Lab Experiments 194 KamalJeeth Instrumentation and Service Unit

Experiment-343

VERIFICATION OF CLAUSIUSCLAPEYRON EQUATION

Jeethendra Kumar P K and Ajeya PadmaJeeth
KamalJeeth Instrumentation & Service Unit, No-610, Tata Nagar, Bengaluru-560 092. INDIA.

Email:labexperiments@rediffmail.com

Abstract Using a 3-litre pressure cooker, pressure gauge (2kg/cm2) and a digital thermometer, the temperature and pressure variation at water steam interface are recorded. From the data the Clausius-Clapeyron equation is verified and specific enthalpy of vapourization is determined.

Introduction
The Clausius-Clapeyron equation is used to estimate the vapour pressure of pure liquids or solids. It relates the pressure and temperature at which two phases of a substance are in equilibrium. It allows one to determine and understand the shape and location of liquidvapour and solid- phase boundaries. It predicts the variation of pressure with temperature and how the boiling temperature varies with pressure. Water starts boiling at 1000C at which there is a phase change from liquid to vapour. The variation of pressure and temperature is given by Clausius-Clapeyron equation [1].

Enthalpy
When a liquid is heated to the evapouration temperature, the liquid evapourates changing its state from liquid to gas. The vapour further gets heated above the evapouration temperature and become super heated. The heat transferred to the substance to change its state from liquid to gas is known as latent heat of evapouration [2]. The most common liquid is water which changes its liquid state to steam at 100C. The water-steam system is a good example of a two phase system. The enthalpy (H) of a system is defined as the product of mass (m) of system and its specific enthalpy (h) as H =mh Where h is the enthalpy (kJ) m is the mass of the substance (kg) h is the specific enthalpy (kJ/kg) Specific enthalpy is a property of a liquid expressed as Vol-11, No-3, Sept.-2011 1

Lab Experiments 195 KamalJeeth Instrumentation and Service Unit h = u+pv where u is the internal energy (kJ/kg) p is the absolute pressure (N/m2) v is the specific volume (m3/kg) 2

Specific enthalpy of saturated water and saturated steam

The specific enthalpy of saturated water (hf) depends on its pressure in accordance with Equation-2. For saturated water at normal pressure (1 atmosphere), hf =419kJ/kg. Similarly, the specific enthalpy of saturated steam is hg =2676kJ/kg. We have used two subscripts to differentiate the two different systems; the subscript f is used for saturated liquid (water) and subscript g refers to saturated vapour (steam). Therefore, the specific enthalpy of evapourations is the difference between these two enthalpies. Specific enthalpy of evapourations is given by Specific enthalpy of evapouration hgf = hg-hf For water hgf = hg-hf =2676-419=2257kJ/kg, at one atmospheric pressure. 3

Enthalpy of vapourizations
Enthalpy of vapourization is defined as the change in enthalpy required to completely change the state of one mole of substance between the liquid and the gaseous state. There are various other types of enthalpy used in chemistry, such as enthalpy of fusion, enthalpy of sublimation, lattice enthalpy etc.

Clausius-Clapeyron equation
T P

T T-dT

P P-dP

Sf

Sg

Vf

Vg

Figure-1: Carnot cycle devised to test the validity of two laws of thermodynamics For a two phase-system undergoing change in phase, one can apply Carnot engine between temperatures T and (TdT), from which one can derive an important relation known as the Clausius-Clapeyron equation, which gives the slope of the vapour pressure curve. One can then construct the vapour pressure curve for various substances and compare the measured

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Lab Experiments 196 KamalJeeth Instrumentation and Service Unit slope of the Clausius-Clapeyron equation with it. This can be viewed as an experimental proof of the general validity of the first and second laws of thermodynamics [3]. Considering the infinitesimal Carnot cycle abcd shown in Figure-1, heat is absorbed between the states a and b. For vapourizing an arbitrary amount of mass m, the amount of heat required is given by Q=mhgf where Q is the amount of heat energy hfg is the enthalpy of vapourizations m is the mass This is the heat supplied to the system containing mass m. From the first and second laws of thermodynamics, the thermal efficiency of the Carnot cycle can be written as = W Q Q T T = = Q Q T 4

Hence, for the infinitesimal cycle considered above

()

The work along bc and da, nearly cancel out, with the result that the net amount of work done is the difference between the work along ab and cd, and dW can be viewed as the area enclosed by the rectangle abcd: dW = pm(vg-vf) (p-dp)m(vg-vf) =m( vg-vf)dp Substituting Equations-1 and 3 in Equation-2, one obtains mv v dp dT = mh T Rearranging the terms yields the Clausius-Clapeyron equation, which defines the slope of the vapour pressure curve

The quantities appearing in Equation-7 are experimentally measurable quantities from the first principles (employing the first and second laws of thermodynamics) In order to plot the Clausius-Clapeyron relation and for comparing it against the experimentally measured vapour pressure curves, we need to integrate Equation-7. For this, the heat of vapourization and the specific volumes must be known functions of temperature.

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Lab Experiments 197 KamalJeeth Instrumentation and Service Unit This is an important problem in physical chemistry but it will not be pursued here further except mentioning that 1. Variation in the heat of vapourization can be neglected. 2. The phase is assumed to behave as an ideal gas, and 3. The specific volume of the liquid is small compared to that of the phase hgf const, vf vg

The integration of Equation-7 can be readily carried out now. Making these approximations, the Clausius-Clapeyron equation becomes

The resulting expression is

+ ln (C). In p = -

10

This equation represents a straight line in ln(P) versus 1/T with slope = hfg/R and the Yintercept as ln(C). The quantity h /R; is directly related to the heat of vapourization. Equation-10 is known as Clausius-Clapeyron equation. It connects temperature and pressure at the interface of a liquid and gaseous phase in this experiment.

Apparatus used
Figure-2 shows the experimental set-up used. It consists of a 3 liter pressure cooker fitted with a pressure gauge (2Kg/cm2), a digital thermometer 0-360C, and a hot plate.

Figure-2: Experimental set-up for verification of Clausius-Clapeyron equation

Experimental procedure
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Lab Experiments 198 KamalJeeth Instrumentation and Service Unit 1. The volume of the pressure cooker is noted as 3 litres. 2. The pressure cooker fitted with a pressure gauge is filled with water up to two-third of its volume. 3. The lid is closed and placed on hot plate which is switched on. 4. The digital thermometer is now placed in its position and the room temperature is noted as 28C. 5. The rise in temperature with time is noticed by the thermometer. When temperature reaches 90C, both the temperature and pressure gauges are monitored carefully. Above 100C, the pressure in the gauge starts increasing. 6. The temperature and pressure are recorded in Table-1, at suitable intervals of pressure until the pressure in the cooker is released through the whistle of the cooker. The readings obtained are tabulated in Table-1. Table-1 Temperature Pressure C K Kg/cm2 Pascal ln(P) (1/T)x10-3 4 X10 105.5 378.5 0.20 1.96 9.88 2.64 106.5 379.5 0.25 2.45 10.10 2.63 108.0 381.0 0.30 2.94 10.28 2.62 110.5 383.5 0.40 3.92 10.57 2.60 113.0 386.0 0.50 4.90 10.80 2.59 115.0 388.0 0.60 5.88 10.98 2.57 117.5 390.5 0.75 7.35 11.20 2.56 119.0 392.0 0.80 7.84 11.27 2.55 120.5 393.5 0.90 8.82 11.38 2.54 121.5 394.5 0.95 9.31 11.44 2.53 Pressure and temperature variation of water 7. A graph is drawn taking (ln P) on Y-axis and (1/T) along X-axis as shown in Figure3. From the straight line graph, the slope is calculated as Slope = (.).= R=8.3144 hgf = 118777.1 J/mole = 118.777kJ/mole The molecular weight of water is 18, hence hgf =118.777 x 18 kJ/kg =2137.98 kJ/kg; hgf =2138 kJ/kg.
.. . .

= 14285.7=

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Lab Experiments 199 KamalJeeth Instrumentation and Service Unit

11.8 11.6 11.4 11.2 11 ln(P) 10.8 10.6 10.4 10.2 10 9.8 9.6 2.52 2.54 2.56 2.58 2.6 2.62 2.64 2.66 1/T(K-1x10-3)

Figure-3: The Clausius-Clapeyron straight line obtained for water

Results
Specific enthalpy of evapouration of water hgf 2257kJ/kg at one atmospheric pressure.
=

2138kJ/kg; its standard value being

Discussion
During the experiment temperature and pressure variation at water-steam interface are recorded. From the data obtained the Clausius-Clapeyron equation is verified and specific enthalpy of vapourization is determined. In the experiment, the pressure in the pressure cooker varied from 2 to 9 Pascal (or N/m2).

References:
[1] Rudolf Julius Emmanuel Clausius http://www.gap-system.org/~history/Biographies/Clausius.html http://www.engineeringtoolbox.com/steam--enthalpy-d The Clausius-Clapeyron Equation (application of 1st and 2nd laws of thermodynamics) http://mit.edu/16.unified/www/FALL/thermodynamics/notes/node64.html

[2] [3]

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