Content

9.1 Ideal gas equation

9.2 Pressure of a gas
9.3 Molecular kinetic energy
9.4 The r.m.s. speed of molecules
9 Kinetic Theory of Gases 9.5 Degrees of freedom and law of
equipartition of energy
By Liew Sau Poh 9.6 Internal energy of an ideal gas

1 2

Objectives
(a) use the equation of ideal gas, pV = nRT
(b) state the assumptions of the kinetic theory of
an ideal gas
(c) derive and use the equation for the pressure
exerted by an ideal gas, p = 1/3 <c2>
(d) state and use the relationship between the
Boltzmann constant and molar gas constant
k = R / NA
(e) derive and use the expression for the mean
translational kinetic energy of a molecule,
½ m<c2> = 3/2 kT
(f) calculate the r.m.s. speed of gas molecules
3 4
Objectives
g) sketch the molecular speed distribution graph
and explain the shape of the graph
(description of the experiment is not required)
h) predict the variation of molecular speed
distribution with temperature
i) define the degrees of freedom of a gas
molecule
j) identify the number of degrees of freedom of a
monatomic, diatomic or polyatomic molecule
at room temperature
k) explain the variation in the number of degrees
of freedom of a diatomic molecule ranging
from very low to very high temperatures

Objectives
l) state and apply the law of equipartition of
energy
m) distinguish between an ideal gas and a real gas
9.1 Ideal gas equation
n) explain the concept of internal energy of an
ideal gas
o) derive and use the relationship between the
internal energy and the number of degrees of
freedom.

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9.1 Ideal gas equation 9.1 Ideal gas equation

1
P
Gases at low pressures are found to obey V
the ideal gas law: PV nRT Equation above also can be write as
P1V1 = P2V2
at constant temperature is inversely Where P1 = initial pressure
P2 = final pressure
1 V1 = initial volume
P if T = constant
V V2 = final volume

7 8
 P P
T2

T1

T2
T1
0 V 0 1/ V
9 10

PV PV

T2 T2
T1 T1

0 P 0 V
11 12

States :
constant pressure is directly proportional to its
V V
V T if P = constant, thus

V V1 V2
constant
T T1 T2
Where V1 = initial absolute volume,
T1 = initial absolute temperature,
V2 = final volume, T2 = final temperature -273.15 0 T/ oC 0 T/ K
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Gay- Graphs of Gay-

States :
constant volume is directly proportional to its P P

P T if V = constant
Equation above also can be write as
P/T = constant or P1/T1 = P2/T2 where

T1 : initial absolute temperature P1 : initial pressure

T2 : final absolute temperatu re P2 : final pressure -273.15 0 T/ oC 0 T/ K
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Equation of State for an Ideal Gas Equation of State for an Ideal Gas
An ideal gas is defined as a perfect gas which Consider an ideal gas in a container changes its
pressure, volume and temperature as shown in
Gay- figure below.

P1 P2 P2
2nd stage
V1 1st stage V' V2
T1 T1 T2

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Equation of State for an Ideal Gas Equation of State for an Ideal Gas

P1 P2 P2 P1 P2 P2
2nd stage 2nd stage
V1 1st stage V' V2 V1 1st stage V' V2
T1 T1 T2 T1 T1 T2

1st stage, temperature is kept at T1 2nd stage, pressure is kept constant at P2 ,

P2V ' P1V1 P1V1 V' V2 V2T1
V' V'
P2 T1 T2 T2
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Equation of State for an Ideal Gas Equation of State for an Ideal Gas
Thus P1V1 P2V2
T1 T2
PV nRT
Or PV Where n : the number of mole gas
constant
T
m m : mass of the gas
Hence, n where M : molecular mass
PVm M
R
T N
For n mole of an ideal gas, the equation of n where N : number of molecules
NA
state is written as PVm nRT 23
N A : Avogadro' s constant 6.02 x10 mol -1
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Equation of State for an Ideal Gas Real Gases

