III.

Kinetic theory of gases

Outcomes
• Apply the ideal gas law
• Apply relationship between pressure, temperature,
kinetic energy and speeds of molecules
• Apply relationship between mean free path,
diameter of molecules, and number of molecules
per unit volume
• Apply the molar specific heats and of adiabatic
expansion an ideal gas
1
III. Kinetic theory of gases
Introduction
◦ One of the main subjects in thermodynamics:
physics of gases
◦ Three variables associated with a V, T, P—are
all a consequence of the motion of the atoms
◦ Kinetic theory of gases: A model of behavior
of gases that relates the motion of the atoms
to V, T, P of the gas

2
III. Kinetic theory of gases
Introduction
Assumptions:
◦ The gas consists of very small particles
◦ The particles have the same mass
◦ The number of particles is so large that
statistical treatment can be applied
◦ All collisions are perfectly elastic
◦ Except during collisions, the interactions
among molecules are negligible.
3
III. Kinetic theory of gases
Introduction
Some applications:
◦ The combustion of vaporized fuel (a gas) in the
automobile engines
◦ The production rate of the fermentation gas that
causes bread to rise as it bakes
◦ How heat exchanges between the oceans and the
atmosphere can affect weather conditions
◦ Etc.

4
III. Kinetic theory of gases
Introduction
Four main relationships:
◦ Pressure and kinetic energy
◦ Temperature and kinetic energy
◦ Collision with container
◦ Speeds of molecules

5
Avogadro’s number

One mole?
◦ « Old definition»: The number of atoms in a 12 g
sample of carbon-12
◦ «New definition»: One mole contains exactly
6.022 140 76 × 1023 elementary entities
NA = 6.02 x 1023 mol-1
◦ Amedeo Avogadro (1776–1856): “all gases
occupying the same volume under the same conditions of
temperature and pressure contain the same number of
atoms or molecules”
6
 Avogadro’s number
The number of moles n
𝑁 n: the number of moles
contained in a sample of any
𝑛= N: the number of molecules
𝑁𝐴 NA: the number of molecules in 1 mol substance is equal to the ratio
of the number of molecules N
in the sample to the number of
Msam: the mass of the sample molecules NA in 1 mol
𝑀𝑠𝑎𝑚 𝑀𝑠𝑎𝑚
𝑛= = M: the molar mass (the mass of 1 mol)
𝑀 𝑚𝑁𝐴 m: the molecular mass

7
Ideal gas law
• Goal: explain macroscopic properties
of a gas in terms of behavior of the
molecules that make it up
• If we confine 1 mol samples of
various gases in boxes of identical V
and T, their measured P are almost
the same, and at lower densities the
differences tend to disappear.
• All real gases approach the ideal state
at low enough densities
• Ideal gas concept allows to gain
insights into the limiting behavior of
real gases.
8
Ideal gas law (general gas equation)

P: absolute pressure
n: number of moles of gas

𝑃𝑉 = 𝑛𝑅𝑇 T: temperature (in kelvins)

R: ideal/universal gas constant

9
Ideal gas law
Question:
What is the value
(and unit) of the
gas constant?

10
Ideal gas law (general gas equation)

k: Boltzmann constant

𝐽
𝑅 8.31
𝑃𝑉 = 𝑁𝑘𝑇 𝑘= = 𝑚𝑜𝑙. 𝐾
23 _1
𝑁𝐴 6.02 𝑥 10 𝑚𝑜𝑙

𝑘 = 1.38 𝑥 10−23 𝐽/𝐾

11
Ideal gas law

◦ A stainless-steel tank was filled with steam of

110°C. Water was poured onto the tank to
rapidly cool it. Within less than a minute, the
tank was crushed. Why?

