Chap 3 Gas Kinetic Theory for Ideal Gases

Lecture notes of Chin-Hsiang Cheng

 Analytical mechanics, Celestial mechanics, Mathematical analysis,
Number theory, Theory of equations

Joseph-Louis Lagrange (1736–1813)

Italian/French mathematician and astronomer.

Electromagnetic radiation, Maxwell's equations for

electromagnetism, Gas kinetic theory

James Clerk Maxwell (1831 – 1879)

Scotch mathematical physicist
 Statistical mechanics, Boltzmann constant, H-theorem,
Maxwell–Boltzmann distribution, Maxwell-Boltzmann statistics,
Statistical definition of entropy

Ludwig Boltzmann (1844-1906)

Austrian physicist and philosopher
Kinetic Theory for Ideal Gases

ASSUMPTIONS:

1. Any finite volume of a gas is comprised of a large number of molecules.

2. A gas is composed of identical molecules which behave like hard spheres moving
about in random direction in a state of continuous motion.
3. Molecules exert no forces on each other except when they collide.
4. Collisions between molecules and with the walls are perfectly elastic; i.e. there is no
decrease of kinetic energy when they take place.
5. In the absence of external force, the molecules are distributed uniformly throughout
the container.
6. All directions of molecular velocities are assumed to be equally probable.
7. Temperature of ideal gas is proportional to the kinetic energy of molecules.
Assumption 7:

1
m𝑉𝑉� 2 = C T
2

1 3
m𝑉𝑉� 2 = kT k: Boltzmann constant, =1.3806 x 10-23 J/K
2 2

Example: Determine average kinetic energy and velocity of a single Argon molecule
at T=300 K
Sol:
1 3 3
m𝑉𝑉� 2 = k T = (1.3806 x 10-23 J/K) (300 K) = 6.3 x 10-21 J = 4 x 10-2 eV
2 2 2

1 eV = 1.602 x 10-19 J

m= 6.63 x 10-26 kg for an Argon molecule

1
(6.63 x 10-26 )𝑉𝑉� 2 = 6.3 x 10-21 J � 435 m/s
𝑉𝑉=
2
 Ideal-Gas Equation of State

� Ru T
PⱯ=N Ru: universal gas constant, = 8.314 J/mol-K;
� : molar number N: total number of molecule
N

�
N Ru 8.314 J/mol−K
Since Ru = = = 1.3806 x 10-23 J/K = k Boltzman constant
N 6.023 x 1023 6.023 x 1023 1/mol

One has

�
3 NR
� Ru T)/ Ɐ = (m N uT 1
P = (N 𝑉𝑉� 2 )/(3 Ɐ) or = m𝑉𝑉� 2
2 N 2

1
For idea gas , internal energy U = N m𝑉𝑉� 2 (molecular kinetic energy only, no penitential energy)
2
3 �
NR uT
= N
2 N
3
= N � Ru T
2
3
�=
Specific internal energy per molecule u = U/ N RT
2 u
 𝜕𝜕𝜕𝜕 3 3
Cv = = Ru ∵ u = RuT
𝜕𝜕𝜕𝜕 𝑣𝑣 2 2

3 5
Cp = Cv + Ru = Ru + Ru= Ru
2 2

3
For monatomic gases , degree of freedom=3, which behave like perfect idea gases u = R T.
2 u

Equipartition of Energy:

The theorem of equipartition of energy states that molecules in thermal equilibrium

have the same average energy associated with each independent degree of freedom.
1
Therefore, each independent degree of freedom shares RuT in energy.
2
For monatomic gases, f = 3, which is independent of
temperature:
3 5
Cv = Ru Cp = Ru
2 2

For diatomic gases,

3 5
f = 3 at low temperature, Cv = Ru Cp = Ru
2 2
5 7
f = 5 at medium temperature, Cv = Ru Cp = Ru
2 2
7 9
f = 7 at medium temperature, Cv = Ru Cp = Ru
2 2

For polyatomic gases, f = 3+K, which is complicated and needs further study for individual gases.
 9
Ru
2