If the Boltzmann constant, k is defined as Assumptions of real gases by van der Waals:
R 23 1 The volume of the molecules may not be
k 1.38 x10 JK negligible in relation to the volume V occupied
NA
then the equation of state becomes by the gas.
The attractive forces between the molecules may
not negligible.
PV NkT
Therefore the equation of state for an ideal gas
Where k = R/NA has to be modified i.e.
PV = nRT = (N/NA)RT = N(R/NA)T = NkT PV nRT
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Real Gases Graphs representing the real gases
>T4 > T3

an 2 T3 T2 T1
P (V nb) nRT P
V2
T4
van der Waals equation of state
T3
The constants a and b are empirical constants,
different for different gases. Where a volume T2
of 1 mole of the gas molecules & depends on the T1
attractive intermolecules forces
nb total volume of the molecules 0 T
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Graphs comparing the real-ideal gases

PV
J K 1 mol 1
T
9.2 Pressure of a gas

Ideal gas
8.31

n / mol

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9.2 Pressure of a gas Kinetic Theory of Gases Assumptions

The macroscopic behaviour of an ideal
gas can be describe by using the
equation of state but the microscopic
behaviour only can be describe by
kinetic theory of gases.
29
The main assumptions of the kinetic theory
of gases are:
a) All gases are made up of identical atoms
or molecules.
b) All atoms or molecules move randomly
and haphazardly.
c) The volume of the atoms or molecules is
negligible when compared with the
volume occupied by the gas. 30

Kinetic Theory of Gases Assumptions 9.2 Pressure of a gas

d) The intermolecular forces are negligible Pressure of a gas, P is defined as:
except during collisions.
1
e) Inter-atomic or molecular collisions are P c2
3
elastic. P : pressure by gas
where
f) The duration of a collision is negligible : density of the gas
compared with the time spent travelling 2
c : mean square velocity of the gas molecules
between collisions.
g) Atoms and molecules move with constant
How to get this?
velocity between collisions. Gravity has no
effect on molecular motion. 31 32
9.2 Pressure of a gas 9.2 Pressure of a gas
Consider the molecules are contained in If a molecule of
a cubic box with the side length d as mass, m collides
shown in figure (a). with wall A hence it
will bounce off in
opposite direction
Assume the velocity of a
with velocity, -vx
molecule v
because of elastic
The velocity,v can be
collision as shown
resolved into components
in figure (b).
of vx, vy and vz.

33 34

9.2 Pressure of a gas 9.2 Pressure of a gas

Therefore the By assuming the
change in linear molecule move
momentum for x- from wall A to B
component : and bounce back to
Px mv x mv x wall A without
collides with other
Px 2mv x molecules, the time
taken for that
movement is 2d
t
vx
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9.2 Pressure of a gas 9.2 Pressure of a gas

From the definition of the impulse, For N molecules of ideal gas in the cubic
box, m 2 m 2 m 2
J x1 Fx1 t Px1 Fx v x1 v x 2 ....... v xN
d d d
Px1
Fx1 m 2
t
2mv x1 where Fx1 is the Fx v x1 v x22 ....... v xN
2

Fx1 average force of one d

2d The mean square of vx is
molecule.
v x1
v 2x1 v x22 ....... v xN
2
m 2 v 2x
Fx1 v x1 N
d 37 38

9.2 Pressure of a gas 9.2 Pressure of a gas

so the x-component for total force exerted Since the velocities of the molecules in the
on the wall of the cubic box: ideal gas are assumed to be random, there
Nm is no preference to one direction or
Fx v x2
d another. Hence
The velocity v is resolved into vx, vy and vz, v x2 v 2y v z2
hence 2
v vx2 v 2y vz2 then v2 3 v x2

v2 vx2 v 2y v z2 v2
v x2
39
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9.2 Pressure of a gas 9.2 Pressure of a gas
By substituting the relationship above in From the definition of pressure,
the equation for total force, Fx hence the F N m v2
total force exerted on the wall in all
P
A
where A d 2 and F
3 d
direction is given by 1 Nm v 2 1 Nm
P P v2
N m v 2
3 d3 3 V
F
3 d
because d3 V Then

