Chapter 8 Kinetic Theory of Gas

PETROVIETNAM UNIVERSITY
FACULTY OF FUNDAMENTAL SCIENCES
Fundamental Physics
Chapter 8
Pham Hong Quang
E-mail: quangph@pvu.edu.vn
Hanoi, August 2012
Chapter 8. The Kinetic Theory of Gases

8.1 Molecular Model of an Ideal Gas
8.2 Molar Specific Heat of an Ideal Gas
8.3 Adiabatic Processes for an Ideal Gas
8.4 The Equipartition of Energy
8.5 The Boltzmann Distribution Law
8.6 Distribution of Molecular Speeds
Pham Hong Quang
Faculty of Fundamental Physics

Macroscopic vs. Microscopic
So Descriptions
far we have dealt with macroscopic variables:
Pressure
Volume
Temperature
These can be related to a description on a
microscopic level.
Matter is treated as a collection of molecules.
Applying Newtons laws of motion in a statistical
manner to a collection of particles provides a
reasonable description of thermodynamic
processes.
Pressure and temperature
relate directly to
Pham Hong Quang

Avogadro's Number!
We ask the following question: How many
carbon-12 atoms are needed to have a mass of
exactly 12 g? That number is NA - Avogadro's
number.
Careful measurements yield a value for
NA = 6.0221367x10^+23.
1 mole = 6.022 x 1023 particles of any
substance
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Ideal Gas Assumptions
The average separation between the molecules
is large compared with their dimensions.
The molecules occupy a negligible volume
within the container.
This is consistent with the macroscopic model
where we modeled the molecules as pointlike particles.
The molecules obey Newtons laws of motion,
but as a whole they move randomly.
Any molecule can move in any direction with
any speed.
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Ideal Gas Assumptions.
Cont.
The molecules interact only by short-range

forces during elastic collisions.
This is consistent with the macroscopic model,
in which the molecules exert no long-range
forces on each other.
The molecules make elastic collisions with the
walls.
These collisions lead to the macroscopic
pressure on the walls of the container.
The gas under consideration is a pure
substance.
All molecules are identical.
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Ideal Gas Equation
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Ideal Gas Equation, Cont.
The conditions 0 0C and 1 atm are called
standard temperature and pressure (STP).
Experiments show that at STP, 1 mole of an
ideal gas occupies 22.414 L.
R = 8.31
J/mol.K
Pham Hong Quang

Pressure and Kinetic
Energy
Consider a collection
of N
molecules of an ideal gas in a
container of volume V.
Assume the container is a cube.
Only molecules moving toward the
surface hit the surface. Assuming
the surface is normal to the x axis,
half the molecules of speed vx
move toward the surface.
Only those close enough to the
surface hit it in time dt, those
1 N
within the distance
A v vxdt
x dt
2 V
The number of collisions hitting an

area
A inQuang
Pham
Hong

Assume perfectly elastic
collisions with the walls of
the container.
The molecules velocity
component perpendicular
to the wall is reversed.
The mass of the wall is
much greater than the
mass of the molecule.
The wall causes a change
in the molecules
momentum:
2mv
x
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10

Momentum in time dt
Force:
Pressure:
1 N
dp 2mv x
A v x dt
2 V
dp
1 N
F
2mv x
A vx
dt
2 V
F N 2
P mv x
A V
Not all molecules have the same v x
average vx
N 2
P mv x
V
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11

2
vx
1 2 1 2 2 2
= v v x v y vz
3
3
2
vx
Pressure:
1 2 1 2
= v vrms
3
3
1 N 2 2 N 1 2
P
mv
mv
3V
3 V 2
1 2 1 2
K mv mvrms
2
2
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2 N
P K
3 V
12
This equation relates the macroscopic

quantity of pressure with a microscopic
quantity of the average value of the square of
the molecular speed.
One way to increase the pressure is to
increase the number of molecules per unit
volume.
The pressure can also be raised by
increasing the speed (kinetic energy) of the
molecules.
This can be accomplished by raising the
temperature
of the gas.
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13

Molecular Interpretation of
Temperature
We can take the pressure as it relates to the

kinetic energy and compare it to the pressure
from the equation of state for an ideal gas.
2 1 ___2
PV N m v NkBT
3 2
R
kB
NA
k B 1.38.10 23 J / K 8.62.10 5 eV / K
Therefore, the temperature is a direct measure
of the average molecular kinetic. energy
Simplifying the equation relating temperature
and kinetic energy gives
___
1
3
mo v 2 kBT
2
2
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14
From
an
d
1
2
PV N mvrms
3
N
PV nRT
RT
NA
vrms
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3RT
15

Internal Energy
For monatomic gas: the internal energy
= sum
of the kinetic energy of all molecules:
Eint
3
3
N K nN A k BT nRT
2
2
Eint
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3
nRT T
2
16

