial EOS is most useful for low to moderate density gases.
For very dense gases or liquids the convergence of the series
becomes poor and the series is not useful.

Predicting the Future

Radio has no future
Lord Kelvin, 1896.
Heavier-than-air flying machines are impossible
Lord Kelvin, 1896.
William Thomson, physicist, engineer and inventor, later (1892-)
Lord Kelvin, was famous for his work on the transatlantic
telegraph and for determining the absolute zero of temperature
as t = -273.15oC. The Kelvin unit is named after him. The name
Kelvin refers to the Kelvin River in Scotland.

William Thomson, Lord Kelvin (1824-

2007)