Statistical Molecular

Thermodynamics
Christopher J. Cramer
Video 2.5
Virial Equation of State

Virial Expansion
The compressibility is expressed as an infinite series
expansion in either the density (V1) or the pressure

PV
B2V (T) B3V (T) B4V (T)
Z=
= 1+
+
+
+ ...
2
3
RT
V
V
V

PV
2
3
Z=
= 1+ B2P (T)P + B3P (T)P + B4 P (T)P + ...
RT
BnX are virial coefficients (B2V is a second virial coefficient)
Note that at very low pressures or densities (large molar
volumes) Z 1, reflecting ideal behavior.

The 2nd Virial Coefficient

ammonia (NH3)

At low pressure

Z = 1+ B2P (T)P

Slope(T) = B2P(T)

Z is linear in B2P

Through manipulation of the two virial

expansions, one can also show that

B2V (T) = RT B2P (T)

Virial Terms for Argon at 298 K

B2V (T) B3V (T)

1+
+
+ (L)
2
V
V

units of B2V:
volumemol-1

P (bar)
1
1 - 0.00064 + 0.0000 + (0.00000)
10

1 - 0.00648 + 0.0020 (0.00007)

100

1 - 0.06754 + 0.0213 (0.00036)

What Does B2V Mean?

At low pressure:

PV
= 1+ B2P (T)P
RT

RT
+ RTB2P (T)
or: V =
P

Videal

B2V (T )

so:

V = Videal + B2V (T)

or:

B2V (T) = V Videal

B2V is the difference

between the
observed molar
volume and the ideal
gas molar volume

B2V(T) for Various Gases

B2V (T) = V Videal

Again: attractive forces dominate at low T, repulsive at high T