UNIVERSIDAD NACIONAL DE COLOMBIA

Faculty of Engineering - Department of Chemical Engineering

PRE - LABORATORY REPORT
Laboratory of Thermodynamic and Transport Properties.
PRACTICE 6: SPECIFIC HEAT RELATIONS
GROUP 1: Professor: Ruth Lancheros and Edwin Chingate
Students: Daniel Andrés Gutiérrez Forero, Juan Sebastian Larrahondo Cruz and Sergio Esteban
Meneses Diaz.1

April 8th, 2018

ABSTRACT: In this document the theoretical foundations and the mathematical modeling are exposed
to perform the calculations for the adiabatic expansion coefficient (γ) of gases Carbon Dioxide (CO2)
and Air using the methods of Clément - Désormes and Rüchardt. The basic principles of the operation
of each assembly are shown, where different variables (time and pressure) will be measured in each
practice to calculate the ratio of specific heats, and finally perform a statistical analysis determining
which of the 2 methods is more accurate.
Keywords: Adiabatic expansion coefficient (γ), Clément – Désormes’ method, Rüchardt’s method.

1. INTRODUCTION development of the mathematical model, which

To determine the relation of specific heats of
some substances, it is necessary to understand
the thermodynamic system for each method. In
the present practice the methods that are
described to obtain these coefficients are
related to some basic concepts of physics and
laws of thermodynamics.
The Rüchardt method uses the thrust generated
by a gas to a sphere of known mass that is
introduced into a tube where it is assumed to be
in the absence of friction. By means of a
balance of forces on the sphere, and the
mathematical development that integrates
concepts of mechanics (waves) with
thermodynamics, it is possible to determine the
adiabatic coefficient of a gas.
The Clément - Désormes method produces an
adiabatic compression (or expansion) of the
gas, which causes its intensive properties P, V,
T to undergo changes when passing from one
state to another. By means of the analogy of the
experiment with respect to a piston begins the
makes use of thermodynamic laws and perfect
gases to calculate the ratio of specific heats of
the gas.
2. OBJECTIVES
1. General objective
Determine the relation between specific heats
under constant pressure and volume for Carbon
Dioxide (CO2) and Air using the methods of
Clément - Désormes and Rüchardt
2. Specific objectives
 Compare the results obtained in both
methods and verify them with the data
reported in the literature.
 Perform a statistical analysis of the data
obtained in the experiments.
 Compare the observed phenomena
with an event of everyday life using the
concepts of thermodynamic laws and
basic physical laws that are going to be
applied in the experiment.
 For a mechanically reversible process at
constant pressure, the energy balance is written:
3. THEORETICAL FRAMEWORK
𝑇2
Heat capacity 𝑄 = 𝑛 𝛥𝐻 = 𝑛 ∫ 𝐶𝑃 𝑑𝑇
𝑇1
Generally, the heat capacity is defined as the
necessary amount of energy to increase the For an ideal gas where Pv = nRT the following
temperature of an object by one degree. relation can be written:
Mathematically, the heat capacity of a stated ℎ = 𝑢 + 𝑃𝑣
quantity of substance can be expressed as 𝐶 =
𝑑𝑄/𝑑𝑇, the difficulty assosiated with this ℎ = 𝑢 + 𝑅𝑇
expression is that it causes C, like Q, to be
𝑑ℎ = 𝑑𝑢 + 𝑅𝑑𝑇
process-dependent quantities rather than a state
function, this variation of energy by exclusively 𝐶𝑃 𝑑𝑇 = 𝐶𝑣 𝑑𝑇 + 𝑅𝑑𝑇
thermal effects involves the various internal
modes through the molecules store energy 𝐶𝑃 = 𝐶𝑉 + 𝑅
individually [1]. Adiabatic expansion coefficient
Then the heat capacity at constant volume of a The adiabatic expansion coefficient is the ratio
substance is defined as: between the heat capacity at constant pressure
𝛿𝑈 𝐶𝑃 and the heat capacity at constant volume
𝐶𝑉 = ( )𝑉 𝐶𝑉 . Sometimes it is also known as isentropic
𝛿𝑇
expansion factor or specific heat ratio, it is
Although this definition does not refer strictly denoted by the expression [2]:
to any process, it is related in a particularly
simple way to a constant volume process within 𝐶𝑃
𝛾=
closed system: 𝐶𝑉

