Exercise A - Determination of Heat Capacity Ratio

Objective:
This experiment is a modern version of the original experiment attributed to the
names Clement and Desormes (or alternatively to Shoemaker).
The heat capacity ratio =

C p / C v can be determined for air near standard

temperature and pressure. The demonstration gives students experience with

properties of an ideal gas, adiabatic processes and the first law. It also illustrates
how P-V-T data are used to measure other thermodynamic properties.

Method:
The experiment involves a two-step process. In the first step a pressurised vessel
is depressurised briefly by opening then closing a large bore valve very quickly.
The gas inside the vessel expands from Ps to Pi - a process that can be assumed
to be adiabatic and reversible (P/ T

1
)

is constant).

NOTE: It has been argued that this is in fact an irreversible expansion doing work
against atmospheric pressure. The resulting equation assuming an irreversible
process yields virtually identical results to that where reversible conditions are
assumed, providing the pressure differential between the vessel and atmosphere
is small with respect to atmospheric pressure. Thus the assumption of a
reversible process is reasonable under the experimental conditions described.
The volume of gas inside the vessel is then allowed to return to thermal
equilibrium, attaining a final pressure Pf. The second step is therefore a constant
volume process (P/T is constant).

Theory:
For a perfect gas,

Cp =

Cv

+R

Where

Cp

= molar heat capacity at constant pressure, and

Cv

= molar heat capacity at constant volume.

For a real gas a relationship may be defined between the heat capacities, which
is dependent on the equation of state, although it is more complex than that for
a perfect gas. The heat capacity ratio may then be determined experimentally
using a two steps process:
1. An adiabatic reversible expansion from the initial pressure

Ps

to an

intermediate pressure Pi

2. A return of the temperature to its original value

Ts

at constant volume

Vol i

For a reversible adiabatic expansion

dq = 0
From the First Law of Thermodynamics,
dU = dq + dw
Therefore during the expansion process
dU = dW or dU = -pdV
At constant volume the heat capacity relates the change in temperature to the
change in internal energy
dU =

CV

dT

Substituting in to equation x,

CV

dT = -pdV

Substituting in the ideal gas law and then integrating gives

CV ln

Tf
Vol 1f
=R ln
Ti
V ol1i

( )

Now, for an ideal gas

Ti
Ts
Therefore

Pi Vol 1i
P s Vol 1s

CV ln

Pi
Vi
Vol1i
+ ln
=R ln
Ps
V ol 1s
V ol 1s

Rearranging and substituting in from equation x,

ln

Pi C p Vol 1i
=
ln
P s CV
V ol 1s

During the return of the temperature to the starting value,

Vol 1i Ps
=
V ol 1s P f
Thus

ln

Pi C p P s
=
ln
P s C V Pf

Rearranging gives the relationship in its required form:

C p ln Psln Pi
=
C V ln Ps ln P f

Equipment Set Up
Before starting the exercise ensure that both rigid vessels are at atmospheric
pressure by opening ball valves V1 and V3 on top of the vessels (open to
atmosphere). Close all other valves before commencing the exercise.
A data logger (teaching software) or chart recorder will be required to observe
the transient nature of the pressure and temperature inside the vessel and to
obtain an accurate value for the instantaneous intermediate pressure. The
logger/recorder should be configured and ready for use to record P and T(R)1
with respect to time when required during the exercise.
Procedure
1.
2.
3.
4.

Patm are measured and recorded by using a barometer.

Ball valves V1 and V3 are closed and valve 4 are opened.
The data logger/chart recorder are started as appropriate.
The large vessel are pressurised by switching on the air pump. The air
pump are switched off and valve v4 are closed when P reached
approximately 30kN/ m

(indicated on console).

5. Pressure P in the large vessel are waited until stabilised (P will fall slightly
as the vessel contents cools to room temperature).
6. The starting pressure

Ps

is recorded.

7. Valve V1 is opened then closed very rapidly with a snap action to allow a
small amount of air to escape from the vessel.

Pi (accurate instantaneous value can obtained from the data logger or

8.

chart recorder) is recorded.

9. The vessel contents are allowed to return to ambient temperature then the
final pressure

Pf

are recorded.

10.The exercise are repeated at 5 different initial pressures (10, 15, 20, 25,
35 kN/ m

) in the vessel ( Pf

becoming

Ps

for the subsequent run)

as the pressure falls towards atmospheric pressure following each step

change.

Results
Record your results under the following headings:
Atmospheric pressure (absolute) Patm ______ N/m2
Starting pressure (measured) P1s _______ N/m2
Starting pressure (absolute) P1abss _____ N/m (= Ps + Patm)
Intermediate pressure (measured) Pi ________ N/m
Intermediate pressure (absolute) P1absi _____ N/m (= Pi + Patm)
Final pressure (measured) Pf ________ N/m
Final pressure (absolute) P1absf _____ N/m (= Pf + Patm)
For each step response calculate the heat capacity ratio (Cp/Cv) for air as
follows: