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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
makes use of thermodynamic laws and perfect
To determine the relation of specific heats of gases to calculate the ratio of specific heats of
some substances, it is necessary to understand the gas.
the thermodynamic system for each method. In
the present practice the methods that are 2. OBJECTIVES
described to obtain these coefficients are
related to some basic concepts of physics and 1. General objective
laws of thermodynamics.
Determine the relation between specific heats
under constant pressure and volume for Carbon
The Rüchardt method uses the thrust generated
Dioxide (CO2) and Air using the methods of
by a gas to a sphere of known mass that is
Clément - Désormes and Rüchardt
introduced into a tube where it is assumed to be
in the absence of friction. By means of a 2. Specific objectives
balance of forces on the sphere, and the
mathematical development that integrates  Compare the results obtained in both
concepts of mechanics (waves) with methods and verify them with the data
thermodynamics, it is possible to determine the reported in the literature.
adiabatic coefficient of a gas.  Perform a statistical analysis of the data
obtained in the experiments.
The Clément - Désormes method produces an  Compare the observed phenomena
adiabatic compression (or expansion) of the with an event of everyday life using the
gas, which causes its intensive properties P, V, concepts of thermodynamic laws and
T to undergo changes when passing from one basic physical laws that are going to be
state to another. By means of the analogy of the applied in the experiment.
experiment with respect to a piston begins the

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. The adiabatic index is related to 𝐶𝑉 𝑎𝑛𝑑 𝐶𝑃 through the following expressions Now. THEORETICAL FRAMEWORK 𝑇2 Heat capacity 𝑄 = 𝑛 𝛥𝐻 = 𝑛 ∫ 𝐶𝑃 𝑑𝑇 𝑇1 Generally. 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. V and simple way to a process under constant pressure T. but at constant pressure. 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]. To determine This heat capacity is related in a particularly the adiabatic equations as functions of P. like Q. 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. Many common diatomic gases have an 𝛥𝑈 = ∫ 𝐶𝑉 𝑑𝑇 adiabatic index of approximately 1.4 at ambient 𝑇1 temperature. when integrating we obtain: . the energy balance is written: 3. For a mechanically reversible process at constant pressure. it is Although this definition does not refer strictly denoted by the expression [2]: to any process. to be 𝑑ℎ = 𝑑𝑢 + 𝑅𝑑𝑇 process-dependent quantities rather than a state function. Sometimes it is also known as isentropic 𝛿𝑇 expansion factor or specific heat ratio. relation can be written: Mathematically. the heat capacity of a stated ℎ = 𝑢 + 𝑃𝑣 quantity of substance can be expressed as 𝐶 = 𝑑𝑄/𝑑𝑇. 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.67. 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 . 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. the difficulty assosiated with this ℎ = 𝑢 + 𝑅𝑇 expression is that it causes C.

a sphere is placed inside a tube and a valve is opened to allow the passage of the gas from the bottom. 4. 𝑇3 ). 𝑇2 𝑉2 = ( )γ−1 𝑇1 𝑉1 Then applying equation of state. 𝑇1 ). To perform this. . letting out a quantity of matter. after stabilized pressure the first data pair will be taken (𝑃1 . then the second pair of data is taken (𝑃2 . 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. immediately the adiabatic expansion is made quickly.. 𝑇2 ) and again it will rise until it stabilizes again (𝑃3 . 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. 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. 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.

5. in order to use the force equation it is assumed that the movement occurs in the absence of friction.  Analytical weighing scale  Digital cronometer 5. 4. made in glass with an accuracy of one tenth of mL. It can be written: Equipment 𝐹 = 𝑃𝐴 (1) Since the area is constant. also will be used:  CO2 bulb with a high pressure valve. Metalic sphere 7. and that the oscillations are symmetric with respect to the hole. Matrass flask (1000ml) 8. and a supply valve.5 cm height (equipped with 2 gate Writing equation 5 in terms of height (𝑑𝑉 = valves and one ball valve). connected to a 𝑃(−𝛾)𝐴 burette of 49 ml as maximum height 𝑑𝑃 = 𝑑𝑥 (6) 𝑉 . then: 𝑃𝑉 𝛾 = 𝑘 (4) Figure 1: Equipment outline Replacing equation 4 in equation 3: 1. Glass tube 6. 3. Copper cylinder of 16 cm diameter and 𝑉 51. the restoring force is constant. CALCULATIONS Ruchardt’s method of self-sustained oscillations The oscillation performed by the sphere can be described as a harmonic movement. therefore. Gas supply to pressure gauge. Pressure gauge which consists of a 𝐴𝑑𝑥): cuvette in acrylic. Gas input Algonside this equipment. Thermometer 𝑃(−𝛾) 𝑑𝑃 = 𝑑𝑉 (5) 2. a low pressure valve. 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.

