Molecular collisions

Mean free path

λ between two collisions
r.m.s. speed c= = λz z = collision frequency
1
z Time of flight
between two collisions
σ = collision cross-
section (target area)
= πd2

RT 2 N Aσpc
⇒ λ= ;z = Nils Walter: Chem 260
2 N Aσp RT
In reality: Gases have attractive and
repulsive forces
Lennard-Jones
6-12 potential At high T: perfect
gas isotherms

⇒
e.g.,
CO2 At low T:
liquefaction
Nils Walter: Chem 260
The critical point: Gas and liquid
density become equal
Heating a liquid in a container

At critical point
(for water 373oC
@ 218 atm!) the
boundary is lost

⇒ Application:
Extraction of caffeine
from coffee with
supercritical CO2

Nils Walter: Chem 260

Describing the deviation from the perfect gas
Introducing the molar volume of real gas
compression factor Z: Z= molar volume of perfect gas

Vm Vm pVm
Z= perfect
= =
Vm RT RT
p
Z = 1 ⇒ perfect gas
Z < 1 ⇒ molecules cluster, attractive
forces are dominant
Z > 1 ⇒ molecules repel each other,
repulsive forces are dominant
Nils Walter: Chem 260
The virial equation of state
virial coefficients
B C
Empirically: Z = 1 + + 2 + ...
Vm Vm
B > 0 ⇒ Z > 1, e.g., H2
B < 0 ⇒ Z < 1, e.g., CH4, NH3

C > 0 ⇒ Z > 1 at high pressure (Vm small)

and Z =
pVm
very accurate
RT
nRT  nB n 2C 
⇒ p= 1 + + 2 + ...
V  V V 
Nils Walter: Chem 260
 Physically more palpable:
The van der Waals equation
[Johannes van der Waals 1873]
Lennard-Jones
molecules have a molecules have 6-12 potential
non-zero volume attractive forces

⇒ reduction in exerted
pressure: a(n/V)2
[molecules strike less
frequently and with
reduced force]

 an 
2
⇒ additional volume ⇒  p + 2 (V − nb ) = nRT
needed: nb  V 
Nils Walter: Chem 260
Plotting the van der Waals equation:
In reasonable agreement with reality

only the van

der Waals
loops are
unrealistic

in 3D
p

T 260
Nils Walter: Chem

V
 Liquefaction of real gases:
The Joule-Thomson effect
Linde refrigerator
Real gases have attractive
forces

⇒ if they are allowed to

expand through a throttle
without outside heat
entering (“adiabatic”
process) they will use their
kinetic (heat) energy to
escape each other’s
attraction
⇒ they will cool down Nils Walter: Chem 260