Contents

Exercise A - Determination of Heat Capacity Ratio......................................................1

OBJECTIVE..............................................................................................................1
METHOD...................................................................................................................1
THEORY....................................................................................................................2
APPARATUS/EQUIPMENT.....................................................................................4
PROCEDURE............................................................................................................5
RESULTS...................................................................................................................6
CONCLUSION & DISCUSSION.............................................................................7
REFERENCE.............................................................................................................8
Exercise B Determination of Ratio of Volumes using an Isothermal Process............9
OBJECTIVE..............................................................................................................9
METHOD...................................................................................................................9
THEORY....................................................................................................................9
APPARATUS/EQUIPMENT...................................................................................11
PROCEDURE..........................................................................................................11
RESULTS.................................................................................................................12
CONCLUSION & DISCUSSION...........................................................................13
REFERENCE...........................................................................................................15

TF7: Expansion Processes of A Perfect Gas

Exercise A - Determination of Heat Capacity Ratio
OBJECTIVE
1. To determine the heat capacity ratio, = C p/Cv for air near standard temperature
and pressure by studying the properties of an ideal gas, adiabatic processes and
the first law of thermodynamics.
2. To measure other thermodynamic properties using P-V-T data.
METHOD
The experiment involves a two-step process. In the first step a pressurized vessel is
depressurized 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

) 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

The design of this experiment is modified version from the original experiment
attributed to the names Clement and Desomes (or alternatively to Shoemaker). The
concept is based on the above pressure-volume diagram,
For a perfect gas,
(1)

C p =C v +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:
An adiabatic reversible expansion from the initial pressure P s to an intermediate
pressure Pi

{ Ps , Vol l s , T s } {Pi , Vol l i ,T i }

A return of the temperature to its original value Ts at constant volume Vol1i

{ Pi ,Vol li , T i } {P f ,Vol l f , T f }
For a reversible adiabatic expansion,
dQ=0

From the First Law of Thermodynamics,

(2)

dU =dQ+dW
Therefore during the expansion process
dU =dW

(3)

or dU =PdV

At constant volume the heat capacity relates the change in temperature to the change
in internal energy
(4)

dU =C v dT
Substituting (4) into (3),

(5)

C v dT =PdV

Substituting in the ideal gas law and then integrating gives

C v ln

Ti
Vi
=R ln
Ts
Vs

( )

( )

(6)

Now, for an ideal gas,

T i Pi V i
=
T s Ps V s

(7)

therefore
(8)
3

C v ln

Pi
Vi
Vi
+ ln
=R ln
Ps
Vs
Vs

( )

Rearranging and substituting in from (8),

ln

Pi C p V i
=
ln
Ps Cv
Vs

(9)

During the return of the temperature to the starting value,

V i Ps
=
V s Pf

(10)

Thus
ln

P s C p Ps
= ln
P i C v Pf

(11)

Rearranging gives the relationship in its required form:

C p ln P sln Pi
=
C v ln P sln P f

(12)

APPARATUS/EQUIPMENT

Valve 1
Valve 2
Valve 4
Valve 3

Air Pump

Large Vessel

Small Vessel

Pressure, Volume & Temperature Indicator (P-V-T indicator)

Figure 1: Set-up of Apparatus
PROCEDURE
1. Valves V1 and V3 on top of the vessels are opened to ensure that both rigid
vessels are at atmospheric pressure. Meanwhile, all other valves are closed.
2. The logger/recorder is configured and ready for use to record P and T(R)1 with
respect to time.
3. Valves V1 and V3 are closed and valve V4 is opened. The data logger/chart
recorder is started as appropriate.
4. The air pump is switched on to pressurize the large vessel. When an approximate
P value of 10kN/m2 is indicated on the console, the air pump is switched off and
the valve V4 is closed.
5. Pressure P in the vessel is given some time to stabilize as P will fall slightly due to
the vessel contents cools to room temperature.

The starting pressure, P s is

recorded. The starting temperature, Ts is also recorded for checking purpose

afterwards.
6. Valve V1 is opened and then closed very rapidly with a snap action allow a small
amount of air to escape from the vessel. Instantaneous pressure during the snap
action, Pi is recorded as accurate instantaneous value can obtained from the data
logger or chart recorder.
7. The vessel contents are allowed to return to ambient temperature before the final
pressure Pf is recorded. The final temperature, Tf is recorded and checked to
ensure the temperature remains constant throughout the experiment.
8. The exercise is repeated at different initial pressures in the vessel and the results
are tabulated.