7
Ru
2

5
Ru
2

Effect of temperature on specific heats of various gases

N number of molecules in volume Ɐ

n number density (average number of molecules per unit volume)

n=N/Ɐ

𝑉𝑉 velocity of molecule

𝑉𝑉� average velocity of molecules

1 d𝑛𝑛
�
𝑉𝑉 = ∫𝑁𝑁 𝑉𝑉 d𝑛𝑛 = ∫𝑁𝑁 𝑉𝑉 = ∫𝑁𝑁 𝑉𝑉 d𝑓𝑓
𝑁𝑁 𝑁𝑁
Probability distribution
𝑓𝑓
𝑓𝑓 probability

1
1 = � d𝑓𝑓
0
𝑉𝑉
 Velocity Space (2D) y Molecule 3
v

y v
Molecule 1

Molecule 2
u x u

x
 Velocity Space (3D) vz=w

vy=v

u vx=u

v
dNu : Number of nodes within u ~ u+du
d2Nuv : Number of nodes within u ~ u+du and v ~ v+dv
d3Nuvw : Number of nodes within u ~ u+du , v ~ v+dv , and w ~ w+dw

dNV : Number of nodes within V ~ V+dV V= 𝑢𝑢2 + 𝑣𝑣 2 + 𝑤𝑤 2

 Velocity Space

𝑉𝑉 > 𝑟𝑟

𝑟𝑟

𝑉𝑉 < 𝑟𝑟
 Velocity Space

𝑉𝑉 > 𝑟𝑟

𝑟𝑟

𝑉𝑉 < 𝑟𝑟
 w

dA=(rdθ) (rsinθ dφ)

v v

u
u

dNθ : Number of nodes within θ ~ θ+dθ

d2Nθφ : Number of nodes within θ ~ θ+dθ and φ~ φ+dφ
d3NVθφ : Number of nodes within V ~ V+dV, θ ~ θ+dθ, and φ~ φ+dφ
 𝑟𝑟 dA

1. Average number of nodes per unit area at r is: N/4πr2

2. dA=(rdθ) (rsinθ dφ) and

dA is the area within θ ~ θ+dθ and φ~ φ+dφ at r

3. Number of nodes within dA at r is equal to the number of nodes within θ ~ θ+dθ

and φ~ φ+dφ at r, d2Nθφ :
𝑁𝑁
d2Nθφ = dA(N/4πr2)=(rdθ) (rsinθ dφ) (N/4πr2) = sinθ dθ dφ (r is NOT important.)
4π

4. Number density of molecules within θ ~ θ+dθ and φ~ φ+dφ, d2nθφ :

𝑛𝑛
d2nθφ = d2Nθφ / Ɐ = sinθ dθ dφ
4π
 Physical space
z z

x x

y y

dNV N
dnV = dNV /Ɐ n=N/Ɐ
 z z

θ θ

x x
φ φ

y y
d3NVθφ d2Nθφ

d3nVθφ =d3NVθφ /Ɐ d2nθφ =d2Nθφ /Ɐ

dnV d3nV
=
n
 Collisions with Stationary Wall
7. No. of collisions on wall dA′ in time dt by molecules with V
z and from angle θ and φ:

V
d3nVθφ (Vdt dA′ cosθ) = dn sinθ cosθ dθ dφ dt dA′
4π V
Vdt
θ 8. No. of collisions on wall per unit area per unit time by
molecules with V and from angle θ and φ:

dA′ V
x dn sinθ cosθ dθ dφ
4π V
φ
9. No. of collisions on wall per unit area per unit time by
molecules with V: This is obtained by integration w.r.t. θ (from
y
0 to π/2) and φ (from 0 to 2π) as
π
2π 2
V V
� � dnV sinθ cosθ dθ dφ = dnV
4π 4
0 0
 10. No. of collisions on wall per unit area per unit time: This is obtained by integration
w.r.t. nV (associated V varying from 0 to ∞) as

V 1
�
� dnV = n V
4 4

where

1
�
V = ∫N VdnV
N

Increase P ⇒ Increase n ⇒ Increase no. of collisions

� ⇒ Increase no. of collisions

Increase T ⇒ Increase V
The Maxwell-Boltzmann distribution is shifted to higher speeds
and is broadened at higher temperatures.
 Solid angle is in Sr (steradian). Sphere has a solid angle of 4π Sr.