Mean Free Path
Molecules collide elastically with other
molecules
Mean Free Path : average distance
between
1
two consecutive collisions
2d N / V
The bigger the molecules the more

collisions
The more molecules the more
collisions
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17
8.2 Molar Specific Heat

Several processes can
change the temperature of
an ideal gas.
Since T is the same for
each process, Eint is also
the same.
The work done on the gas is
different for each path.
The heat associated with a
particular change in
temperature is not unique.
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18

We define specific heats for two processes that
frequently occur:
Changes with constant pressure, isobaric
Changes with constant volume, isochoric
Using the number of moles, n, we can define molar
specific heats for these processes.
Molar specific heats:
CV for constant-volume processes Q = n CV T
CP for constant-pressure processes Q = n CP T
Q (constant pressure) must account for both the
increase in internal energy and the transfer of
energy out of the system by work.
Qconstant P > Qconstant V for given values of n and T
C >C
V
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19

Ideal Monatomic Gas
A monatomic gas contains one atom per
molecule.
When energy is added to a monatomic gas in a
container with a fixed volume, all of the energy
goes into increasing the translational kinetic
energy of the gas.
There is no other way to store energy in such a
gas.
Therefore, Eint = 3/2 nRT
In general, the internal energy of an ideal gas is
a function of T only.
The exact relationship depends on the type of
gas.
constant
volume,
= EintPhysics
= nCV T
PhamAt
Hong
Quang
Faculty ofQ
Fundamental
20

Solving for CV gives CV = 3/2 R = 12.5 J/mol . K
For all monatomic gases
This is in good agreement with experimental
results for monatomic gases.
In a constant-pressure process, Eint = Q -W
(W is positive when work is done by the system
and negative when work is done on the system)
So: Q = Eint +W and PdV =nR Then: Cp = CV
+R
Cp = 5/2 R = 20.8 J/mol . K
Pham Hong Quang
21

Ratio of Molar Specific Heats
We can also define the ratio of molar specific
heats.

CP 5R / 2
1.67
CV 3R / 2
Theoretical values of CV , CP , and are in

excellent agreement for monatomic gases.
But they are in serious disagreement with the
values for more complex molecules.
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22

An adiabatic process is one in which no energy is
transferred by heat between a system and its
surroundings.
All three variables in the ideal gas law (P, V, T )
can change during an adiabatic process.
Assume an ideal gas is in an equilibrium state
and so PV = nRT is valid.
The pressure and volume of an ideal gas at
any time during an adiabatic process are
related by PV = constant.
= CP / CV is assumed to be constant during the
process.
Pham Hong Quang
23

Proof of equation: PV =
constant.
dEint dW pdV
dEint dQ dW
pdV
pV nRT
pdV Vdp nRdT nR

nCV
E nC T
int
Divide by pV:
C p CV R
Cp
CV
Pham Hong Quang
C p CV dV
dV dp
dV
(1 )
V
p
V
CV V
dV dp
dV
(1 )
V
p
V
24
dp
dV
0
p
V
ln p ln V ln( pV ) = const.
pV = const.
nRT
(
)V = const.
V
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TV
= const.
25

The PV diagram shows
an adiabatic expansion
of an ideal gas.
The temperature of
the gas decreases
Tf < Ti in this
process
For this process
pV = const.
TV
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= const.
26
8.4 Equipartition of Energy

With complex
molecules, other
contributions to internal
energy must be taken
into account.
One possible energy is
the translational motion
of the center of mass.
The center of mass can
translate in the x, y,
and z directions.
This gives three
degrees of freedom for
translational motion.
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27

Rotational motion about
the various axes also
contributes.
We can neglect the
rotation around the y
axis since it is
negligible compared
to the x and z axes.
Ideally, if the two
atoms can be
modeled as
particles, Iy is zero.
Rotational motion
contributes two degrees
of freedom.
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28
The molecule can

also vibrate.
There is kinetic
energy and potential
energy associated
with the vibrations.
The vibrational mode
adds two more
degrees of freedom.
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29
Taking into account the degrees of freedom from

just the translation and rotation contributions.
Eint = 5/2 n R T and CV = 5/2 R
This gives CP = 7/2 R
This is in good agreement with data for
diatomic molecules.
However, the vibrational motion adds two more
degrees of freedom .
Therefore, Eint = 7/2 nRT and CV = 7/2 R
This is inconsistent with experimental results.
Pham Hong Quang
30

Molar Specific Heat: Agreement with
Experiment
Molar specific heat is a function of temperature.
At low temperatures, a diatomic gas acts like a
monatomic gas.
CV = 3/2 R
At about room temperature, the value increases
to CV = 5/2 R.
This is consistent with adding rotational
energy but not vibrational energy.
At high temperatures, the value increases to CV
= 7/2 R.
This includes vibrational energy as well as
rotational and
translational.
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31
Pham Hong Quang
32