1 where
PV Nm v 2
3 Nm : mass of the gas in the box.
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9.2 Pressure of a gas

Since the density of the gas, is given by
Nm
hence equation (15.1)
V can be written as 9.3 Molecular Kinetic Energy
1 1
P v2 OR P c2
3 3
where P : pressure by gas
: density of the gas
v 2 : mean square velocity of the gas molecules
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9.3 Molecular Kinetic Energy 9.3 Molecular Kinetic Energy

Rearrange equation Rearrange eq. P 2 N 1
m v2
3 V 2
P
1 Nm
v2 into P 2 N 1 m v 2 2 1
3 V 3 V 2 into PV N m v2
This equation shows that P increases ( ) When 3 2

N 1 From the equation of state in terms of

increases and m v2 increases Boltzmann constant, k : PV NkT
V 2
By equating eq. 2 1 2
PV N m v
3 2
with eq. PV NkT
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9.3 Molecular Kinetic Energy 9.3 Molecular Kinetic Energy

1 3 1 For N molecules of ideal gas in the cubic
thus m v2 kT and m v2 K tr
2 2 2 box, the total average (mean) translational
3
K tr kT where kinetic energy, E is given by
2
Ktr : average translational kinetic energy 3
E NKtr E N kT
2
of a molecule
T : absolute temperature 3 3
E NkT nRT
2 2
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 Distribution of molecular speeds
Not all the molecules have the same
speed
9.4 The root mean square (R.m.s.) Apparatus for studying molecular speed
speed of molecules distribution (1831-1879)

49 50

Distribution of molecular speeds Maxwell Distribution

Gas molecules constantly collide elastically with
each other and with the wall of the container distribution law:
Under the collision, kinetic energy transfer 3/ 2 Mv2
M 2 2 RT
from one molecule to another, hence the P (v) 4 v e
kinetic energy of one molecule increases while 2 RT
the other one decreases P(v)dv fraction
Molecules move in difference speed as the of molecules with
speed changes after each collision speeds in the James Clerk Maxwell
The distribution of molecular speed is known as range from v to v (1831-1879)
Maxwell distribution + dv
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P(v)dv fraction of molecules with

Maxwell Distribution
speeds in the range from v to v + dv
Number of molecules,
n (v) V0 < Vm < Vrms
V0 = Most probable
speed
Vm = mean speed
Vrms = root mean square
speed

T1
0 V0 Vm Vrms Speed, v
53 54

P(v)dv fraction of molecules with The distribution of speeds for nitrogen gas
speeds in the range from v to v + dv molecules at three different temperatures

3RT
urms =

55 56
 The distribution of speeds of three different
Maxwell distribution
gases at the same temperature
Number of molecules, n (v)

T2 > T1
T1
0
Speed, v
57 58

9.4 The r.m.s. speed of molecules 9.4 The r.m.s. speed of molecules
1 3
Because of m v2 kT 1 3P
2 2 Since P v2 thus v2
3kT 3
thus v2
m therefore the equation of root mean square
3kT velocity also can be written as
Then vrms v2 or v rms
m
where vrms : root mean square velocity (speed) 3P
m : mass of a molecule gas vrms
M : relative molecular mass of gas
T : absolute temperature 59 60

9.4 Distribution of molecular speeds 9.4 Distribution of molecular speeds

Distribution Most probable
function is P(v )dv 1 speed:
normalized to 1: 0 dP
vP 0
8RT dv
vavg vP (v)dv
Average speed: M 2 RT
0 vP
Root mean M
3RT
square speed: vrms v 2 P(v)dv Gas diffusion is the gradual mixing of molecules
M
0 of one gas with molecules of another by virtue of
61
their kinetic properties. 62