RESULTS
The raw data obtained in this exercise is shown in Table 1 below.
Atmospheric pressure (absolute)
Patm (kN/m2)
Starting pressure (measured),
Ps (kN/m2)
Starting pressure (absolute),
Pabss = Ps+Patm kN/m2
Intermediate pressure (measured),
Pi (kN/m2)
Intermediate pressure (absolute),
Pabsi (kN/m2)
Final pressure (measured),
Pf (kN/m2)
Final pressure (absolute),
Pabsf (kN/m2)

101.325

101.325

101.325

101.325

10

16.2

22.13

30

111.325

117.525

123.455

131.325

8.37

14.24

20.95

28.84

109.695

115.565

122.275

130.165

8.76

14.54

21.23

29.1

110.085

115.865

122.555

130.425

Starting temperature, Ts (C)

27

27

28

28

Final temperature, Tf (C)

27

27

28

28

1.317

1.182

1.313

1.290

Heat Capacity Ratio, Cp/Cv

Table 1:

The atmospheric pressure, Patm is assumed to be 101.325 kPa since we do not have a
barometer to measure it. The calculation of each heat capacity ratio for different
starting pressure is based on equation (12). The experimental heat capacity ratio for
air can be determined by calculating their mean:
Cp
Cv

( )

=
avg

1.317 +1.182+ 1.313+ 1.290

=1.276
4

Hence, the percent error can be calculated as follow:

ValueTheoretical Value
| ExperimentalTheoretical
|100
Value

Percent Error=

The theoretical value of heat capacity ratio for air = 1.40 (J.Moran, 2011)

|1.2761.40
| 100 =8.86
1.40

Percent Error=

CONCLUSION & DISCUSSION

Adiabatic is a process that there is no transfer of heat into or out of a system, which
Q=0 (First law of thermodynamics equation: U=Q+W). The initial expansion
process of the gas inside the vessel can be considered adiabatic because under rapid
compression, the closed system does not have sufficient time to dissipate a significant
amount of heat energy that will affect the temperature of the system. When the
pressure is increased rapidly from work done on it by the air pump, the gas volume
decreases and the temperature increases as work is done on the system, causing the
internal energy to increase. This process is known as adiabatic heating as the closed
system is said to be adiabatically isolated, which the transfer of heat energy out or in
is infinitely slow and thus, the little heat dissipated during the expansion process is
negligible.
The experimental result obtained (1.276) for the heat capacity ratio of air is very close
to its theoretical value (1.40) with a small percent error of 8.86%. The result is
satisfying as the difference between it and the expected result is small. In this
experiment, there are several factors which contribute to the difference:
a) Fluctuation of starting pressure, Ps reading on the P-V-T indicator
After the vessel is pressurized, it is hard for P s to stabilize because it will always
fall slightly as the vessel content cools to room temperature once the air pump is
switched off. There is little heat dissipation of the system which is actually being
neglected in adiabatic process assumption. Therefore, the longer time it takes for
the reading to stabilize, the more amount of heat will dissipate as a result of
expansion, even though the expansion process is very slow.
b) Time reaction error when recording instantaneous value of intermediate pressure,
Pi
8

In order to record Pi, we have to open and close valve V1 very rapidly to ensure
the gas can expand rapidly with a small amount of gas. Therefore, it is difficult for
us to determine the exact point where the snap action is completed and take the
reading. We may take the reading at a moment before or after the snap action is
completed and this will cause the deviation of P i result. Moreover, the amount of
gas released during the snap action is inconsistent for multiple experiments with
different Ps. We may open the valve to a greater or a lower extent.
c) Unavailability of a barometer to measure the atmospheric pressure, Patm
Patm is assumed to be 101.325 kPa in the experiment as we dont have a barometer
to measure it. Luckily, our lab is located on ground level and thus the assumption
is said to be quite true. Nevertheless, assumed value of P atm will still affect our
calculation slightly as Patm can also be affected by other factors like air movement
inside the lab. Altitude is not the only factor which will affect Patm.
The transient response of the pressure and temperature sensors during gas
compression and expansion have been observed in this experiment. During
compression process, the pressure rises drastically until the desired value is reached
whereas the instantaneous resistance of thermistor sensor drops slightly, indicating
that the temperature encounters a slight rise within the range of 1C. On the other
hand, during expansion process, the pressure drops slightly as the vessel contents cool
to room temperature whereas the instantaneous resistance of thermistor sensor rises
slightly, indicating that the temperature encounters a slight rise, also within the range
of 1C.
Expansion processes of a perfect gas is ideal for studying adiabatic process and
thermodynamic properties of the gas. The heat capacity ratio can be determined and
calculated by using the heat capacity equation. The first law of thermodynamics is
proven.
REFERENCE
J.Moran, M. (2011). Fundamentals of Engineering Thermodynamics. United
States of America: Don Fowley.