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. Transformations" and the period of oscillation is given by 𝑃(−𝛾)𝐴2 √| | . When the pressure decreases. 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. and because it is a 𝑅𝑇 method perfect gas (𝑃 = ). where 1 corresponds to the first conditions.Replacing equation 6 in equation 2: through a line of constant enthalpy to a different isotherm. the volume of the cylinder has already 𝐹 𝑥 𝑃(−𝛾)𝐴2 been filled and the pressure will stabilize. 𝑇2 𝑉2 𝐶𝑉 𝑙𝑛 = −𝑅𝑙𝑛 (17) that is. 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. the expression leads to: 𝑉 A balance will be made making the analogy 𝑅𝑇 with a cylinder-piston system. ∫ 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. 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. where the pressure descends . once the tank has been filled. The passage Solving for the integral expression: from point 2 to 3 is the increase in isochoric pressure. 𝐶𝑉 ∫ = −𝑅 ∫ 𝑇1 𝑇 𝑉1 𝑉 The process can be plotted in a diagram of P vs V. volume "Adiabatic The movement made by the sphere is harmonic. The 𝑇1 𝑉1 passage from point 1 to 2 is the adiabatic From figure 2 can be concluded: expansion. the 𝑇2 𝑉2 𝑑𝑇 𝑑𝑉 effects of irreversibility are ignored. 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.

095238095 Solving for the adiabatic coefficient: 3 5.52 0.01980198 𝑃2 𝑉2 𝑉2 4 5.1 a 2 (𝑃1 .02970297 𝐶𝑉 + 𝑅 𝑉2 𝑃1 𝑙𝑛 = 𝑙𝑛 7 5.0123 Cross sectional área obtained by: msphere(Kg) 0.7300 assembly are known: Tabla 2.066831683 𝐶𝑃 𝑉2 𝑃1 9 5. Se trabaja con el promedio para realizar los cálculos For the perfect gases.52632 𝜋 2 𝐴= ∗ (0.398514851 Fort he perfect gases.34 0. 𝑉2 .55 0. from 1 to 3 we have: Average (s) 5.02970297 𝑃1 𝑉1 𝑉1 6 5.37 0.42 0.43 0.095238095 𝑙𝑛 = 𝑙𝑛 (21) 𝐶𝑉 𝑃3 𝑃2 2 5. 𝑇1 ) entonces se conservan todos los tiempos 1 a 3 (𝑃1 . 𝑇1 ) tomados para una significancia del 5%. 𝑉1 .18 0.1381 𝐴= ∗ 𝐷2 4 Patm(Pa) 74660. dsphere(m) 0. 𝑉2 .36 0.035714286 𝛾= (22) 𝑙𝑛𝑃1 − 𝑙𝑛𝑃3 6 5.9 0.0123𝑚)2 g(m/s ) 9. 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 5.8 4 Vflask(m3) 0.76 0.6325 0.657 Tabla 1.00012𝑚2 The total volumen: .023809524 10 6. CALCULATIONS SAMPLE 7 5.45 0.03 0.081683168 𝐶𝑉 𝑉1 𝑃2 8 5.99 0. 𝑉2 . 𝑇2 ) → (𝑃3 .01980198 𝐶𝑉 𝑙𝑛 + 𝐶𝑉 𝑙𝑛 = −𝑅𝑙𝑛 5 5. 𝑉1 .023809524 Ruchardt’s method of self-sustained oscillations 9 6. 𝑇2 ) Se hace la prueba de rechazo de datos.05 0. 𝑇1 ) → (𝑃3 .53 0.000618 𝐴 = 0.066831683 𝑙𝑛 = 𝑙𝑛 (19) 𝐶𝑉 𝑉1 𝑃2 10 6. y ya que todos los valores cumplen el criterio QExp<QC 2 a 3 (𝑃2 .39 0.154761905 The following measures of experimental Average (s) 5.047619048 8 6.0075 𝜋 htube(m) 0.02970297 𝑃2 𝑉2 𝑉2 2 5.5 0 𝑙𝑛𝑃1 − 𝑙𝑛𝑃2 5 5. = (20) 𝑇1 𝑇1 CO2 Regrouping and replacing equation 18 en 19: Test t(s) Qexp 𝐶𝑃 𝑃1 𝑃1 1 5. Resultados prueba Q para cada ensayo de 𝑃1 𝑉1 𝑃3 𝑉2 tiempo al realizar 10 oscilaciones con aire. 𝑉2 . 𝑇1 ) → (𝑃2 .02970297 𝐶𝑉 𝑙𝑛 = −𝑅𝑙𝑛 𝑃1 𝑉1 𝑉1 3 5.273809524 6. Resultados prueba Q para cada ensayo de tiempo al realizar 10 oscilaciones con CO2.9675 0.5 0 4 5.