12
Work done by an ideal gas
At constant
𝑛𝑅𝑇 1
𝑃= = (𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡) temperature
𝑉 𝑉
Consider an isothermal
𝑉𝑓 𝑉𝑓
𝑛𝑅𝑇 expansion (the reverse
W = න 𝑃𝑑𝑉 = න 𝑑𝑉 is called an isothermal
𝑉 𝑉 𝑉
𝑖 𝑖 compression)
𝑉𝑓
𝑑𝑉 𝑉𝑓
W = 𝑛𝑅𝑇 න = 𝑛𝑅𝑇𝑙𝑛 ቤ
𝑉 𝑉 𝑉𝑖
𝑖

𝑉𝑓
W = 𝑛𝑅𝑇𝑙𝑛
𝑉𝑖 13
Work done Ideal gas law
At constant
volume
Consider an isochoric
process
𝑊=0

14
Work done Ideal gas law
At constant
pressure
Consider an isobaric
process
W = 𝑃 𝑉𝑓 − 𝑉𝑖 = 𝑃Δ𝑉

15
Work done Ideal gas law
At constant
pressure
Consider an isobaric
process
W = 𝑃 𝑉𝑓 − 𝑉𝑖 = 𝑃Δ𝑉

16
Exercise
1. Which of the following term does not involve in ideal gas law?
a) Pressure
b) Volume
c) Temperature
d) Time
2. Which of the following is not true about ideal gas molecules?
a) They have negligible size
b) They do not have attractive forces
c) They do not apply pressure
d) They move in random motion

17
 Exercise
A cylinder contains 12 L of oxygen at 20°C
and 15 atm. The temperature is raised to 35°C,
and the volume is reduced to 8.5 L. What is
the final pressure of the gas in atmospheres?
Assume that the gas is ideal.

Copyrights @ Hello Techie Vietnam 18

 Exercise
One mole of oxygen (assume it to be an ideal
gas) expands at a constant temperature T of
310 K from an initial volume Vi of 12 L to a
final volume Vf of 19 L.
a) Establish the PV diagram
b) How much work is done by the gas
during the expansion?

Copyrights @ Hello Techie Vietnam 19

Pressure, Temperature, and RMS Speed

◦ We ignore (for the time being) collisions of the

molecules with one another and consider only
elastic collisions with the walls

What is the connection between the pressure P

A cubical box of edge length L,
containing n moles of an ideal gas.
exerted by the gas on the walls and the speeds
A molecule of mass m and velocity of the molecules?
is about to collide with the shaded
wall of area L2 and temperature T.

20
Pressure, Temperature, and RMS Speed

◦ When this molecule collides with the shaded

wall, the only component of its velocity that is
changed is the x component, and that
component is reversed (because we consider
only elastic collisions)
◦ The only change in the particle’s momentum is
A cubical box of edge length L, along the x axis:
containing n moles of an ideal gas.
A molecule of mass m and velocity
∆𝑝𝑥 = −𝑚𝑣𝑥 − 𝑚𝑣𝑥 = −2𝑚𝑣𝑥
is about to collide with the shaded ◦ Hence, the momentum ∆𝑝𝑥 delivered to the wall
wall of area L2 and temperature T. by the molecule during the collision is +2𝑚𝑣𝑥

21
Pressure, Temperature, and RMS Speed

◦ The time ∆𝑡 between collisions is the time the

molecule takes to travel to the opposite wall and
back again (a distance 2L) at speed vx
2𝐿
∆𝑡 =
𝑣𝑥
◦ The average rate at which momentum is
A cubical box of edge length L, delivered to the shaded wall by this single
containing n moles of an ideal gas. molecule is
A molecule of mass m and velocity
∆𝑝𝑥 2𝑚𝑣𝑥 𝑚𝑣𝑥 2
is about to collide with the shaded = =
wall of area L2 and temperature T. ∆𝑡 2𝐿/𝑣𝑥 𝐿

22
Pressure, Temperature, and RMS Speed

◦ From Newton’s second law (𝐹Ԧ = 𝑑𝑝/𝑑𝑡), Ԧ the

rate at which momentum is delivered to the wall
is the force acting on that wall.
◦ Pressure P = Total force Fx (of all molecules of
different speeds)/area (L2)
A cubical box of edge length L, 𝑚𝑣𝑥12 𝑚𝑣𝑥𝑁2
containing n moles of an ideal gas. 𝐹𝑥 + ⋯+
𝑃= 2= 𝐿 𝐿
A molecule of mass m and velocity 𝐿 𝐿2
is about to collide with the shaded 𝑚
= 3 (𝑣𝑥12 +… 𝑣𝑥𝑁2)
wall of area L2 and temperature T. 𝐿