8. No. of collisions on wall per unit area per unit time by molecules with V
and from angle θ and φ can be expressed in terms of dw as

V V
dnV sinθ cosθ dθ dφ = dn cosθ dw
4π 4π V
11. No. of collisions on wall per unit area per unit time per unit solid angle by
molecules with V and from angle θ and φ then is

V 1
dn cosθ π
4π V 0 8
V
dn cosθ
4π V

3
π
8

As θ= 12 π , no collision (number of collisions = 0)

As θ=0, maximum number of collisions 1
π
2
θ
 Gas Pressure

Normal velocity component Vcosθ ⇒ - Vcosθ z

Tangential velocity component Vsinθ ⇒ Vsinθ

Let m be the mass of a molecule, the normal momentum -Vcosθ Vsinθ

change of a collision is V θ
Vcosθ
2𝑚𝑚Vcosθ V
Vsinθ
x
7. No. of collisions on wall dA′ in time dt by molecules with V dA′
and from angle θ and φ: φ

V
dn sinθ cosθ dθ dφ dt dA′ y
4π V
12. Change in momentum due to collisions on wall dA′ in time dt by molecules with V and from angle
θ and φ:
V 1
(2𝑚𝑚Vcosθ)( dnV sinθ cosθ dθ dφ dt dA′ )= mV2dnV sinθ cos2θ dθ dφ dt dA′
4π 2π

13. Change in momentum due to collisions on wall dA′ in time dt by molecules with V:
This can be obtained by integrating the above equation w.r.t. θ (from 0 to π/2) and φ (from 0 to 2π)
1
mV2dnV dt dA′
3

14. Rate of change in momentum due to collisions on wall dA′ by molecules with V:

1
dFV = mV2dnVdA′
3

1 1 1
dF = ∫ dFV =
3
m∫ V2dA′ dn V =
3
mn V2 dA′ where V2 =
N
∫N V2dnV

dF 1
15. Pressure P= = mn V2
dA′ 3
16.
1
P= mn V2
3
1 2 1 2 3
P Ɐ = (nⱯ) mV2 = N ( mV2) = N k T = NkT
3 3 2 3 2

�
N
Since k = Ru, the above equation becomes
N

� Ru T
PⱯ=N Ideal-gas equation of state

where Ru: universal gas constant, = 8.314 J/mol-K;

� : molar number
N
N: total number of molecule
 Collisions with Moving Wall
v2=2u-Vcosθ Vsinθ
V′ θ
Moving wall: m1 → ∞
Normal direction: u1=u → v1= u u2=Vcosθ
V
Vsinθ
Molecule: m2
Normal direction: u2=Vcosθ → v2= 2u-Vcosθ

Assumption 4: Perfectly elastic collision

Before After
m1u1 + m2u2 = m1v1 + m2v2 Object 1 u1 m1 → v1 m1
Object 2 u2 m2 → v2 m2
m1u12 + m2u22 = m1v12 + m2v22

m u +2m u −m2u1 m2u2 +2m1u1−m1u2

v1 = 1 1 m +2m2 v2 = m1 + m2
1 2
m1 → ∞

v1 = u1= u (speed of the moving wall is not changed)

v2 = 2u1 − u2 = 2u-Vcosθ

17. Energy loss in kinetic energy with each collision

1 1
m(Vcosθ)2 - m(2u−Vcosθ)2= 2mVucosθ
2 2
8. No. of collisions on wall per unit area per unit time by molecules with V and from angle θ
and φ
V
dn sinθ cosθ dθ dφ
4π V

18. No. of collisions on wall per unit area per unit time by molecules with V and from angle θ:
This is obtained by integration w.r.t. φ (from 0 to 2π) as

2π V V
∫0 4π dnV sinθ cosθ dθ dφ = 2 dnV sinθ cosθ dθ

19. Energy loss in molecular kinetic energy due to collisions on wall per unit area per unit time
by molecules with V and from angle θ:

V
( dnV sinθ cosθ dθ)(2mVucosθ)
2

20. Integration of the above equation w.r.t. θ (from 0 to π/2) leads to energy loss due to
collisions on wall per unit area per unit time by molecules with V:
π
2
V 1
� ( dnV sinθ cos)(2mVucosθ) dθ dφ = mu V2dnV
2 3
0
21. Integration of the above equation w.r.t. V leads to energy loss due to collisions on wall per
unit area by all molecules:

1
nmV2u
3

22. Total kinetic energy loss in molecular kinetic energy per unit time:

dS dⱯ 1
PAu = PA =P = nmV2uA (Total kinetic energy loss per unit time = Output power)
dt dt 3