9.5 Degrees of freedom

Definition is defined as the number of
independent ways in which an atom or
9.5 Degrees of freedom molecule can absorb or release or store
and energy
law of equipartition of energy

63 64
Example Example
Monatomic gas (e.g. He, Diatomic gas (e.g.
Neon, Argon) H2, O2, N2)
The number of The number of
degrees of freedom is 3 degrees of freedom
is:
i.e. three direction of
translational motion Translational
kinetic energy = 3
where contribute
translational kinetic Rotational kinetic
energy = 2/5
energy.
65 66

Example Example: degrees of freedom

Polyatomic gas (e.g. Degrees of Freedom
(f) Average kinetic
H2O, CO2, NH3) Molecule 536
Eg. energy per
2
kT 3 kT
Translat Rotati Tot molecule,<K>
The number of ional onal al
degrees of freedom is 3
Monatomic He 3 0 3 kT
Translational kinetic 2
energy 3 5
Diatomic He 3 2 5 kT
Rotational kinetic 2
energy = 3/6 6
Polyatomic H 2O 3 3 6 kT 3kT
2
67 68

9.5 Degrees of freedom 9.5 Degrees of freedom

Degrees of freedom depend on the Hydrogen gas have the vibrational kinetic
absolute temperature of the gases. energy as shown in figure above where
contribute 2 degrees of freedom which
For example : Diatomic gas (H2) correspond to the kinetic energy and the
potential energy associated with vibrations
H H along the bond between the atoms
At 250 K f=3
vibration At temperature (250 750 K) f = 3
At temperature >750 K f=3
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9.5

energy of every degrees of freedom of a

molecule is 1 kT or 1
RT 9.6 Internal Energy of An Ideal Gas
2 2
f f
K kT RT where
2 2
K : average kinetic energy of a molecule gas
f : degrees of freedom T : absolute temperature

k : Boltzmann constant R : molar gas constant

71 72
9.6 Internal Energy of An Ideal Gas 9.6 Internal Energy of An Ideal Gas
Definition is defined as the sum of total
kinetic energy and total potential energy U N K.E.
of the gas molecules.
But in ideal gas, intermolecular forces are f R
U NkT and
assumed to be negligible hence the 2 k
NA
potential of the molecules can be f
neglected. Thus for N molecules, U nRT where U : internal energy of the gas
2
U N K.E.
73 74

Example Solution
A quantity of plasma is composed of hydrogen (vrms)e=3 x 106 m s-1
ions (protons) and electrons in thermal
equilibrium. Both the protons and electrons are a. By using the equation of vrms,
assumed to behave like molecules of an ideal gas.
The r.m.s. speed of an electron in the plasma is electron : 3kT
estimated to be 3 x 106 m s-1.
(vrms ) e
me
a. Determine the r.m.s. speed of the hydrogen
ions. 3kT
b. Estimate the temperature of the plasma. hydrogen ion : (vrms ) H mH
(Given mass of electron = 9.11 x 10-31 kg, mass of
hydrogen ion = 1.67 x 10-27 kg, Boltzmann
constant, k = 1.38 x 10-23 J K-1)
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Solution Solution
then eq. (1) divided by eq. (2), thus b. The temperature of the plasma is given
by
(vrms ) e mH 3kT
(vrms ) e
(v rms ) H me me

4 1 (vrms ) e 2 (me )
vrms H 7.01x10 m s T
3k
T 1.98x105 K
77 78

Summary
Ideal Gas Equation PV = nRT = (N/NA)RT
Kinetic
Theory Molecular Kinetic Energy ½ mc2 = 3/2 kT
of End of Topic
Gases R.M.S. Speed Molecular speed
distribution & graph
Pressure of a Gas P = 1/3 <c2>

Degree of Freedom & Law K.E. Molecule = f/2 kT

of Equipartition of Energy

Internal Energy Interal energy of n

moles, U = f/2 nRT
79 80