23
Pressure, Temperature, and RMS Speed

◦ By replacing: N = nNA
(𝑣𝑥12 +… 𝑣𝑥𝑁 2) = nNA(vx)2avg
◦ Then:
mnNA
𝑃= (vx)2avg
𝐿3
◦ By replacing: mNA = M (molar mass)
A cubical box of edge length L, L3 = V (volume)
containing n moles of an ideal gas. ◦ Then:
A molecule of mass m and velocity
nM
is about to collide with the shaded 𝑃= (vx)2avg
wall of area L2 and temperature T. 𝑉

24
Pressure, Temperature, and RMS Speed

◦ For any molecule:

𝑣2 = vx2 +vy2 +vz2
◦ Because molecules are all moving in random
directions:
2 2 2
1 2
vx =vy =vz = 𝑣
3
A cubical box of edge length L, ◦ Then:
containing n moles of an ideal gas. nM
A molecule of mass m and velocity 𝑃= (𝑣2) avg
is about to collide with the shaded 3𝑉
wall of area L2 and temperature T.

25
Pressure, Temperature, and RMS Speed

◦ We have:
(𝑣2) avg = 𝑣rms (root-mean square speed)

◦ Then:
nM
𝑃= (𝑣2)rms
3𝑉
A cubical box of edge length L, ◦ Combining with ideal gas law (PV = nRT):
containing n moles of an ideal gas.
A molecule of mass m and velocity 3𝑅𝑇
is about to collide with the shaded 𝑣𝑟𝑚𝑠 =
wall of area L2 and temperature T. 𝑀

26
 nM
◦ 𝑃= (𝑣2)rms : how the pressure
3𝑉
of the gas (a purely macroscopic
quantity) depends on the speed of
the molecules (a purely microscopic
quantity)
◦ 𝑣2rms : only a kind of average
speed; many molecules move much
faster than this, and some much
slower.

27
Exercise
Here are five numbers: 5, 11, 32, 67, and 89.
(a) What is the average value navg of these
numbers?
(b) What is the rms value nrms of these
numbers?

28
Translational kinetic energy

◦ Consider a single molecule of an ideal gas having

speed changes when it collides with other
molecules
◦ Its translational kinetic energy at any instant:
1
𝐾 = 𝑚𝑣2
2
◦ Its average translational kinetic energy over time:
1 2
1 2
1 3𝑅𝑇
𝐾𝑎𝑣𝑔 = 𝑚𝑣 𝑎𝑣𝑔 = 𝑚𝑣 𝑟𝑚𝑠 = 𝑚
2 2 2 𝑀

29
Translational kinetic energy

◦ Substituting:
3𝑅𝑇
𝑣𝑟𝑚𝑠 =
𝑀
𝑁𝐴 = 𝑀/𝑚
◦ Thus:
3 𝑅𝑇 3
𝐾𝑎𝑣𝑔 = = 𝑘𝑇
2 𝑁𝐴 2
At a given temperature T, all ideal gas molecules - no matter
what their mass - have the same average translational kinetic
energy
30
Mean free path

◦ A typical molecule moves through the gas,

changing both speed and direction abruptly as it
collides elastically with other molecules.
◦ Between collisions, the molecule moves in a
straight line at constant speed.
◦ Mean free path λ: the average distance
traversed by a molecule between collisions.

31
Mean free path

◦ Consider a single sphere molecule (diameter d)

traveling with v constant, other molecules at rest.
(a) A collision occurs when the centers of two
molecules come within a distance d of each
other, d being the molecular diameter.
(b) An equivalent representation is to think of the
moving molecule as having a radius d and all
other molecules as being points. The condition
for a collision is unchanged.

