23-Oct-19

Kinetic Theory of Gases

Introduction
• Applies laws of mechanics to individual molecules
• Thereby derive expressions for various properties like
Pressure
Internal Energy
Specific heat capacity etc.

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Basic Assumptions
1. Any macroscopic volume of a gas contains a very large number of
molecules.

No. of molecules in a kilomole NA (Avagadro no)= 6.02214 x 1026

At standard conditions,
- 1 kilomole of an ideal gas occupies 22.4 m3
-approximately 3 x 1025 molecules in a cubic meter
3 x 1019 molecules in a cubic centimetre
3 x 1016 molecules in a cubic millimeter

Basic Assumptions contd…

2. The molecules are separated by distances that are large compared with
their own dimensions and are in a state of continuous motion.

Diameter of a molecule ≈ 2 x 10-10 to 3 x 10-10 m(assumed sphere )

Assume at standard conditions
One molal volume is divided into cubical cells
With one molecule per cubical cell
Volume of a cell ≈ 30 x 10-27 m3
Length of one side of the cube ≈ 3 x 10-9 m
- The approximate distance between molecules is of this order

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Basic Assumptions contd…

3. Molecules exert no forces on one another except when they collide.
Therefore,
- In the absence of external forces
- Between collisions molecules move in straight line

Basic Assumptions contd…

4. Collisions of molecules are perfectly elastic
-Collide with each other and walls of container
-Walls of container assumed perfectly smooth
- So no change in tangential velocity during collision with walls

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Basic Assumptions contd…

5. In the absence of external forces, molecules are distributed
uniformly throughout the container
Average no. of molecules per unit volume
n= N / V where
N – total no. of molecules in a container
V – volume of container
Then, the number of molecules in an elemental volume ∆V
∆N = n ∆V

Basic Assumptions contd…

6.The directions of molecular velocities are assumed to be distributed
uniformly.

Assume each molecule has a vector attached to it

Vector represents magnitude and direction of its velocity
Transfer the vectors of all molecules to a common origin
Construct a sphere of arbitrary radius r with this origin as centre
The velocity vectors (may be extended) intersect the surface of the sphere
As many points of intersection as there are molecules
Uniform distribution of points of intersection over sphere surface

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Basic Assumption- 6 contd…

Average number of points per unit area is

N / 4πr2

No. of points in any elemental area ∆A is

∆ N = ∆A . N/4πr2
Because no. of molecules is very large,
range of directions can be made very small
and still include a large number of points

Basic Assumption- 6 contd- Figure -1…

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Basic Assumption- 6 contd…

In a Polar coordinate system
Any arbitrary direction in space can be specified by
Angles θ and φ as shown in fig
Area of a small element on the sphere surface
∆A ≈ (r sin θ ∆φ) ( r ∆θ ) = r2 sin θ ∆θ ∆φ
∆Nθφ – No. of molecules having velocities in a direction between
θ and θ + ∆θ , and φ and φ + ∆φ
∆Nθφ = ( r2 sin θ ∆θ ∆φ ) ( N / 4π r2 ) = sin θ ∆θ ∆φ

Basic Assumption- 6 contd…

• This quantity can be expressed per unit volume by dividing both sides
by volume to get
∆nθφ = sin θ ∆θ ∆φ
where ∆nθφ is the number density of molecules with velocities having
directions between θ and θ + ∆θ , and φ and φ + ∆φ

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• Finally consider magnitudes of molecular velocities

• To start with, assume that molecules can have speeds from zero to infinity
• Let ∆Nv represents the number of molecules having velocities between v
and v + ∆v
• Geometrically this number equals the number of velocity vectors
terminating within a thin spherical shell between spheres of radii r1=v
and r2 = v + ∆v
• While collisions cause speed of individual molecules to change, we assume
that at equilibrium , the number of molecules with speeds in any specified
range remains constant.

Molecular flux - Ф
• Molecular flux at any surface is defined as the total number of
molecules arriving at the surface per unit area per unit time

∆
Ф = ∆ ∆

where ∆N is the total number of molecules arriving from all

directions and with all speeds on one side of an element of
surface area ∆A during time interval ∆t

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Molecular flux contd..

• For an imaginary surface within the gas ,there will be 2 molecular fluxes on
either side of the surface
- One consisting of molecules arriving at that side
- the other consisting of molecules that have crossed the surface
from the other side
If there is no net motion of molecules, molecular fluxes on either side of the
surface will be equal in magnitude and opposite in directions
• If the surface is at the wall of the container, there are again 2 molecular
fluxes
- One consisting of molecules arriving at the surface
- the other consisting of molecules rebounding from the surface

Molecular flux contd..

Figure -2
• Let shaded area ∆A represent a small
element of surface either within the gas
or at a wall
• Construct
- normal to the area
- some reference plane containing the
normal
- slant cylinder, with axis in the direction
(θ, φ) and of length v∆t- equal to the
distance covered by a molecule with
speed v in time ∆t

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Molecular flux contd..

• Let ∆Nθφv be the number of molecules arriving at the surface during
time interval ∆t , travelling in the particular direction (θ,φ) and with
speed v
Direction θ means between θ and θ + ∆θ
Direction φ means between φ and φ + ∆ φ
Velocity v means between v and v +∆v
• The number of θφv-molecules that arrive at the surface during time
∆t is equal to the number of θφv-molecules in the cylinder
• A θφv-molecule is one with speed v travelling in the (θ,φ) direction

Molecular flux contd..

• There are other types of molecules in the cylinder- not travelling in
(θ,φ) direction or with speed other than v that will not arrive at the
surface element in time ∆t
• Many other molecules , not in the cylinder will arrive at the element
during time ∆t. Some of these may have speed v , but they are not θφ
molecules as they come from other directions.
• Therefore, of all θφv-molecules in the cylinder and only those
molecules will reach the surface during the time ∆t, travelling in
direction (θ,φ) with speed v

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Molecular flux contd..

• Let ∆nv be the number density of molecules with speeds between v
and v + ∆v
• Then , the number density of θφv-molecules is
∆nθφv = ∆nv sin θ ∆θ ∆φ
The volume of the slant cylinder in the fig
∆V = ( ∆A cos θ ) (v ∆t)
The number of θφv-molecules in the cylinder is , therefore,
∆Nθφv = v ∆nv sin θ cos θ ∆θ ∆φ ∆A ∆t

Molecular flux contd..

• The flux ∆Фθφv of θφv-molecules
∆Фθφv = ∆Nθφv = v ∆nv sin θ cos θ ∆θ ∆φ
∆A ∆t

• The flux ∆Фθv due to molecules arriving at an angle θ with speed v for
all angles φ is obtained by replacing ∆φ with dφ and integrating
within limits φ = 0 to φ= 2π
∆Фθv = v ∆nv sin θ cos θ ∆θ

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Molecular flux contd..

• The flux ∆Фθ due to molecules arriving at angle θ, for all angles φ
and all speeds v, is found by summing the expression for ∆Фθv over all
values of v
∆Фθ = sin θ cos θ ∆θ ∑ v ∆nv
• The flux ∆Фv of molecules with speed v for all angles θ and φ, is
obtained by replacing ∆θ with dθ in the expression for ∆Фθv and
integrating over limits θ =0 to θ = π/2
∆Фv = v ∆nv

Molecular flux contd..

• Finally, the total flux Ф , including all speeds and angles is given by
summing ∆Фv over all values of v

Ф = ∑ v ∆nv
• This result can also be expressed in terms of average or arithmetic mean
speed ṽ, which can be obtained by adding the speeds of all molecules and
dividing by total number of molecules
∑
ṽ =

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Molecular flux contd..

• If there are ∆N1 molecules with speed v1, ∆N2 molecule with speed v2
etc. , then
v ∆N + v2 ∆N2 + ……..
ṽ = 1 1 = ∑ v ∆Nv = ∑ v ∆nv

∑ v ∆nv = n ṽ
Therefore the molecular flux Ф of all molecules arriving at one side of
the element from all directions with all speeds is
Ф = nṽ

Molecular flux – Alternate expression

• Consider the area ∆A in figure – 2 to be located at the origin in
Figure -1 and to lie in the x-y plane
• The molecules arriving at this area in the (θ, φ) direction are those
coming in within the small cone in figure-1 whose base is the shaded
area ∆A on the spherical surface in figure -1
• This shaded area is ∆A = r2 sin θ ∆θ ∆φ
• The solid angle of the cone ∆ω is
∆A
∆ω = r2 = sin θ ∆θ ∆φ

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Molecular flux – Alternate expression contd..

• Then θφv molecular flux can be expressed as
∆Фθφv = v ∆nv cos θ ∆ω = ∆Фωv
• The flux per unit solid angle of molecules with speed v is
∆Фωv
= v ∆nv cos θ
∆ω
• The total flux per unit solid angle , including all speeds , is
∆Фω
∆ω = ṽ n cos θ

Molecular flux – Alternate expression contd..

