Determination of Heat Capacity Ratio of Air
Using the Adiabatic Expansion Method
Alicia Theresse Dumlao, Michael Jemziel Gulay, Monique Ramirez, Myka Felice Reyes
Univeristy of the Philippines, Diliman - Department of Chemical Engineering
Quezon City, Philippines
aliciadumlao@gmail.com
Abstract—Heat capacity relates the energy absorbed by
molecules to the change in temperature of a system. Heat
capacity ratio, gamma, is a quantitative property of molecules
based on the constant pressure and constant volume specific
heats of a molecule. Using adiabatic expansion and isochoric
thermal equilibrium, the Clement-Desormes method was
employed to obtain the heat capacity ratio of air. Air molecules
are approximately 99% diatomic in nature. In this experiment,
an average value of 1.635 was calculated as the heat capacity
ratio of air. This result has a 16.8% deviation from the
theoretical value of 1.4. The errors may be contributed by
human error such as recording of data, and application of the
adiabatic step in the method.
(specific heat, heat capacity ratio, adiabatic process,
Clement-Desormes Method)
I. INTRODUCTION
Heat capacity is the amount of energy needed to
increase the temperature of a substance by one degree. The
unit for specific heat is in energy units per degree of
temperature. This is thus an extensive property, which
increases as the amount of substance increases. To make
this property intensive, it must be divided by the total
amount of substance being tested (may be in moles or
grams). This process would then result in the specific heat
capacity, which is usually reported in joules per mole degree
Celsius.[1] One of the main uses of the heat capacity is in
calculating for the internal energy of a system
∆ U =mC p ∆ T . [1]
To simplify the first law of thermodynamics, an
adiabatic process may be used to assume the heat transfer to
be equal to zero. Derivation of the change in internal
energy, dU, should be equal to
C v dT=−PdV . [2]
Where the pressure may be expressed in terms of
volume using the ideal gas assumptions. Upon integration of
sides,
T2 V manometer fluid would not spill out of the manometer
C v ln =−Rln ( 2 ). [3]
T1 V1
From the values and equations of the controlled
volume and the specific heats for constant pressure the heat
capacity ratio may be expressed in this way:
P1
Cp P2
γ = =ln ⁡( ) [4]
Cv P1
P3
The internal energy may also be obtained by
determining the degrees of freedom of a molecule. The
degrees of freedom may be associated ith the internal
motions of the molecule, mainly translation, rotation, and
vibration.
In this experiment, the values of the heat capacity
may be computed using the above equation. The Clement-
Desromes method was used to determine the heat capacity
ratio of air.
II. MATERIALS AND METHODOLOGY
The experiment was rather simple, requiring the use
of minimal equipment, mainly thermometer, an air
compressor, and the carboy.
The room temperature was first recorded, followed
by initial pressure reading. The cork was then used to seal
the carboy. Adjustments in sealing the carboy with the cork
were done in the areas that produced bubbles when squirted
with soapy water. The outer side of the carboy was filled
with water and the water temperature was recorded. The
initial pressure reading of the open carboy was also
recorded as P0.
The air compressor was then connected into the setup
and was turned on. Air was then allowed to flow into the
carboy by opening valve A. Clamp B was then closed
slowly, and the reading in the manometer was recorded.
While reading the recorded data, Clamp B was being closed
fully. This process was done with caution to ensure that the
violently. In case of such cases, clamp B was closed again
slowly to release gas pressure.
The manometer fluid was then allowed to stabilize
and the recorded pressure was noted as P 1. Afterwards, the
cork was removed and replaced quickly. The pressure expansion while the change from P2 to P3 indicates the
reading was recorded as P2. For 10 minutes the system was change of the system during the constant volume process.
allowed to stabilize. After which, the final pressure reading Using these data and equation 4, the values of the heat
was recorded as P3. These steps were then repeated three capacity ratio were obtained and recorded in the table
times for more data comparisons and analysis. below.
III. RESULTS AND DISCUSSIONS
The setup was simple, with a carboy serving as space Table 3. Values of Heat Capacity Ratio
for the various processes (such as the adiabatic expansion). Trial gamma
The air compressor was used to supply the air needed to 1 1.59424729
conduct the experiment. The valves were opened to allow 2 1.54251521
air to fill the carboy. Meanwhile the carboy was also 3 1.76899715
connected to a manometer tube so that the pressure may be Average 1.63525322
read for every step in the process. The properties of the
system were obtained to assure that the process is being Air is composed of more than two different types of
done in the normal standard environment. A water bath was molecules, nitrogen, oxygen, argon, and other inerts.
used to make sure that the temperature of the carboy was However the inerts may be considered negligible since the
held constant. Table 1 holds the values of the determined mole fraction of inert compounds are much smaller than the
properties during the experiment. mole fraction of the nitrogen and oxygen. Since nitrogen
and oxygen are both diatomic in nature, the theoretical value
Table 1. Properties of System for the heat capacity ratio of air is 1.4. This value may be
Property Value Units calculated using the ideal heat capacities of diatomic
Room molecules. The heat capacities of molecules are
Temperature 27.1 deg C theoretically obtained and are based on the definitions of
Water Bath heat capacity, internal energy, and also on the Law of
Temperature 26.1 deg C Equipartition of Energy.
Room Pressure 1 Atm The internal energy of a substance is defined as the
energy brought about by the energy of the molecules that
After obtaining the data for the properties of the are internal to the substance. This means that external
system, the experiment was then conducted and the various energy such as energy brought by external position and
pressure readings, as found in Table 2, were obtained. macroscopic movement, is not added. Internal energy can
The pressures were only recorded once the pressure then be described by various motions such as translational,
readings stabilized. Especially in the case of the pressure P 2, rotational, and vibrational.
wherein the pressure was first allowed to stabilize after it Translational is the free movement of molecules
achieved a rapid change from when it was subjected to the along the 3 axes (x,y, and z). This motion is the only motion
adiabatic process. The change was fast since the removal available for monoatomic molecules since a single atom can
and insertion of the cork in the carboy were done fast freely move about in space, in all 3 planes. On the other
enough to ensure that at that time interval, no heat exchange hand the rotational movement is constrained only to the 2
occurred between the insides of the carboy and the axes (x and y axes), thus including only clockwise and
environment. This would then validate that the expansion of counterclockwise motion of molecules. This type of internal
the gas is indeed adiabatic. motion, along with the translational motion, is present in
diatomic molecules. This is because the added linearity of
Table 2. Pressure readings the diatomic molecules. Once the whole molecule moves, it
P0 P1 P2 P3 would seem like it is rotating instead of simply moving
Trial
(inH2O) (inH2O) (inH2O) (inH2O) around the way monoatomic molecules. To account for the
1 0.3 12.4 2.8 4.8 one dimensional movement of molecules, the change in
2 0.3 12.2 2.6 4.4 kinetic energy brought about by vibrational motion is also
3 0.4 13.7 3.1 5.8 accounted for. The vibrational motion may be described by
this equation[3]:
From the table above the data seem to be consistent. The θ vib 2 eθ / T
vib

values under the P0 column responds to the pressure (C v ) vib=N x R x ( ) x θ −1 2 [5]

obtained when the valve from the compressor to the system
was still closed. This value was set as the reference
pressure, meaning that to obtain the absolute pressure
readings, the initial pressure readings were to be subtracted
with the value of P0. The change of pressure from P1 to P2
describes the change of the system during the adiabatic
T (e vib
)
The quantity theta is the vibrational temperature,
which can only be defined when the system’s heat capacity
is thermally accessible. It is described by this equation:
 hcv induce motion among the molecules. However, for the
θ vib = [6] constant pressure specific heat, the expansion work done by
k
the molecules should be compensated with a higher value of
energy needed. Thus the relationship between a constant
where
volume and constant pressure specific heat is
h = Planck’s constant v = frequency
c = speed of light k = Boltzmann constant C p=C v + R . [11]
From these relations, the values of Cv and Cp may
With these information on internal types of motion, be obtained. Since air is mostly composed of diatomic
the concept of specific heat may further be examined. molecules, the kinetic energy associated with the internal
specific heat may be measured in two ways, in constant motions of the molecule would include translational and
pressure environments, and in constant volume processes. A rotational. A value of 5/2 for the constant volume heat
ratio of these two specific heats is defined as the heat capacity is obtained by integrating the energy expression
capacity ratio. The heat capacity ratio is often expressed as derived using the Principle of Equipartition of Energy. The
gamma, with the equation: internal motions that were accounted for in the computation
for the energy equation that was modified using the
Cv Principle of Equipartition of Energy are the translational and
γ= [7] rotational motions of the molecule.
Cp
For monoatomic molecules, there is are three degrees From the table below, it can be seen that the
of freedom, which accounts for the translational energy experimental heat capacity ratio is close to the theoretical
motion in the x, y, and z planes, present for the calculation value, and only has minimal error.
of the internal energy. Thus, the amount of energy in it is
equal to three times the kinetic energy of the movement in
each axis. Table 4. Percentage error
Trial 1 %error
1 1 1 1 13.87
Etrans = mv x 2+ m v y 2 + m v z2 [8]
2 2 2 2 10.18
The law of equipartition of energy states the total 3 26.36
energy is equally distributed within the system and that the Average 16.80
energy of the system is related to its temperature. Using this
law, each term may then be related to the average kinetic The deviations may be accounted for by human error
energy of the system in the following form: when conducting the process. The human error that may
1 have caused such deviations include the lag time in
E= k B T . [9] removing and replacing the cork from the carboy. The lag
2 time would invalidate the assumption that the expansion of
the gas is adiabatic since heat would be exchanged between
To achieve the energy per mole of substance, the
the carboy and the surroundings. Another factor that may
above equation must be multiplied with the Avogadro’s
have contributed to the deviations is the presence of
number to simplify the energy equation into this[2]:
microleaks in the system. Since the only sealing mechanism
1 is through the use of corks, spacing in between the cork and
E= RT . [10]
2 the carboy opening may have contributed to microleaks,
Thus for monoatomic molecules, the total internal thus invalidating assumptions that the system has constant
energy is equal to 3/2RT. as the number of atoms per volume and/or constant pressure. The valves may also
molecule increase, more internal motions become contribute to these microleaks since the equipment is
achievable for the molecule, thus adding more terms to the already old and some of the valves are not secure anymore.
equation for internal energy. Another error may be contributed for by the presence of
Since the specific heat is a measure of change in other molecuels in air that are not diatomic, unlike nitrogen
energy per degree of temperature, it is thus a derivative of and oxygen, in nature. However small the contribution of
the internal energy with respect to temperature. This these changes in structure may be, it is still valid to include
relationship would then solve for the value of the specific this as a possible source of deviation from the computed
heats. value of 1.4.
dU d (3/2 RT ) 3 These errors may be eradicated using different
C v= = = R methods for gathering heat capacity ratio. Examples of other
dT dT 2 methods include Kundt’s method, which utilizes the
relationship between heat capacity ratios and sound waves.
The constant volume specific heat only
Another method that may be used is the Ruchardt method.
accommodates instances wherein the temperatures only
This method on the other hand utilizes oscillations of a mass
supported by pressure of gases. The oscillations’ frequency
are hard to measure and so magnetic pickups that act as
speed sensors may be used. With these methods, human
error may be minimized since the signals are produced,
transmitted and read by advanced types of equipment.
IV. CONCLUSIONS AD RECCOMMENDATIONS
From the experiment, it can be concluded that the
Clement and Desormes setup would result in a reversible
heat capacity ratio of 1.635, a value with 16.80% error. For
the irreversible process, a value of 2.384 was obtained, a
value with 70.27% error.
The factors contributing to these deviations from the
theoretical value of 1.4 may be eliminated by making sure
that the expansion process is fast enough to make sure that it
is adiabatic and by ensuring that the carboy is indeed sealed
tightly. Another recommendation is by using other methods
such as those stated above, which will indeed minimize the
deviations caused by human error.
REFERENCES
[1] Smith, J.M., Van Ness, H.C., Abbott, M.M. “Introduction to
Chemical Engineering Thermodynamics.” Seventh Edition. 2005
[2] “Degree of Freedom and Heat Capacities of Gas.” December 2017.
Retrieved from
https://hemantmore.org.in/foundation/science/physics/specific-heat-
capacities/4534/
[3] Clayborne, A., Morris, V. “Measuring the Ratio of the Heat Capacity
at Constant Pressure to the Heat Capacity at Constant Volume for a
Gas (Cp/Cv)” Howard University 2017Retrieved from
https://chem.libretexts.org/Courses/Howard_University/Howard
%3A_Physical_Chemistry_Laboratory/8._Heat_Capacity_Ratios_for
_Gases_(Cp%2F%2FCv) March 3, 2019
[4] Rebillot, P.F. “Determining the Ratio Cp/Cv using Ruchardt’s
Method” Physics Department, The College of Wooster, Wooster,
Ohio. April 30, 1998
[5] Ayers, P., “Heat Capacity Ratio by Kundt’s Method” 2009