32
Mean free path

◦ In time Δ𝑡 the moving molecule sweeps out a

cylinder of length 𝑣Δ𝑡 and radius d and volume
(𝜋𝑑2)(𝑣Δ𝑡)
◦ The number of collisions that occur in time
Δ𝑡 is then equal to the number of (point)
molecules that lie within this cylinder.
◦ Number of molecules in the cylinder
= number of molecules per unit volume x volume
= 𝑁/𝑉 𝑥 (𝜋𝑑2)(𝑣Δ𝑡)
33
Mean free path

𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑝𝑎𝑡ℎ 𝑑𝑢𝑟𝑖𝑛𝑔 Δ𝑡

𝜆 =
number of collisions in Δ𝑡
𝑣Δ𝑡
𝜆≈
(𝜋𝑑2)(𝑣∆𝑡)𝑁/𝑉
1
= 2
𝜋𝑑 𝑁/𝑉
◦ Be careful: This equation is based on the
assumption that all the molecules except one
are at rest.
In fact, all the molecules are moving!!!
34
Mean free path

𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑝𝑎𝑡ℎ 𝑑𝑢𝑟𝑖𝑛𝑔 Δ𝑡

𝜆 =
number of collisions in Δ𝑡
𝑣Δ𝑡
𝜆≈
(𝜋𝑑2)(𝑣∆𝑡)𝑁/𝑉
1
= 2
𝜋𝑑 𝑁/𝑉
◦ Be careful: This equation is based on the
assumption that all the molecules except one
are at rest.
In fact, all the molecules are moving!!!
35
Mean free path

𝑣Δ𝑡
𝜆≈
(𝜋𝑑2)(𝑣∆𝑡)𝑁/𝑉
1
= 2
𝜋𝑑 𝑁/𝑉
◦ We have canceled two v symbols:
- The vavg in the numerator: the mean speed of the
molecules relative to the container.
- The vrel in the denominator: the mean speed of
our single molecule relative to the other molecules,
which are moving.
36
Mean free path

• A recall of mathematics….

• Since 𝑣1 = 𝑣2 → 𝑣𝑟𝑒𝑙 = 2𝑣ҧ

37
Mean free path

• Let’s re-write our formula:

𝑣Δ𝑡
ҧ
𝜆 =
(𝜋𝑑2)(𝑣𝑟𝑒𝑙 ∆𝑡)𝑁/𝑉
1
=
2𝜋𝑑2𝑁/𝑉
• Air molecules:
At sea level:  = 0.1 mm.
At h = 100 km,  = 16 cm.
At h = 300 km,  = 20 km.
38
Exercise
a) What is the mean free path  for oxygen
molecules at temperature T = 300 K and
pressure p = 1.0 atm? Assume that the
molecular diameter is d = 290 pm and the gas
is ideal.

(b) Assume the average speed of the oxygen

molecules is v = 450 m/s. What is the average
time t between successive collisions for any
given molecule?

39
The distribution of molecular speeds

• What fraction of the molecules have speeds

greater than the rms value?

• We need to know how the possible values of

speed are distributed among the molecules to
answer the above question

• In 1852, Scottish physicist James Clerk Maxwell

first solved the problem of finding the speed
distribution of gas molecules
40
The distribution of molecular speeds

• Maxwell’s speed distribution law:

P(v): probability distribution function

M: Molar mass
T: Temperature
v: molecular speed
R: gas constant

41
The distribution of molecular speeds

• P(v) dv: fraction of molecules with speeds in the

interval dv centered on speed v
• The total area under the distribution curve
corresponds to the fraction of the molecules
whose speeds lie between zero and infinity,
having value:

• The fraction of molecules with speeds in an

interval of v1 to v2 is then:

42
Average, RMS, and Most probable speeds

• Average speed:

• RMS speed:

• Most probable speed:

43
 Exercise
In oxygen (molar mass M = 0.0320 kg/mol) at room
temperature (300 K)
(a) What is the average speed vavg of oxygen gas molecules
at T = 300 K?
(b) What is the root-mean-square speed vrms at 300 K?
(c) What is the most probable speed vP at 300 K?

44
Molar specific heats of an ideal gas

◦ Considering a monatomic ideal gas (individual

atoms rather than molecules: He, Ar …)
◦ Assuming Eint = sum of the translational kinetic
energies of the atoms (Quantum theory disallows
rotational kinetic energy for individual atoms.)
◦ Average translational kinetic energy of a single
3
atom: 𝐾𝑎𝑣𝑔 = 𝑘𝑇 = 𝐸𝑖𝑛𝑡
2
3
◦ For sample of n moles: 𝐸𝑖𝑛𝑡 = 𝑛𝑁𝐴 𝑘𝑇
2
◦ With k = R/NA:
3
𝐸𝑖𝑛𝑡 = 𝑛𝑅𝑇 (𝑚𝑜𝑛𝑎𝑡𝑜𝑚𝑖𝑐 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠)
2 45
Molar specific heat at constant volume (Cv)

◦ Considering n moles of an ideal gas at P and T,

confined to a fixed V
◦ The gas temperature rises from T to T +ΔT, and
its pressure rises from P to P+ΔP
◦ The heat Q is related to the temperature
change Δ T by:
𝑄 = 𝑛𝐶𝑣ΔT

The temperature of an ideal gas is

raised from T to T+ΔT in a constant
volume process
46
Molar specific heat at constant volume (𝐶𝑣 )

◦ Substituting 𝑄 = 𝑛𝐶𝑣 ΔT in the first law:

Δ𝐸𝑖𝑛𝑡 = 𝑛𝐶𝑣 ΔT – W
◦ With V = const, W = 0:
Δ𝐸𝑖𝑛𝑡 = 𝑛𝐶𝑣 ΔT
◦ Then:
Δ𝐸𝑖𝑛𝑡
𝐶𝑣 =
nΔT
3
◦ Substituting Δ𝐸𝑖𝑛𝑡 = 𝑛𝑅ΔT:
2
The temperature of an ideal gas is 3
raised from T to T+ΔT in a constant 𝐶𝑣 = 𝑅 = 12.5 𝐽/𝑚𝑜𝑙. 𝐾 (𝑚𝑜𝑛𝑎𝑡𝑜𝑚𝑖𝑐 𝑔𝑎𝑠)
2
volume process
47
Molar specific heat at constant volume (𝐶𝑣 )

◦ The values of 𝐶𝑣 for diatomic gases (having

molecules with two atoms) and polyatomic gases
(having molecules with more than two atoms)
are greater than those for monatomic gases (the
more complex molecules can rotate and thus
have rotational kinetic energy)

◦ When Q is transferred to a diatomic or

polyatomic gas, only part of it goes into the
translational kinetic energy, increasing T

48
Molar specific heat at constant volume (Cv)

◦ Substituting 𝐶𝑣 = 3/2R:

𝐸𝑖𝑛𝑡 = 𝑛𝐶𝑣 𝑇
(𝑎𝑛𝑦 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠: 𝑚𝑜𝑛𝑎 − 𝑑𝑖𝑎 − 𝑝𝑜𝑙𝑦)

∆𝐸𝑖𝑛𝑡 = 𝑛𝐶𝑣 ∆𝑇 (𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠, 𝑎𝑛𝑦 𝑝𝑟𝑜𝑐𝑒𝑠𝑠)

A change in the internal energy Eint of a confined ideal gas

depends on only the change in the temperature, not on what
type of process produces the change.

49
Molar specific heat at constant pressure(Cp)

◦ Considering n moles of an ideal gas at T and V,

constant P
◦ The gas temperature rises to T +ΔT, and its
pressure rises to P+ΔP
◦ The heat Q is related to the temperature
change Δ T by:
𝑄 = 𝑛𝐶𝑝 ΔT
◦ 𝐶𝑝 is greater than 𝐶𝑣 , because energ must now be
The temperature of an ideal supplied not only to raise T but also for the gas
gas is raised from T to T + Δ T in a to do work
constant pressure process. Heat is
added and work. 50
Molar specific heat at constant pressure (Cp)

◦ To relate molar specific heats 𝐶𝑝 and 𝐶𝑣

∆𝐸𝑖𝑛𝑡 = 𝑛𝐶𝑣 ∆𝑇; 𝑄 = 𝑛𝐶𝑝 ∆𝑇
𝑃𝑉 = 𝑛𝑅𝑇 → 𝑊 = 𝑃∆𝑉 = 𝑛𝑅∆𝑇
◦ Then:
∆𝐸𝑖𝑛𝑡 = 𝑄 − 𝑊 → 𝑛𝐶𝑣 ∆𝑇 = 𝑛𝐶𝑝 ∆𝑇 − 𝑛𝑅∆𝑇
◦ Finally:
𝐶𝑣 = 𝐶𝑝 − 𝑅 𝑜𝑟 𝐶𝑝 = 𝐶𝑣 + 𝑅

The temperature of an ideal

gas is raised from T to T + Δ T in a
constant pressure process. Heat is
added and work. 51
The relative
values of Q for a
monatomic gas
and a diatomic gas
undergoing a
constant-volume
process (labeled
“con V”)
and a constant-
pressure
process (labeled
“con p”) 52
Exercise
1. The amount of heat required to raise the temperature of the unit mass of gas through one degree at
constant volume is
a) Cv
b) Cp
c) Latent heat
d) none of the mentioned

2. Which one of correct relation ?

a) Cp + Cv = 0
b) Cp = 1 + R/Cv
c) 1 = Cp/Cv
d) Cp = R + Cv

53
Exercise
3. The heat capacity depends on whether the heat is added at constant __________ or constant ________
a) Volume, Temperature
b) Pressure, Volume
c) Pressure, Temperature
d) Temperature, Pressure

4. Consider He gas an ideal gas, What is Cv for He?

a) 1.5 R
b) 2.5 R
c) 3.5 R
d) 4.5 R

54
Exercise
A bubble of 5.00 mol of helium is submerged at a certain depth in
liquid water when the water (and thus the helium) undergoes a
temperature increase T of 20.0°C- at constant pressure. As a result,
the bubble expands. The helium is monatomic and ideal.
(a) How much energy is added to the helium as heat during
the increase and expansion?
(b) What is the change Eint in the internal energy of the helium
during the temperature increase?
(c) How much work W is done by the helium as it expands against
the pressure of the surrounding water during the temperature
increase?

55
How do we measure specific heat of
a substance?

56
Degrees of freedom and
molar specific heats
• Molecules with more than one atom can store Eint
in forms other than translational kinetic energy.
• Considering He (monatomic gas), O2 (diatomic
gas), and CH4 (polyatomic gas)
• All three can have translational motions (moving
left–right and up–down) and rotational motions
(spinning about an axis like a top).
• Diatomic and polyatomic molecules can have
oscillatory motions, with the atoms oscillating
slightly toward and away from one another.
57
Degrees of freedom and
molar specific heats
The theorem of the equipartition of energy (James
Clerk Maxwell):

“Every kind of molecule has a certain number f of degrees of

freedom, which are independent ways in which the molecule can
store energy. Each such degree of freedom has
associated with it—on average—an energy of 1/2kT per
molecule (or 1/2RT per mole)”

58
Degrees of freedom and
molar specific heats
• What is the associated energy per molecule for a:
- monatomic gas?
3 degrees of translational freedom, no rotational freedom:
3(1/2kT)
- diatomic gas?
3 degrees of translational freedom + 2 degrees of
rotational freedom (can rotate like a top only about axes
perpendicular to the line connecting the atoms) → an
associated energy of 5(1/2kT) per molecule
• Replacing Eint = 3/2nRT with Eint = (f/2)nRT:
𝑓
𝐶𝑣 = 𝑅 = 4.16𝑓 𝐽/𝑚𝑜𝑙. 𝐾
2
59
Degrees of freedom and molar specific heats

◦ What can we see when looking at these tables?

60
Degrees of freedom and molar specific heats

1. What is the value of ratio between Cp and Cv for a gas of monatomic molecules?

Answer: For a monatomic gas:

Cv = fR/2 = 3R/2, Cp = (2+f)R/2 = 5R/2 → Cp/Cv = 5/3

2. What is the value of molar specific heat of a diatomic gas at constant pressure?
Answer: For a diatomic gas:
Cv = fR/2 = 5R/2, Cp = (2+f)R/2 = 7R/2

61
Adiabatic expansion of an ideal gas

◦ First law for a tiny volume change (P =

const):
𝑑𝐸𝑖𝑛𝑡 = 𝑄 − 𝑑𝑊 = 𝑄 − 𝑃𝑑𝑉
◦ Substituting:
𝑄 = 0 (no heat transfer)
𝑑𝐸𝑖𝑛𝑡 = 𝑛𝐶𝑣 𝑑𝑇
◦ Then:
𝑛𝐶𝑣 𝑑𝑇 = 0 − 𝑃𝑑𝑉
𝑃
𝑛𝑑𝑇 = − 𝑑𝑉
𝐶𝑣

62
Adiabatic expansion of an ideal gas

◦ From the ideal gas law:

𝑑 𝑃𝑉 = 𝑑 𝑛𝑅𝑇 → 𝑉𝑑𝑃 + 𝑃𝑑𝑉 = 𝑛𝑅𝑑𝑇
◦ Substituting 𝑅 = 𝐶𝑝 – 𝐶𝑣 :
𝑉𝑑𝑃 + 𝑃𝑑𝑉
𝑛𝑑𝑇 =
𝐶𝑝 − 𝐶𝑣
◦ Then:
𝑃 𝑉𝑑𝑃 + 𝑃𝑑𝑉
𝑛𝑑𝑇 = − 𝑑𝑉 =
𝐶𝑣 𝐶𝑝 − 𝐶𝑣
𝑃
− 𝑑𝑉 𝐶𝑝 − 𝐶𝑣 = 𝑉𝑑𝑃 + 𝑃𝑑𝑉
𝐶𝑣
𝑑𝑃 𝐶𝑝 𝑑𝑉
+ =0
𝑃 𝐶𝑣 𝑉
63
Adiabatic expansion of an ideal gas

◦ Subtituting γ = Cp/Cv and integrating:

𝑙𝑛𝑃 + γ𝑙𝑛𝑉 = 𝑎 𝑐𝑜𝑛𝑠𝑡
𝑙𝑛𝑃𝑉 γ = 𝑎 𝑐𝑜𝑛𝑠𝑡
γ
𝑒 𝑙𝑛𝑃𝑉 = 𝑎 𝑐𝑜𝑛𝑠𝑡
◦ Finally: 𝑃𝑉 γ = 𝑎 𝑐𝑜𝑛𝑠𝑡
𝑃𝑖𝑉𝑖 γ = 𝑃𝑓𝑉𝑓 γ
◦ Subtituting 𝑃 = 𝑛𝑅𝑇/𝑉:
𝑛𝑅𝑇𝑉 γ
= 𝑎 𝑐𝑜𝑛𝑠𝑡 → 𝑇𝑉 γ−1 = 𝑎 𝑐𝑜𝑛𝑠𝑡
𝑉
𝑇𝑖𝑉𝑖 γ−1 = 𝑇𝑓𝑉𝑓 γ−1
◦ Remark: For an adiabatic free expansion: 𝑇𝑖 =
𝑇𝑓 (above equations cannot be applied)
64
Four special
processes that
an ideal gas can
undergo

65
Exercise
Initially an ideal diatomic gas has pressure Pi =
2.00 x105 Pa and volume Vi = 4.00 x 10-6m3.
How much work W does it do, and what is the
change in its internal energy if it expands
adiabatically to volume Vf = 8.00 x 10-6m3?
Throughout the process, the molecules have
rotation but not oscillation.

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Summary
• Concept of kinetic theory of gases
• Ideal gas law (PV = nRT)
• Work done by an ideal gas
• Pressure, Temperature, and Molecular Speed
• Temperature and Kinetic Energy
• Mean Free Path
• Maxwell Speed Distribution
• Molar Specific Heats
• Degrees of Freedom and CV
• Adiabatic process

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