𝑑𝑈 = 𝑐𝑉 𝑑𝑇 The value of γ is in the narrow range of 1 to

𝑇2
1.67. Many common diatomic gases have an
𝛥𝑈 = ∫ 𝐶𝑉 𝑑𝑇 adiabatic index of approximately 1.4 at ambient
𝑇1 temperature. The adiabatic index is related to
𝐶𝑉 𝑎𝑛𝑑 𝐶𝑃 through the following expressions
Now, for the energy balance of a mechanically [2]:
reversible process at constant volume we have:
𝑅
𝑇2 𝐶𝑉 =
𝑄 = 𝑛𝛥𝑈 = 𝑛 ∫ 𝐶𝑉 𝑑𝑇 𝛾−1
𝑇1
𝑅𝛾
However if the process is no longer given at 𝐶𝑃 =
𝛾−1
constant volume, but at constant pressure, the
heat capacity can be defined as follows: Adiabatic transformation

𝛿𝐻 An adiabatic transformation is a transformation

𝐶𝑃 = ( )𝑃 during which the system does not exchange
𝛿𝑇
heat with the medium at any time. To determine
This heat capacity is related in a particularly the adiabatic equations as functions of P, V and
simple way to a process under constant pressure T, we must start from the differential equation
in a closed system: for an adiabatic [2]:
𝑑𝐻 = 𝐶𝑃 𝑑𝑇 𝑑𝑇 𝑑𝑉
= −(γ − 1)
𝑇2 𝑇 𝑉
𝛥𝐻 = ∫ 𝐶𝑃 𝑑𝑇
𝑇1
If γ is constant, when integrating we obtain:
 𝑇2 𝑉2
= ( )γ−1
𝑇1 𝑉1
Then applying equation of state, we obtain:
𝑃2 𝑉2 𝑉1
= ( )γ−1
𝑃1 𝑉1 𝑉2
𝑃2 𝑉1
= ( )𝛾
𝑃1 𝑉2
𝑃𝑉 γ = 𝑐𝑡𝑒
This last expression is known as the Poisson
equation and expresses the relation between
pressure and volume along an adiabatic system.
4. EXPERIMENTAL METHOD
Ruchardt’s method of self-sustained
oscillations
The purpose of this assembly is to take
advantage of the thrust generated by a gas to a
known mass, so that by means of a balance of
forces and the equilibrium assumptions of the
movement of the mass in the system we can
determine the adiabatic coefficient of the fluid.
To perform this, a sphere is placed inside a tube
and a valve is opened to allow the passage of
the gas from the bottom, then the ball is dragged
upwards and an oscillatory movement occurs
around the side of the tube.. Clement & Desormes’ adiabatic expansion
method
In the assembly of this method, a tank will be
filled with the gas up to a pressure in
equilibrium, after stabilized pressure the first
data pair will be taken (𝑃1 , 𝑇1 ), immediately the
adiabatic expansion is made quickly, letting out
a quantity of matter, then the second pair of data
is taken (𝑃2 , 𝑇2 ) and again it will rise until it
stabilizes again (𝑃3 , 𝑇3 ).
 made in glass with an accuracy of one
tenth of mL.
4. Gas supply to pressure gauge.
5. Glass tube
6. Metalic sphere
7. Matrass flask (1000ml)
8. Gas input

Algonside this equipment, also will be used:

 CO2 bulb with a high pressure valve, a

low pressure valve, and a supply valve.
 Analytical weighing scale
 Digital cronometer

5. CALCULATIONS
Ruchardt’s method of self-sustained
oscillations
The oscillation performed by the sphere can be
described as a harmonic movement, in order to
use the force equation it is assumed that the
movement occurs in the absence of friction, the
restoring force is constant, and that the
oscillations are symmetric with respect to the
hole, therefore, It can be written:
Equipment 𝐹 = 𝑃𝐴 (1)
Since the area is constant, by its differential
form we obtain:
𝑑𝐹 = 𝐴 𝑑𝑃 (2)
The change in pressure dP and the volume
change dV can be related through the
differential form of the Poisson equation:
𝑑𝑃 𝑘(−𝛾)
= 𝛾 (3)
𝑑𝑉 𝑉 𝑉
Since the process is reversible, then:
𝑃𝑉 𝛾 = 𝑘 (4)