Exercise B Determination of Ratio of Volumes using an Isothermal Process

OBJECTIVE
To determine the ratio of volumes for two vessels by using an isothermal expansion
process.
METHOD
One vessel is initially pressurised and allowed to stabilise at ambient temperature.
Then air is allowed to leak very slowly from the pressurised vessel into another vessel
of different size via a needle valve. This process is isothermal.
Observation of the pressure before and after the process enables the ratio of the
volumes of the vessels to be calculated.
THEORY
The theory for this experiment makes the assumption that air behaves as a perfect gas.
The final equilibrium pressure Pabsf can be determined from the ideal gas equation of
state:
Pab s f =

mRT
Vol

(13)

Where m is the sum of the initial mass present in the two vessels, m1 + m2,
Vol is the total volume of the two vessels, Vol1 + Vol2, and
T is the final equilibrium temperature.
Substituting in for m and Vol gives
Pab s f =

( m1+ m2 ) RT
Vol 1+Vol2

(14)

Both vessels are at room temperature before the valve is opened. As the process is
isothermal, the initial temperature will be the same as the final temperature, (T = T1 s
= T2s = T1f = T2f). Taking the ideal gas equation of state once again gives:
(15)
10

m1=

Vol 1 P 1 ab s s
RT

For the volume of the first vessel, and

m2=

Vol 2 P 2 ab s s
RT

(16)

For the volume of the second vessel. Substituting equations 15 and 16 into equation
14 then gives:
Vol 1 P 1 ab s s Vol 2 P 2 ab s s
+
RT
RT
RT
Pab s f =
Vol 1+Vol 2

(17)

Cancelling R and T, and rearranging gives

Pab s f =

( Vol 1 P 1 ab s s +Vol2 P 2 ab s s )

(18)

Vol1+Vol2

Dividing top and bottom by Vol2, this becomes:

Vol 1
P 1 ab s + P 2 ab s
(
Vol 2 )
Pab s =
+1
( Vol1
Vol2 )
s

(19)

This can be rearranged to give the equation for the volume ratio of the vessels,
Vol 1 P 2 ab s s Pab s f
=
Vol 2 Pab sf P 1 ab s s

(20)

11

APPARATUS/EQUIPMENT

Valve 1
Valve 2
Valve 4
Needle Valve 5
Valve 3
Valve 6

Air Pump

Large Vessel

Small Vessel

Pressure, Volume & Temperature Indicator (P-V-T indicator)

Figure 2: Set-up of Apparatus
PROCEDURE
1. Valves V1 and V3 on top of the vessels are opened to ensure that both rigid
vessels are at atmospheric pressure. Meanwhile, all other valves are closed.
2. The logger/recorder is configured and ready for use to record P, V, T(R)1 and
T(R)2 with respect to time.
3. Valves V1 and V3 are closed and valve V4 is opened. The data logger/chart
recorder is started as appropriate.
4. The air pump is switched on to pressurize the large vessel. When an approximate
P value of 16kN/m2 is indicated on the console, the air pump is switched off and
the valve V4 is closed.
5. Pressure P in the vessel is given some time to stabilize as P will fall slightly due to
the vessel contents cools to room temperature.

The starting pressure, P s is

recorded. The initial vacuum for second vessel, Vs is also recorded.

12

6. Valve V1 is opened and then closed very rapidly with a snap action allow a small
amount of air to escape from the vessel. Instantaneous pressure during the snap
action, Pi is recorded as accurate instantaneous value can obtained from the data
logger or chart recorder.
7. The needle valve V5 is ensured that it is fully closed and then the isolating valve
V6 is opened. Needle valve V5 is opened very slightly to allow air to leak from
the large vessel to the small vessel. V5 is adjusted to so that P falls slowly with no
change in T1 or T2 (if the flow of air is too fast then T1 and T2 will change and
the exercise must be repeated).
8. As the pressure P falls in the large vessel and the pressure rises in the small vessel
(negative readings for V) valve V5 can be opened slightly to reduce the duration
of the exercise.
9. The contents of both vessels are allowed to stabilise in pressure and temperature,
Then the final pressure, Pf (Vf = - Pf) is recorded.
10. The exercise is repeated at different initial pressures in the large vessel and the
results are tabulated.
RESULTS
For this exercise the raw data is tabulated under the following headings in Table 2
below.
Constant temperature for both
vessels, T (C)
Atmospheric pressure (absolute)
Patm (kN/m2)
Initial pressure for first vessel
(measured),
P1s (kN/m2)
Initial pressure for first vessel
(absolute),
P1abss = Ps+Patm kN/m2
Initial vacuum for second vessel
(measured),
Vs (kN/m2)
Initial pressure for second vessel
(absolute), P2abss = Patm Vs
(kN/m2)
Final pressure of vessels (measured),
Pf (kN/m2)
Final pressure of vessels (absolute),
Pabsf = Patm + Pf (kN/m2)
13

