TOPIC 6.

Kinetic Theory of Gases 9

6.6.2 The Kinetic Theory of Gases

1. HEAT CAPACITIES OF IDEAL GASES:

Compare the molar isobaric heat capacities of Argon,
cP = 20.786 Jmol K
-1 -1
and Nitrogen, c P  29.124Jmol -1 -1
K , to the heat
capacity predicted by the kinetic theory of gases; justify any significant
differences found. These heat capacities were obtained from Wikipedia.

From kinetic gas theory we have direct access to the isochoric heat
capacity only. However, we know that (for ideal gases) it is related to the
isobaric heat capacity via
cP = cV + R

To distinguish molar heat capacities this can be written as

cPn = cVn + R

Heat Capacity Definition

æ ¶u ö
cVn = ç ÷
è ¶T ø V

m 2
U=N v from kinetic gas theory
2
3 m 2 3
U= NkT since we have identified v = kT
2 2 2
3
u = N A kT where U = nu
2
3
u = RT
2

¶ æ3 ö
cVn = ç RT ÷ø
¶T è 2
3
cVn = R
2
3 J J
cVn   8.314  12.47
2 mol K mol K

cPn = cVn + R
J J J
cPn  12.47  8.314  20.78
mol K mol K mol K

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TOPIC 6. Kinetic Theory of Gases 10

Explain & Justify Results

The cP of Argon, given in the question as 20.786 J/mol.K, is nearly identical
to prediction form kinetic gas theory for monatomic ideal gases. This is to
be expected, as Argon is indeed a monatomic gas with very weak
intermolecular interactions.

However, the cP of Nitrogen is very different, i.e. inconsistent with a

monatomic ideal gas. The reason is that Nitrogen is actually not a
monatomic but a diatomic gas. This provides the molecules with more
options to store energy; the nitrogen molecules can rotate and also vibrate.
We say that Nitrogen has three translational, two rotational and one
vibrational degree of freedom. For quantum mechanical reasons not all
degrees of freedom are “switched on” at room temperature. This also
makes the heat capacities temperature dependent.

1
Each translational and rotational degree of freedom contributes kT to the
2
internal energy, while vibrational degrees of freedom contribute kT . Thus,
for Nitrogen we expect:
5
cVn = R
2
5 J
cPn  R  R  29.1
2 mol K
5 J J J
cPn   8.314  8.314  29.1
2 mol K mol K mol K

This is very close to the measured value.

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TOPIC 6. Kinetic Theory of Gases 11

2. KINETIC THEORY:
Estimate the root-mean-square velocity ( vRMS  v 2 ) of the atoms of
Xenon gas at a pressure of 1 MPa and a density of 52.6 kg/m 3. Provide the
root-mean-square velocities in both m/s and km/h. Additionally calculate
the temperature of the Xenon gas under these conditions.

As we want to calculate the root-mean-square velocity, we need some

expression that contains the velocity. We have derived two such
expressions: one for the pressure and the other for the internal energy.
Here we want to use the internal energy.
To use this equation we now what the internal energy is. We have found
that it is equal to the thermal energy. In the equation for the thermal energy
the temperature is unknown, but we can substitute it using the ideal gas
law.

m 2 3
UN v E therm = NkT PV  NkT
2 2

U = E therm
m 2 3
N v = NkT
2 2
3
= PV
2
PV m total nM Nm
v2  3 introducing the density   
Nm V V V
P
3


P
v2  3
ρ
1MPa
v2  3
52.6kg m 3
10 6 kg m 1s 2
v 2  3  3
 57034.2 m 2 s 2  238.8 m s 1
52.6 kg m
3600 s hr 1
v 2  238.8 m s 1  1
 859.68 km h -1
1000 m km

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TOPIC 6. Kinetic Theory of Gases 12

The Temperature

Finding the temperature is straightforward. We just use the ideal gas law.

PV  nRT
PV
T
nR
m nM
ρ 
V V
PM
T
Rρ
1MPa  0.1313 kg mol 1
T
8.314 J mol 1 K 1  52.6 kg m 3

1 J = 1 Pa m3, so simplification of units is simple

1MPa  0.1313 kg mol 1

T  300.24K
8.314 Pa m3 mol 1 K 1  52.6 kg m 3

Note that we have changed the units of M from g/mol to kg/mol to simplify
the calculation of the units. Always remember that kilograms are the SI
base unit of mass, not grams, whereas moles are the SI base unit of
substance amount, not kilomoles!
When all quantities are expressed in SI units the numerical result is the one
that belongs to the SI unit of the quantity of interests, here K. However, it is
always advisable to calculate the units to check that we get the correct unit
for the result. If that is not the case an error has occurred – usually one of
the variables has no been replaced by its numerical value.

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TOPIC 6. Kinetic Theory of Gases 13

3. KINETIC THEORY:
The UK motorway speed limit is 80 mph, estimate the temperature of Argon
gas at which the root-mean-square velocity is 80 mph. Be careful to check
all units.

This problem is very similar to the previous.

U  Ek
m 3
N v 2  NkT
2 2
mv  3kT
2

Rearrange for T and Simplify

mv 2 M
T m
3k NA
Mv 2
T kN A  R
3kN A
Mv 2
T
3R

Change Units of RMS Velocity from Mph to m/s

1 Mile = 1.61 km & 1 Hour = 3600s
miles km m m
v 2  80  128.8  128800  35.7
h h h s

Mv 2
T
3R
0.040kg  35.7 2 m 2s 2 0.040 kg  35.7 2 m 2s 2
T   2.04K
3  8.314 J mol 1K 1 3  8.314 kg m 2s 2 mol 1K 1

Together with the results of the previous problem this shows that at room
temperature the random motion of the molecules is much faster than any
flow velocity.

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TOPIC 6. Kinetic Theory of Gases 14

4. IDEAL GAS:
Derive equations for both the isobaric thermal expansion coefficient  and
the isothermal compressibility  for an ideal gas. Both expressions are
defined below

1  V  1  V 
      
V  T  P V  P  T

Isothermal Compressibility
1  V  nRT
    We need V=V(P) . Use ideal gas EOS V  .
V  P  T P
1   nRT 
   
V  P P  T

   nRT P 2 
1
V

κ  P  P 2 
κ  P 1

Isobaric Thermal Expansion Coefficient

1  V  nRT
   We need V=V(T) . Use ideal gas EOS V  .
V  T  P P
1   nRT 
  
V  T P  P
1 nR

V P
1 VR

V PT
1

T

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TOPIC 6. Kinetic Theory of Gases 15

5. STATE VARIABLES:
An ideal gas undergoes three processes in the following sequence: first,
isothermal compression from state “1” (original state) to state “2”; second,
isobaric expansion from state “2” to state “3”, where state “3” has the same
volume as state “1”; and finally isochoric cooling back to the original state
“1”. Sketch this cycle in P  V , T  V and P  T diagrams.

P-V Diagram

T-V Diagram

T-P Diagram

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