Figure 1: Equipment outline Replacing equation 4 in equation 3:

1. Thermometer 𝑃(−𝛾)
𝑑𝑃 = 𝑑𝑉 (5)
2. Copper cylinder of 16 cm diameter and 𝑉
51.5 cm height (equipped with 2 gate
Writing equation 5 in terms of height (𝑑𝑉 =
valves and one ball valve).
3. Pressure gauge which consists of a 𝐴𝑑𝑥):
cuvette in acrylic, connected to a 𝑃(−𝛾)𝐴
burette of 49 ml as maximum height 𝑑𝑃 = 𝑑𝑥 (6)
𝑉
Replacing equation 6 in equation 2: through a line of constant enthalpy to a different
isotherm; the volume will increase because the
𝑃(−𝛾)𝐴2 gas contained in the control volume will find
𝑑𝐹 = 𝑑𝑥 (7)
𝑉 free space that will be occupied. The passage
Solving for the integral expression: from point 2 to 3 is the increase in isochoric
pressure, the volume of the cylinder has already
𝐹 𝑥
𝑃(−𝛾)𝐴2 been filled and the pressure will stabilize.
∫ 𝑑𝐹 = ∫ 𝑑𝑥
0 0 𝑉

𝑃(−𝛾)𝐴2
𝐹= 𝑥+𝐶 (8)
𝑉
𝑑2 𝑥
Rewriting the equation 8 (𝐹 = 𝑚𝑎 = 𝑑𝑡 2
𝑚):

𝑑2 𝑥 𝑃(−𝛾)𝐴2 𝐶
2
= 𝑥+ (9)
𝑑𝑡 𝑚𝑉 𝑚
Solving the second order differential equation:

𝑃(−𝛾)𝐴2
𝑥 = 𝐴𝑠𝑒𝑛√| |𝑡 (10)
𝑚𝑉
Figure 2: Plot of pressure vs. volume "Adiabatic
The movement made by the sphere is harmonic,
Transformations"
and the period of oscillation is given by
𝑃(−𝛾)𝐴2
√| | , written in terms of the frequency
𝑚𝑉
𝑛 1
The equation used for a cylinder-piston system:
(𝑓 = 2𝜋 𝜏 = 𝑓 ):
𝛿𝑊 = −𝑃𝑑𝑉 (13)
2𝜋
𝜏= (11) Writing the first law, as it is an adiabatic
𝑃(−𝛾)𝐴2 process:
√|
𝑚𝑉 |
𝛿𝑊 = 𝑑𝑈 (14)
Obtaining and expression for the adiabatic
coefficient: As it is at constant volume, the internal energy
can be expressed in terms of the 𝐶𝑉 :
4𝜋 2 𝑚𝑉
𝛾= (12) 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 (15)
𝑃𝐴2 𝜏 2
Clement & Desormes’ adiabatic expansion Replacing equation 15 in 13, and because it is a
𝑅𝑇
method perfect gas (𝑃 = ), the expression leads to:
𝑉
A balance will be made making the analogy 𝑅𝑇
with a cylinder-piston system. It is supposed to 𝐶𝑉 𝑑𝑇 = − 𝑑𝑉 (16)
𝑉
be an adiabatic system since the change in
pressure occurs so quickly that there are no heat Solving the integral:
transfers. When the pressure decreases, the 𝑇2 𝑉2
𝑑𝑇 𝑑𝑉
effects of irreversibility are ignored. 𝐶𝑉 ∫ = −𝑅 ∫
𝑇1 𝑇 𝑉1 𝑉
The process can be plotted in a diagram of P vs
V, where 1 corresponds to the first conditions, 𝑇2 𝑉2
𝐶𝑉 𝑙𝑛 = −𝑅𝑙𝑛 (17)
that is, once the tank has been filled. The 𝑇1 𝑉1
passage from point 1 to 2 is the adiabatic
From figure 2 can be concluded:
expansion, where the pressure descends
1 a 2 (𝑃1 , 𝑉1 , 𝑇1 ) → (𝑃2 , 𝑉2 , 𝑇2 ) Se hace la prueba de rechazo de datos, y ya que
todos los valores cumplen el criterio QExp<QC
2 a 3 (𝑃2 , 𝑉2 , 𝑇2 ) → (𝑃3 , 𝑉2 , 𝑇1 ) entonces se conservan todos los tiempos
1 a 3 (𝑃1 , 𝑉1 , 𝑇1 ) → (𝑃3 , 𝑉2 , 𝑇1 ) tomados para una significancia del 5%. Se
trabaja con el promedio para realizar los cálculos
For the perfect gases, from 1 to 2 we have: posteriores:
𝑃1 𝑉1 𝑃2 𝑉2
= (18) Air
𝑇1 𝑇2
Test t(s) Qexp
Regrouping and replacing equation 18 in 17:
1 5,36 0,02970297
𝑃2 𝑉2 𝑉2 2 5,39 0,02970297
𝐶𝑉 𝑙𝑛 = −𝑅𝑙𝑛
𝑃1 𝑉1 𝑉1 3 5,43 0,01980198
𝑃2 𝑉2 𝑉2 4 5,45 0,01980198
𝐶𝑉 𝑙𝑛 + 𝐶𝑉 𝑙𝑛 = −𝑅𝑙𝑛 5 5,52 0,02970297
𝑃1 𝑉1 𝑉1
6 5,55 0,02970297
𝐶𝑉 + 𝑅 𝑉2 𝑃1
𝑙𝑛 = 𝑙𝑛 7 5,6325 0,081683168
𝐶𝑉 𝑉1 𝑃2
8 5,9 0,066831683
𝐶𝑃 𝑉2 𝑃1 9 5,9675 0,066831683
𝑙𝑛 = 𝑙𝑛 (19)
𝐶𝑉 𝑉1 𝑃2 10 6,37 0,398514851
Fort he perfect gases, from 1 to 3 we have: Average (s) 5,657
Tabla 1. Resultados prueba Q para cada ensayo de
𝑃1 𝑉1 𝑃3 𝑉2 tiempo al realizar 10 oscilaciones con aire.
= (20)
𝑇1 𝑇1
CO2
Regrouping and replacing equation 18 en 19:
Test t(s) Qexp
𝐶𝑃 𝑃1 𝑃1 1 5,34 0,095238095
𝑙𝑛 = 𝑙𝑛 (21)
𝐶𝑉 𝑃3 𝑃2 2 5,42 0,095238095
Solving for the adiabatic coefficient: 3 5,5 0
4 5,5 0
𝑙𝑛𝑃1 − 𝑙𝑛𝑃2 5 5,53 0,035714286
𝛾= (22)
𝑙𝑛𝑃1 − 𝑙𝑛𝑃3 6 5,76 0,273809524
6. CALCULATIONS SAMPLE 7 5,99 0,047619048
8 6,03 0,023809524
Ruchardt’s method of self-sustained
oscillations 9 6,05 0,023809524
10 6,18 0,154761905
The following measures of experimental Average (s) 5,7300
assembly are known: Tabla 2. Resultados prueba Q para cada ensayo de
tiempo al realizar 10 oscilaciones con CO2.
dsphere(m) 0,0123
Cross sectional área obtained by:
msphere(Kg) 0,0075
𝜋
htube(m) 0,1381 𝐴= ∗ 𝐷2
4
Patm(Pa) 74660,52632 𝜋
2 𝐴= ∗ (0,0123𝑚)2
g(m/s ) 9,8 4
Vflask(m3) 0,000618 𝐴 = 0,00012𝑚2
The total volumen:
 𝜋 ∗ (0,0123𝑚)2 CO2
𝑉 = 6,18 ∗ 10−4 𝑚3 +
4
First process Second process Third process
∗ 0,1381 𝑚 = 6,34 ∗ 10−4 𝑚 3
Test h(cm) T(°C) h(cm) T(°C) h(cm) T(°C)
The pressure exerted on the sphere by the action
1 0,1 17 20,2 17 17,5 16
of the gas will be:
2 0,5 17 15,5 18 13,2 17
𝑚𝑔
𝑃 = 𝑃𝑎𝑡𝑚 + 3 1,1 17 22,6 19 19 18
𝐴
0,0075534𝑘𝑔 ∗ 9,81𝑠𝑚2
𝑃 = 74660,53𝑃𝑎 + We proceed to calculate the pressures
𝜋
4
(0,0123𝑚)2 𝑃1 , 𝑃2 𝑎𝑛𝑑 𝑃3 according to the following
formula, where 𝑃𝑎𝑡𝑚 is the atmospheric
𝑃 = 75279,09 𝑃𝑎
pressure, in the initial height (49,2cm):
With the average time the oscillation period is
𝑃𝑖 = 𝑃𝑎𝑡𝑚 + 𝜌𝐻20 ∗ 𝑔 ∗ (ℎ𝑎𝑡𝑚 − ℎ𝑖 )
obtained, to finally calculate the adiabatic
expansion coefficient (γ): Here ℎi is the height indicated by the water
gauge at the pressure 𝑃𝑖 , and we proceed to
For the air:
find:
5,657𝑠
𝜏= = 0,5657 𝑠 Air
10
4𝜋 2 ∗ 7,5 ∗ 10−3 𝐾𝑔 ∗ 6,34 ∗ 10−4 𝑚3 Test P1(Pa) P2(Pa) P3(Pa) γ
𝛾=
75293,4 𝑃𝑎 ∗ (1,19 ∗ 10−4 𝑚2 )2 ∗ (0,5657𝑠)2 1 79144,887 76951,662 77294,354 1,1878099
2 79409,249 76187,95 76618,762 1,1576242
𝛾 = 0,5523
3 79262,381 77264,98 77548,924 1,1678458
For the CO2:
5,7300𝑠 CO2
𝜏= = 0,573 𝑠
10
Ensayo P1(Pa) P2(Pa) P3(Pa) γ
4𝜋 2 ∗ 7,5 ∗ 10−3 𝐾𝑔 ∗ 6,34 ∗ 10−4 𝑚3 1 79467,996 77499,969 77764,33 1,1571333
𝛾=
75293,4 𝑃𝑎 ∗ (1,19 ∗ 10−4 𝑚2 )2 ∗ (0,573𝑠)2
2 79428,831 77960,154 78185,351 1,1828021
𝛾 = 0,5383 3 79370,084 77264,98 77617,463 1,2038427
Clement & Desormes’ adiabatic expansion
method Here the adiabatic expansion coefficient (γ)
were determined by the formula:
The following data are obtained from the
heights indicated by the pressure gauge in the 𝑙𝑛𝑃1 − 𝑙𝑛𝑃2
three states: 𝛾=
𝑙𝑛𝑃1 − 𝑙𝑛𝑃3