5 17 15. 𝑃2 𝑎𝑛𝑑 𝑃3 according to the following formula. 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 3.381 77264.573 𝑠 10 Ensayo P1(Pa) P2(Pa) P3(Pa) γ 4𝜋 2 ∗ 7.354 1.657𝑠 𝜏= = 0.6 18 19.5657 𝑠 Air 10 4𝜋 2 ∗ 7.2038427 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 7.5 ∗ 10−3 𝐾𝑔 ∗ 6.5 18 13.1878099 2 79409. where 𝑃𝑎𝑡𝑚 is the atmospheric 𝑃 = 75279. and we proceed to For the air: find: 5.19 ∗ 10−4 𝑚2 )2 ∗ (0.1 17 22.0123𝑚)2 𝑃1 .5383 3 79370.6 19 19 18 𝐴 0.2 17 𝑚𝑔 𝑃 = 𝑃𝑎𝑡𝑚 + 3 1.98 77548.4 𝑃𝑎 ∗ (1.34 ∗ 10−4 𝑚3 1 79467.95 76618.924 1.34 ∗ 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 0.3 16 relativo.5657𝑠)2 1 79144.249 76187.53𝑃𝑎 + We proceed to calculate the pressures 𝜋 4 (0.351 1.1381 𝑚 = 6. to finally calculate the adiabatic expansion coefficient (γ): Here ℎi is the height indicated by the water gauge at the pressure 𝑃𝑖 .0075534𝑘𝑔 ∗ 9.6 17 29.81𝑠𝑚2 𝑃 = 74660.4 𝑃𝑎 ∗ (1.0123𝑚)2 CO2 𝑉 = 6.573𝑠)2 2 79428.18 ∗ 10−4 𝑚3 + 4 First process Second process Third process ∗ 0.831 77960.3 Ruchardt’s method of self-sustained oscillations .5 ∗ 10−3 𝐾𝑔 ∗ 6.7 16 33.34 ∗ 10−4 𝑚3 Test P1(Pa) P2(Pa) P3(Pa) γ 𝛾= 75293.463 1. 𝜋 ∗ (0.1576242 𝛾 = 0.154 78185.084 77264.8 16 22.7 17 𝛾𝐴𝑖𝑟𝑒 = 1.19 ∗ 10−4 𝑚2 )2 ∗ (0.662 77294.2 17 22.33 1.5523 3 79262.1 17 20.401 𝛾𝐶𝑂2 = 1.1828021 𝛾 = 0.4 16 25.762 1.1571333 𝛾= 75293.969 77764. donde se toma como datos teóricos los 2 0.09 𝑃𝑎 pressure.2cm): With the average time the oscillation period is 𝑃𝑖 = 𝑃𝑎𝑡𝑚 + 𝜌𝐻20 ∗ 𝑔 ∗ (ℎ𝑎𝑡𝑚 − ℎ𝑖 ) obtained.996 77499.2 17 17.7300𝑠 CO2 𝜏= = 0.2 16 siguientes valores: 3 2.1678458 For the CO2: 5. in the initial height (49.98 77617.5 16 of the gas will be: 2 0.887 76951.

𝛾𝐴𝑖𝑟𝑒 = 0. y se compara con el valor teórico.573 0. Termodinámica. [2] K. Introducción a la termodinámica en Ingeniería Química.37% 3 1.17% 1. .64% CO2 Ensayo γ %Error 1 1.Se obtuvo el siguiente valor de coeficiente adiabático al trabajar con el tiempo promedio de los ensayos. McGraw-Hill.15762416 17.3 Clement & Desormes’ adiabatic expansion method Se realizó el cálculo del coeficiente adiabático para cada ensayo en donde hay diferentes valores de presiones. Smith. 5th Ed.3 %𝐸𝑟𝑟𝑜r = | | ∗ 100 = 55. obteniéndose para cada gas: Aire Ensayo γ %Error 1 1.99% 2 1. ANÁLISIS DE RESULTADOS 9.40% 8. 1999. REFERENCES [1] J.20384271 7. 2007. et al.16784583 16.92% 1.502 0.15713328 10.18280211 9.401 𝛾𝐶𝑂2 = 0. 7th Ed.02% 3 1.18780988 15. M.502 − 1.573 − 1. Wark Jr.401 %𝐸𝑟𝑟𝑜r = | | ∗ 100 = 64. McGraw-Hill.22% 2 1.