28
28
28
101.32 101.32 101.32
5
5
5
16

30.5

33.1

117.32 123.42 131.82

5
5
5

134.42
5

0.06

22.1

28
101.32
5

0.05

0.05

0.05

101.26 101.27 101.27

5
5
5

101.27
5

11.5
15.88
22
112.82 117.20 123.32
5
5
5

23.3
124.62
5

Volume Ratio,

Vol 1 P 2 ab s s Pab s f
=
Vol 2 Pab sf P 1 ab s s

2.569

2.561

2.594

2.383

The atmospheric pressure, Patm is assumed to be 101.325 kPa since we do not have a
barometer to measure it. The calculation of each volume ratio for different starting
pressure is based on equation (20). The experimental volume ratio can be determined
by calculating their mean:

( Vol1
Vol2 )

avg

2.569+ 2.561+ 2.594+2.383

=2.527(4 s . f .)
4

The theoretical value of volume ratio can be calculated by

Vol 1
Vol 2

of two vessels are given in the manual:

Vol1 = 0.0224m3, Vol2= 0.0091m3
Hence, theoretical value of volume ratio is:
Vol 1 0.0224
=
=2.462( 4 s . f .)
Vol 2 0.0091
Hence, the percent error can be calculated as follow:
ValueTheoretical Value
| ExperimentalTheoretical
|100
Value

Percent Error=

|2.4622.527
| 100 =2.64
2.462

Percent Error=

CONCLUSION & DISCUSSION

14

which the volume

The experimental result obtained (2.462) for the volume ratio is precise as compared
to its theoretical value (2.527) with a minimal percent error of only 2.64%. The result
obtained is almost similar to the expected result. In this experiment, there are several
factors which contribute to the difference:
a) Fluctuation of starting pressure, Ps and volume, Vs reading on the P-V-T indicator
After the vessel is pressurized, it is hard for P s and Vs to stabilize because it will
always fall slightly as the vessel content cools to room temperature once the air
pump is switched off. There is little heat dissipation of the system which is
actually being neglected. Therefore, the longer time it takes for the reading to
stabilize, the more amount of heat will dissipate as a result of expansion, even
though the expansion process is very slow.
b) Time constraint to wait for the final pressure, Pf of both vessels to stabilize and
meet
After needle valve V5 and valve V6 are opened, the pressure P falls in the large
vessel and rises in the small vessel as the air leaks from the large vessel to the
small vessel. However, the duration for pressure in both vessels to stabilize and
meet is too long. Therefore, we take the reading of P f when we wait until both
readings (Pf and Vf) are close enough, which is within difference of 2 kN/m2.
c) Unavailability of a barometer to measure the atmospheric pressure, Patm
Patm is assumed to be 101.325 kPa in the experiment as we dont have a barometer
to measure it. Luckily, our lab is located on ground level and thus the assumption
is said to be quite true. Nevertheless, assumed value of P atm will still affect our
calculation slightly as Patm can also be affected by other factors like air movement
inside the lab. Altitude is not the only factor which will affect Patm.
If the rate of change of pressure was sufficient to affect the temperature of the air
inside the vessels, the expansion will not be isothermal anymore but becomes
adiabatic. This is because in the isothermal compression of a gas, work is done on the
system to decrease the volume and increase the pressure. Doing work on the gas
increases the internal energy and will tend to increase the temperature and thus to
maintain the constant temperature, energy must leave the system as heat and enter the
environment. However, an adiabatic process is where a system exchanges no heat
15

with its surroundings. In other words, T = 0 and thus U = 0 for isothermal process
whereas Q=0 is for adiabatic. Hence, if the rate of change of pressure was sufficient
to affect the temperature of the air inside the vessel, the change in internal energy will
increase as a response to decrease the volume of the air.
Isothermal expansion process is ideal to determine the volume ratio of an ideal gas.
The experimental result is very accurate but there is just one thing which extra
caution is needed during the experiment, that is the necessity to ensure that the rate of
flow of pressure is insufficient to affect the temperature of two vessels.

REFERENCE
J.Moran, M. (2011). Fundamentals of Engineering Thermodynamics. United
States of America: Don Fowley.

16