Air 7. RESULTADOS
First process Second process Third process Se puede realizar una comparación de exactitud
Test h(cm) T(°C) h(cm) T(°C) h(cm) T(°C) entre estos dos métodos a partir del error
1 3,4 16 25,8 16 22,3 16 relativo, donde se toma como datos teóricos los
2 0,7 16 33,6 17 29,2 16 siguientes valores:
3 2,2 17 22,6 18 19,7 17 𝛾𝐴𝑖𝑟𝑒 = 1,401
𝛾𝐶𝑂2 = 1,3

Ruchardt’s method of self-sustained

oscillations
Se obtuvo el siguiente valor de coeficiente
adiabático al trabajar con el tiempo promedio
de los ensayos.
𝛾𝐴𝑖𝑟𝑒 = 0,502
0,502 − 1,401
%𝐸𝑟𝑟𝑜r = | | ∗ 100 = 64,17%
1,401

𝛾𝐶𝑂2 = 0,573
0,573 − 1,3
%𝐸𝑟𝑟𝑜r = | | ∗ 100 = 55,92%
1,3

Clement & Desormes’ adiabatic expansion

method
Se realizó el cálculo del coeficiente adiabático
para cada ensayo en donde hay diferentes
valores de presiones, y se compara con el valor
teórico, obteniéndose para cada gas:

Aire
Ensayo γ %Error
1 1,18780988 15,22%
2 1,15762416 17,37%
3 1,16784583 16,64%

CO2
Ensayo γ %Error
1 1,15713328 10,99%
2 1,18280211 9,02%
3 1,20384271 7,40%

8. ANÁLISIS DE RESULTADOS
9. REFERENCES
[1] J. M. Smith, et al. Introducción a la
termodinámica en Ingeniería Química, 7th Ed.
McGraw-Hill, 2007.
[2] K. Wark Jr. Termodinámica, 5th Ed,
McGraw-Hill, 1999.