Statistical Molecular

Thermodynamics
Christopher J. Cramer
Video 2.2
Non-ideal Gas Equations of State

Temperature and the Gas Constant

The Ideal Gas obeys:

PV = nRT

V
PV = RT, V =
n

or

universal gas constant

molar volume

H2

273.15 K measurements
At low pressures, all gases
converge to ideal behavior
PV (273.15) = 22.414 L atm mol1

N2
CO2

Gases Are Rarely Ideal

PV
=Z
RT

compressibility (unitless)
CH4

300 K

Low T and low P: attractive forces

V real < V ideal

High T or high P: repulsive forces

V real > V ideal

Johannes Diderik van der Waals

ideal nonsense!

a
P + 2 (V b) = RT

van der Waals equation of state

a and b are constants that depend on
the specific gas in question:
a ~ intermolecular interaction strength
b ~ molecular size
a (dm6barmol-2)
helium
0.035
ammonia
4.304

b (dm3mol-1)
0.024
0.037

Various Cubic Equations of State

van der Waals

RT a
P =
2
V b V

Redlich-Kwong

RT
A
P =
1/ 2
V B T V V + B

Peng-Robinson

RT

P =

V V V + + V

) (

Various Cubic Equations of State

van der Waals
ethane @ 400 K

Redlich-Kwong

expt (solid)

Peng-Robinson

Improved performance of the

more complex equations of state
at very high pressures

V 1 =

1
mol

L
(
)

1 L = 1 dm3

Various Cubic Equations of State

ethane @ 305.33 K

V
P1 <

liquid/vapor
equilibrium

V
L

P2 <

P3

While Redlich-Kwong and PengRobinson perform reasonably well into

the liquid phase, at a certain point the
van der Waals equation of state predicts
negative pressures!

RT a
P =
2
V b V
=

lim

RT a 2