Advanced Thermodynamics (M2794.

007900)

Chapter 11

Kinetic Theory of Gases (1)

Min Soo Kim

Seoul National University
11.1 Basic Assumption

Basic assumptions of the kinetic theory

1) Large number of molecules

𝑁𝐴 = 6.02 × 1026 molecules per kilomole

2) Identical molecules which behave like hard spheres

3) No intermolecular forces except when in collision

2/20
11.1 Basic Assumption

Basic assumptions of the kinetic theory

4) Collisions are perfectly elastic

5) Uniform distribution throughout the container

N
n= d𝑁 = ndV
V
Average # of molecules per unit volume

3/20
11.1 Basic Assumption

6) Equal probability on the direction of molecular velocity

average # of intersections of velocity vectors per unit area

𝑁
r sin θ d𝜙
4𝜋𝑟 2 rdθ

the # of intersections in dA r

θ
𝑁
d𝐴 𝑟 2 sin θ dθdϕ
4𝜋𝑟 2 ϕ

N sin θ dθdϕ n sin θ dθdϕ

= d2 Nθϕ = , d2 nθϕ =
4π 4𝜋
# of molecules having velocities in a direction (θ< <θ+dθ)
(ϕ< <ϕ+dϕ)

4/20
11.1 Basic Assumption

7) Magnitude of molecular velocity : 0 ~ ∞

c (speed of light)

dN𝑣 : # of molecules with specified speed (v< <v+dv)

5/20
11.1 Basic Assumption

• Let dN𝑣 as # of molecules with specified speed (v< <v+dv)

• ‫׬‬0∞ dN𝑣 = N

• Mean speed is 𝑣ҧ = N1 ‫׬‬0∞ 𝑣dN𝑣

• Mean square speed is 𝑣 2 = N1 ‫׬‬0∞ 𝑣 2 dN𝑣

• Square root of 𝑣 2 is called the root mean square or rms speed:
𝑣𝑟𝑚𝑠 = 𝑣2
• The n-th moment of distribution is defined as
1 ∞
𝑣 𝑛 = N ‫׬‬0 𝑣 𝑛 dN𝑣

6/20
11.2 Molecular Flux

• # of molecules of a gas that strike a surface per unit area and unit time

• Molecules coming from particular direction θ, ϕ with specified speed v in time dt

→ θϕ𝑣 collision θ< <θ+dθ
ϕ< <ϕ+dϕ
v< <v+dv

• # of θϕ𝑣 collisions with dA dt

= θϕ𝑣 molecules in
= θϕ molecules with speed v

Fig. Slant cylinder geometry used to calculate

the number of molecules that strike the area dA in time dt.

7/20
11.2 Molecular Flux

• How many molecules in

dn𝑣 : # density between speed (v< <v+dv)

𝑑𝐴 sin θdθdϕ
d3 nθϕ𝑣 = dn𝑣 ∙ = dn𝑣
𝐴 4𝜋

dV = dA (vdt cosθ ) Volume of cylinder

• # of θϕ𝑣 molecules in the cylinder

sin θdθdϕ
d3 nθϕ𝑣 𝑑𝑉 = 𝑑𝐴 (𝑣dt cosθ )dn𝑣 4𝜋

• # of collisions per unit area and time

d3 nθϕ𝑣 dV 1
= 4π 𝑣dn𝑣 sinθcosθdθdϕ
dA dt

8/20
11.2 Molecular Flux

• Total # of collisions per unit area and time

d3 nθϕ𝑣 dV 2𝜋 𝜋/2 1 1
= ‫׬‬0 ‫׬‬0 sinθcosθdθdϕ ∙ 4π 𝑣dn𝑣 = 4 𝑣dn𝑣
dA dt

• Total # of collisions per unit area and time by molecules having all speed

∞1 1
‫׬‬0 𝑣dn𝑣 = 4 𝑛𝑣ҧ
4

σ 𝑣ത σ 𝑁𝑖 𝑣𝑖 σ 𝑛𝑖 𝑣𝑖 ‫𝑣 ׬‬d𝑛𝑣
Cf. average speed 𝑣ҧ = = = σ 𝑛𝑖
=
𝑁 𝑁 𝑛

9/20
11.3 Gas Pressure and Ideal Gas Law

• Gas pressure in Kinetic theory

Gas pressure is interpreted as impulse flux of particles striking a surface

𝑚𝑣1 𝑚𝑣2

𝜃 𝜃

10/20
11.3 Gas Pressure and Ideal Gas Law

• Perfect elastic 𝑣 = 𝑣′

• Average force exerted by molecules

d(𝑚𝑣)
F= = 𝑚𝑎Ԧ + 𝑚ሶ 𝑣Ԧ
dt

• Momentum change of one molecule (normal component only)

𝑚𝑣cos𝜃 − −𝑚𝑣cos𝜃 = 2𝑚𝑣cos𝜃 𝑣 sin θ

• # of θϕ𝑣 collisions for dA, dt 𝑣

𝑣 cos θ

θ θ
1
𝑣dn𝑣 sinθcosθdθdϕ
4π
ϕ
dA

11/20
11.3 Gas Pressure and Ideal Gas Law

• Change in momentum due to θϕ𝑣 collisions in time dt

1
2𝑚𝑣cos𝜃 × 4π 𝑣dn𝑣 sinθcosθdθdϕ

1
= 2π 𝑚𝑣 2 dn𝑣 sinθcos2 θdθdϕdAdt

𝜋
• Change in momentum in all v collisions 0 < θ ≤ 2 , 0 < ϕ ≤ 2𝜋

𝜋
2𝜋 1 2 dn sinθcos 2 θdθdϕ
‫׬‬0 ‫׬‬0
2 𝑚𝑣 𝑣 ∙ dAdt
2π

1
= 3 𝑚𝑣 2 dn𝑣 dAdt

12/20
11.3 Gas Pressure and Ideal Gas Law

• Change in momentum from collisions of molecules at all speed

1
𝑚 ‫׬‬ 𝑣 2 dn
𝑣 = 𝑑𝐹Ԧ ∙ 𝑑𝑡
3

𝑑𝐹 Ԧ
• Average pressure 𝑃ത =
𝑑𝐴

1 2 dn 1 2 σ 𝑣2 ‫ 𝑣 ׬‬2 d𝑛𝑣
𝑚 ‫׬‬ 𝑣 𝑣 = 𝑚𝑛𝑣 cf. 𝑣2 = =
3 3 𝑁 𝑛

13/20
11.3 Gas Pressure and Ideal Gas Law

𝑁 1𝑁
𝑛= 𝑉
,𝑃 = 3 𝑉 𝑚𝑣 2

1
𝑃𝑉 = 3 𝑁𝑚𝑣 2 ത = mRT = N 𝑅𝑇
cf. EOS of an ideal gas PV = n𝑅𝑇 ത = 𝑁𝑘𝑇
𝑁 𝐴

𝑁𝐴 : Avogadro’s number : 6.02 × 1026 𝑛𝑢𝑚𝑏𝑒𝑟/𝑘𝑚𝑜𝑙𝑒 k: Boltzmann constant

𝑅ത
𝑘𝐵 : Boltzmann constant : 𝑘𝐵 = = 1.38 × 10−23 𝐽/𝐾
𝑁𝐴

1
𝑃𝑉 = 𝑁𝑚𝑣 2 = 𝑁𝑘𝑇
3

1 2 3
𝑚𝑣 = 2 𝑘𝑇
2

14/20
11.4 Equipartition of Energy

• Equipartition of energy

Because of even distribution of velocity of particles,

1 1 1
𝑣 2 = 𝑣𝑥2 + 𝑣𝑦2 + 𝑣𝑧2 , 𝑣𝑥2 = 𝑣𝑦2 = 𝑣𝑧2 = 3 𝑣 2 → 𝑚𝑣𝑥
2
= 2 𝑘𝑇
2

It can be interpreted that a degree of freedom allocate energy of 1/2 𝑘𝑇

15/20
11.4 Equipartition of Energy

𝐸ത = 𝐸ത𝑥 + 𝐸ത𝑦 + 𝐸ത𝑧

energy
1 1 1
= 2 𝑚𝑣𝑥2 + 2 𝑚𝑣𝑦2 + 2 𝑚𝑣z2

𝑘𝑇 𝑘𝑇 𝑘𝑇
𝐸ത𝑥 = 2 , 𝐸ത𝑦 = 2 , 𝐸ത𝑧 = 2

16/20
11.5 Specific Heat

δq = du + δW

1
U = f ∙ 2 𝑁𝑘𝑇 f: number of degrees of freedom

U 1
ത
u = N = f ∙ 2 𝑅𝑘𝑇

𝜕𝑢 1
𝑐𝑣 = 𝜕𝑇 ቁ = f ∙ 2 𝑅ത (n𝑅ത = 𝑁𝑘)
𝑣

𝜕ℎ 𝑓 (𝑓+2)
𝑐𝑃 = = 2 𝑅ത + 𝑅ത = 2 𝑅ത
𝜕𝑇 𝑝

17/20
11.5 Specific Heat

1 2 1 2 1
Monatomic
2
𝑚𝑣𝑥 , 2
𝑚𝑣𝑦 , 2
𝑚𝑣𝑧
2
3 𝑐𝑝 3 + 2
𝑐𝑣
=
3
= 1.67
gas
1 2 1 2 1 2
𝑚𝑣𝑥 , 𝑚𝑣𝑦 , 𝑚𝑣𝑧
2 2 2
Translational
negligible 𝑐𝑝 5 + 2
= = 1.4
1 2 , 1 𝐼𝑤 2 , 1 𝐼𝑤 2 𝑐𝑣 5
Diatomic 𝐼𝑤𝑥 2 𝑦 2 𝑧
2
gas Rotational 7
1 2 , 1 𝑚 𝑥ሶ 2
𝑘𝑥 no y,z vibration
2 2
Vibrational

Near room temperature, rotational or vibrational DOF

are excited, but not both.

18/20
11.5 Specific Heat

CO2 translational 3 𝑐𝑝 7 + 2
Triatomic
gas
rotational 2 9 𝑐𝑣
=
7
= 1.28

vibrational 4

• Vibration modes of CO2

Stretch

Bending

19/20
11.5 Specific Heat

𝑘𝑇
(kinetic)
2
x,y,z direction

𝑘𝑇
(potential)
2
Solid
U = 3𝑁𝑘𝑇

cv = 3𝑅(Dulong-Petit Law)

20/20