Virial Coefficients

Virial equation of state

CO2
PVm = RT (1 + B′P + C ′P + L)2

B C
PVm = RT (1 + + + L)
Vm Vm2
B, C : second & third virial coefficients

Boyle Temperature

P→0
dZ/dP = 0 for perfect gas
For real gases
dZ / dP = B` as P→0
dZ / (1/dVm) = B as Vm→∞
Boyle temperature
Virial coefficient ~ Function (Temp)
Temperature at which
B= dZ/dP = 0 as P→0
Condensation

Isotherm merged to
a single point Tc

* Liquid appears
* No pressure resistance on the
piston due to condensation
* Pressure corresponding to CDE:
vapor pressure

Critical Constants

Critical point : The point at which the volume at each end of the
horizontal part of isotherm have merged to a single point.

Critical temperature Tc
above Tc ~ no liquid phase (gas phase only)
normally denser than typical gases
→ Supercritical fluid

Critical pressure Pc

Critical molar volume Vc

 van der Waals Equation

Johannes Diderik van der Waals (Netherlands, 1873)

: suggesting a modeling equation for a real gas
1. Repulsive interactions: ‘Hard-sphere model’ of gas molecule
V-nb as a volume of real gas
nRT nRT
P= ⇒
V V − nb
2. Attractive interactions: reduce the total pressure
Pressure depends on ‘collision frequency’ and ‘collision force’
Both are proportional to the gas concentration of (n/V)
∴ a(n/V)2 for a reduced pressure
nRT n RT a
P= − a( ) 2 P= − 2
V − nb V Vm − b Vm

van der Waals Equation

nRT n 2
P= − a( )
V − nb V

RT a
P= − 2
Vm − b Vm
Variations

van der Waals Loop

van der Waals gas cf) Perfect gas

Unrealistic oscillations
→ van der Waals loops
 Maxwell Construction

Maxwell construction

Features of the Equation

RT a
P= − 2
Vm − b Vm
1) Perfect gas isotherms are obtained at high temperature and
large molar volumes.

when Vm >> b → Vm - b ≈ Vm

2) Liquids and gases coexist when cohesive and dispersing

effects are in balance.

→ van der Waals loop

3) Critical constants are related to the van der Waals coefficient.

Critical Point

dP RT 2a
=− + =0
dVm (Vm − b) 2 Vm3
d 2P 2 RT 6a
= − =0
dVm (Vm − b) Vm
2 3 4

a 8a
Vc = 3b Pc = Tc =
27b 2 27 Rb

PcVc 3
Zc = = = 0.375
RTc 8

Reduced Variables

Reduced variables
P Vm T
Pr = Vr = Tr =
Pc Vc Tc
Actual variables

P = Pr × Pc Vm = Vr × Vc T = Tr × Tc

Principle of corresponding state

Real gases at the same reduced volume and reduced

temperature exert the same reduced pressure
 Principle of Corresponding State

RTrTc a
Pr Pc = − 2 2
VrVc − b Vr Vc
aPr 8aTr a
= −
27b 2 27b(3bVr − b) 9b 2Vr 2

8Tr 3
reorganized to Pr = − 2 note that NO a and b
3Vr − 1 Vr

Properties of a range of gases can be coordinated on a single diagram

Principle of Corresponding State

(cf)
Mathematical Exercise

Let’s convert van der Waals equation to Virial equation

RT ⎛ 1 ⎞
P= − a⎜⎜ 2 ⎟⎟
Vm − b ⎝ Vm ⎠
⎛ ⎞
⎜ ⎟
RT ⎜ 1 a ⎟
= −
Vm ⎜ 1 − b RTVm ⎟
⎜ V ⎟
⎝ m ⎠
when b / Vm < 1 , we can rewrite this equation as follows

RT ⎧⎪ 2
b ⎛ b ⎞ ⎛ b ⎞
3
a ⎫⎪
P= ⎨1 + ⎜ ⎟ ⎜ ⎟
+ ⎜ ⎟ + ⎜ ⎟ + LL − ⎬
Vm ⎪⎩ Vm ⎝ Vm ⎠ ⎝ Vm ⎠ RTVm ⎪
⎭
RT ⎧ 1 ⎛ a ⎞ ⎫
= ⎨1 + ⎜ b − ⎟ + LL⎬
Vm ⎩ Vm ⎝ RT ⎠ ⎭