Complex
Molecules
For molecules with more than two atoms, the
vibrations are more complex.
The number of degrees of freedom is larger.
The more degrees of freedom available to a
molecule, the more ways there are to store
energy.
This results in a higher molar specific heat.
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33
8.5 Boltzmann Distribution Law

The motion of molecules is extremely chaotic
Any individual molecule is colliding with others
at an enormous rate
Typically at a rate of a billion times per
second
We add the number density nV (E )
This is called a distribution function
It is defined so that nV (E ) dE is the number
of molecules per unit volume with energy
between E and E + dE
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34
8.5 Boltzmann Distribution Law

From statistical mechanics, the number
density is nV (E ) = noe
E /k T
B
This equation is known as the

Boltzmann distribution law
It states that the probability of finding
the molecule in a particular energy
state varies exponentially as the energy
divided by kBT
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35
8.6 Molecular Speed Distribution

Thus far we have
discussed the random
nature of molecular
motion in terms of the
average (root mean
square) speed. But how
is this speed distributed?
The observed
distribution of gas
molecules in thermal
equilibrium is shown at
right
NV is
called the MaxwellPham
Hong Quang
36
The fundamental expression that describes

the distribution of speeds in N gas molecules
is
m
NV 4 N
k
T
B
3/ 2
2 mv 2 / 2 k BT
ve
m is the mass of a gas molecule, kB is

Boltzmanns constant and T is the
absolute temperature
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37

The peak shifts to the
right as T increases
This shows that the
average speed
increases with
increasing
temperature
The distribution
broadens as the
temperature
increases.
The asymmetric
shape occurs because
the lowest possible
speed is 0 and the
highest is infinity
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38

Relationship between molar mass
and
molecular speed
The most probable speed increases as the

molecular mass decreases.
The distribution broadens as the molecular mass
decreases.
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39

Evaporation
The speed distribution for liquids is similar to
that of gases
Some molecules in the liquid are more energetic
than others
Some of the fast moving molecules penetrate
the surface and leave the liquid
This occurs even before the boiling point is
reached
The molecules that escape are those that have
enough energy to overcome the attractive forces
of the molecules in the liquid phase
The moleculesFaculty
leftofbehind
have lower kinetic
Pham Hong Quang
Fundamental Physics
40
Thank you!
Pham Hong Quang
41

Chapter 8 Kinetic Theory of Gas

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PETROVIETNAM UNIVERSITY

FACULTY OF FUNDAMENTAL SCIENCES

Hanoi, August 2012

Chapter 8. The Kinetic Theory of Gases

Pham Hong Quang

Faculty of Fundamental Physics

8.1 Molecular Model of an Ideal Gas

8.1 Molecular Model of an Ideal Gas

Faculty of Fundamental Physics

8.1 Molecular Model of an Ideal Gas

Faculty of Fundamental Physics

8.1 Molecular Model of an Ideal Gas

The molecules interact only by short-range

Faculty of Fundamental Physics

8.1 Molecular Model of an Ideal Gas

Pham Hong Quang

Faculty of Fundamental Physics

8.1 Molecular Model of an Ideal Gas

Pham Hong Quang

Faculty of Fundamental Physics

8.1 Molecular Model of an Ideal Gas

The number of collisions hitting an

8.1 Molecular Model of an Ideal Gas

Pham Hong Quang

Faculty of Fundamental Physics

8.1 Molecular Model of an Ideal Gas

Not all molecules have the same v x

Faculty of Fundamental Physics

8.1 Molecular Model of an Ideal Gas

Faculty of Fundamental Physics

8.1 Molecular Model of an Ideal Gas

This equation relates the macroscopic

8.1 Molecular Model of an Ideal Gas

We can take the pressure as it relates to the

Pham Hong Quang

Faculty of Fundamental Physics

8.1 Molecular Model of an Ideal Gas

Pham Hong Quang

Faculty of Fundamental Physics

8.1 Molecular Model of an Ideal Gas

Faculty of Fundamental Physics

8.1 Molecular Model of an Ideal Gas

The bigger the molecules the more

Faculty of Fundamental Physics

8.2 Molar Specific Heat

Faculty of Fundamental Physics

8.2 Molar Specific Heat

Faculty of Fundamental Physics

8.2 Molar Specific Heat

8.2 Molar Specific Heat

Pham Hong Quang

Faculty of Fundamental Physics

8.2 Molar Specific Heat

Theoretical values of CV , CP , and are in

Faculty of Fundamental Physics

8.3 Adiabatic Processes for an Ideal Gas

Pham Hong Quang

Faculty of Fundamental Physics

8.3 Adiabatic Processes for an Ideal Gas

pdV Vdp nRdT nR

Pham Hong Quang

8.3 Adiabatic Processes for an Ideal Gas

Faculty of Fundamental Physics