• Considering all the cones with apexes in ∆A ,
• The greatest no. of molecules arrives in the cone centered about the
normal as cos θ has the maximum value for this cone ( θ = 0)
• The number of molecules arriving decreases to zero for cones tangent to
∆A where θ = 90⁰
• If ∆A is a hole in the wall of a thin-walled container, small enough that
leakage through the hole does not affect the equilibrium of the gas, then
every molecule coming up to the hole will escape through it
• The number escaping per unit solid angle is maximum in the direction
normal to the plane of the hole and decreases to zero in the tangential
direction

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Equation of state of an ideal gas

Equation of state of an ideal gas contd…

• Figure shows the condition of a θφv-molecule before and after
collision with the wall of a vessel containing a gas
• For a perfectly elastic collision, magnitude of velocity v before and
after collision remain the same
• For a perfectly smooth wall, the tangential component of velocity
v sinθ is also unchanged by collision
• So angle of incidence is equal to the angle of reflection and
the normal component of velocity is reversed in collision from
v cosθ to -v cosθ

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Equation of state of an ideal gas contd…

• The force exerted on the wall by a molecule in a collision is an
impulsive force of short duration
• As per Newton’s law , the average force per unit area exerted on the
surface or the average pressure is equal to the rate of change of
momentum per unit area
• If m is the mass of a colliding molecule,
the change in the normal component of momentum in a θφv-
collision is
mv cosθ – ( - mv cosθ ) = 2 mv cosθ

Equation of state of an ideal gas contd…

• Since change in momentum depend on θ and v , but not on φ,
so we need the no. of θv-molecules arriving at the surface per unit
area , per unit time , i.e., the flux ∆Фθv given by the equation
∆Фθv = v ∆nv sin θ cos θ ∆θ
• The rate of change of momentum per unit area due to all the
molecules arriving at an angle θ with speed v or the pressure ∆Pθv
equals the product of ∆Фθv and the change in momentum of a
θv-molecule
∆Pθv = ( v ∆nv sin θ cos θ ∆θ )(2 mv cosθ ) = mv2 ∆nv sin θ cos2θ ∆θ

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Equation of state of an ideal gas contd…

• To find the pressure ∆Pv due to molecules of speed v coming from all
values of θ , replace ∆θ by dθ and integrate the equation for ∆Pθv
over limits θ =0 to θ = π/2
∆Pv = mv2 ∆nv

• Finally, total pressure P is obtained by summing over all values of v

P= m ∑v2 ∆nv

Equation of state of an ideal gas contd…

• As the molecular flux ∆Фθφv is the same for all surfaces, the above
derivation can be applied to any imaginary surface in the interior of
the gas also
• So the net flux of momentum and the pressure has the same value at
all points both within the gas and at its surface

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Equation of state of an ideal gas contd…

• The equation for pressure can be more conveniently expressed in terms of the average
value of the square of the speed off all molecules – the mean square speed v2m ,
obtained as
∑v2 ∑v2 ∑v2
v2 m = = =

∑v2 Δnv = n v2 m

• So the expression for pressure becomes

P = nmv2m

Equation of state of an ideal gas contd…

• Since the mean kinetic energy of a single molecule is mv2m
the R.H.S. of the equation for pressure equals two-thirds of the
total kinetic energy per unit volume or two – thirds of the
kinetic energy density
• Since n = N/V, equation for pressure can be re-written as
PV = Nmv2m
• This has a similar form to the ideal gas equation PV = yRT
where y represents the number of kilomoles obtained by dividing
total no. of molecules by no. of molecules in a kilomole

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Equation of state of an ideal gas contd…

.
y= .
=
So ideal gas equation can be re-written as
PV = N T
The quotient R/NA is called universal gas constant per molecule or
Boltzmann’s constant and is represented by k
k=
Since R and NA are both universal constants, k is also a universal
constant

Equation of state of an ideal gas contd…

• Substituting values of universal gas constant and Avagadro number
k= 1.381 x 10 -23 J /molecule / K
• In terms of Boltzmann constant, ideal gas equation can be written as
PV = NkT
Equating this to the expression derived from kinetic theory, we get
NkT = Nmv2m

v2m =

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Equation of state of an ideal gas contd…

• Thus absolute temperature T is a quantity proportional to the mean square
speed of the molecules of an ideal gas
• Equation v2m = can be conveniently re-written as
m v2m = kT
• Mean translational kinetic energy of a gas molecule is directly proportional
to the absolute temperature.
• Since k is the same for all molecules, mean kinetic energy depends only
on temperature and not on pressure or volume or species of molecule,
i.e., at the same temperature mean kinetic energy of molecules of all gas
species are same despite the difference in their masses

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