Kinetic theory

Collective behaviour of large

systems
 Why gases exert pressure
 Gases are mostly empty space
 Gases contain molecules which have random
motion
 The molecules have kinetic energy
 The molecules act independently of each other –
there are no forces between them
 Molecules strike the walls of the container – the
collisions are perfectly elastic
 Exchange energy with the container
 The energy of the molecules depends upon the
temperature
 Large collections are very
predictable
 Fluctuations in behaviour of a small group of
particles are quite noticeable
 Fluctuations in behaviour of a large group (a
mole) of particles are negligible
 Large populations are statistically very
reliable
 Pressure and momentum
 Pressure = force/unit area
 Force = mass x acceleration
 Acceleration = rate of change of velocity
 Force = rate of change of momentum
 Collisions cause momentum change
 Momentum is conserved
Elastic collision of a particle with the
wall
 Momentum lost by particle = -2mv
 Momentum gained by wall = 2mv
 Overall momentum change = -2mv + 2 mv =
0
 Momentum change per unit time = 2mv/Δt
momentum change no collisions 1
P x x
collision time area
 Factors affecting collision rate
1. Particle velocity – the faster the particles
the more hits per second
2. Number – the more particles – the more
collisions
3. Volume – the smaller the container, the
more collisions per unit area
vN o 2mv 2 N o
P  2mv  
V V
 Making refinements
 We only considered one wall – but there are
six walls in a container 2 2
1 2mv N o mv N o
 Multiply by 1/6 P x 
6 V 3V
 Replace v2 by the mean square speed of the
ensemble (to account for fluctuations in
velocity)
2
1 m v No
P
3 V
 Boyle’s Law
 Rearranging the previous equation:
2  m v 2
 2
PV    N o  N o Ek
3 2  3
 
 Substituting the average kinetic energy
 Compare ideal gas law PV = nRT:
3
Ek  nRT
2
 The average kinetic energy of one mole of
molecules can be shown to be 3RT/2
 Root mean square speed
 Total kinetic energy of one mole
1 3
Ek  N o m v  RT
2

2 2
 But molar mass M = Nom
3RT 3RT
vRMS  
mN o M

 Since the energy depends only on T, vRMS

decreases as M increases
 Speed and temperature
 Not all molecules move at the same speed
or in the same direction
 Root mean square speed is useful but far
from complete description of motion
 Description of distribution of speeds must
meet two criteria:
 Particles travel with an average value speed
 All directions are equally probable
 Maxwell meet Boltzmann
 The Maxwell-Boltzmann
distribution describes the
velocities of particles at a
given temperature
2  mv 2 / 2 k BT
F (v)  Kv e
3/ 2
 m 
K  4  
 2 k B T 
 Area under curve = 1
 Curve reaches 0 at v = 0
and ∞
 M-B and temperature
 As T increases vRMS
increases
 Curve moves to right
 Peak lowers in height
to preserve area
 Boltzmann factor: transcends
chemistry
 Average energy of a particle
mv 2

2
 From the M-B distribution
   1
exp   
 k B T  exp   
 
k T
 B 
 The Boltzmann factor – significant for any and all
kinds of atomic or molecular energy
 Describes the probability that a particle will adopt
a specific energy given the prevailing thermal
energy
  
P ( )  exp   
k
 B  T
 Applying the Boltzmann factor
 Population of a state at a level ε above the
ground state depends on the relative value
of ε and kBT
 When ε << kBT, P(ε) = 1   
P ( )  exp   
 When ε >> kBT, P(ε) = 0  kBT 

 Thermodynamics, kinetics, quantum

mechanics
 Collisions and mean free path
 Collisions between
molecules impede
progress
 Diffusion and effusion
are the result of
molecular collisions
 Diffusion
 The process by which gas molecules
become assimilated into the population is
diffusion
 Diffusion mixes gases completely
 Gases disperse: the concentration
decreases with distance from the source
 Effusion and Diffusion
 The high velocity of molecules leads to rapid
mixing of gases and escape from punctured
containers
 Diffusion is the mixing of gases by motion
 Effusion is the escape of a gas from a
container
 Graham’s Law
 The rate of effusion of a gas is inversely
proportional to the square root of its mass
1
Rate 
m

 Comparing two gases

Rate1 m2 m2
 
Rate2 m1 m1
 Living in the real world
 For many gases under most conditions, the
ideal gas equation works well
 Two differences between the ideal and the
real
 Real gases occupy nonzero volume
 Molecules do interact with each other –
collisions are non-elastic
 Consequences for the ideal gas
equation
1. Nonzero volume means actual pressure is
larger than predicted by ideal gas equation
 Positive deviation
2. Attractive forces between molecules mean
pressure exerted is lower than predicted –
or volume occupied is less than predicted
 Negative deviation
 Note that the two effects actually offset
each other
 Van der Waals equation:
tinkering with the ideal gas equation
 Deviation from ideal is more apparent at
high P, as V decreases
 Adjustments to the ideal gas equation are
made to make quantitative account for these
effects  an 2 
 P  2 V  nb   nRT
 V 
Correction for Correction for
intermolecular molecular
interactions volume
 Real v ideal
 At a fixed temperature
(300 K):
 PVobs < PVideal at low P
 PVobs > PVideal at high P
Effects of temperature on deviations
 For a given gas the
deviations from ideal
vary with T
 As T increases the
negative deviations
from ideal vanish
 Explain in terms of van
der Waals equation
 an 2 
 P  2 V  nb   nRT
 V 
 Interpreting real gas behaviors
 First term is correction for
volume of molecules
 Tends to increase Preal  an 
2
 Second term is correction  P  2 V  nb   nRT
for molecular interactions  V 
 Tends to decrease Preal 2
 At higher temperatures, nRT na
P  2
molecular interactions are V  nb V
less significant
 First term increases relative to
second term