Experiment 4 UP204 Thermal and Physics of Material

Clausius - Clapeyron Equation and Phase Transition

Introduction: In this lab session there are two experiments to study the phase transition of substance
from liquid to vapor state. The first experiment, the variation of vapor pressure of water with
temperature is studied and compared to Clausius Clapeyron equation. In the second experiment, the
phase transition of SF6 is observed at critical point to determine its critical temperature Tc.

Theory:

a) Clausius- Clapeyron equation: This applies to any first order phase change or transition that
occurs at constant temperature (T) and pressure (P). It is given by the equation

dP H f  Hi
 .
dT T (V f  V i )

( H f  H i ) is the difference in molar

enthalpies at a fixed pressure. It is also
known as molar latent heat.

The above equation can be derived

by studying Carnot engine, which operates
in a two-phase hydrostatic system shown in
the adjacent figure. Consider a Carnot
engine operating in the two-phase region Liquid vapor region T
of the liquid-vapor, as illustrated.
T- dT
The processes a to b and c to d is
isothermal while processes b to c and
d to a is adiabatic. During a to b the liquid
gets converted to vapor at pressure P and
temperature T and during c to d, vapor gets
converted to liquid at pressure P-dP at the temperature T-dT.

The efficiency of Carnot engine is given by

W T  dT dT
  1  .
QH T T

Where W is the work done and QH is the heat absorbed.

The work done by the system during the Carnot cycle is the area (dP)(n∆V). Here ∆V is the change of
molar volume at temperature T. The heat absorbed by the system during the isothermal process a to b
is (n∆h). Thus within the two phase region
Experiment 4 UP204 Thermal and Physics of Material

dP(nV ) dT

nh T
dP h

And this simplifies to dT T V

The equation can also be derived using change in entropy or Gibbs function which is mathematically
more rigorous.

In case of water, the critical temperature is 647.067 K and in the experiment the temperature range is
much below this (ice point to boiling point at atmospheric pressure), the equation can be simplified
using the following approximations.

(i) When liquid vaporizes, the volume of the vapor is larger than that of liquid. Hence
V  (Vg  VL )  Vg
(ii) Using Ideal gas equation PVg  nRT , the Clausius Clapeyron equation can be written as
dP Ph
 2
dT T nR

Thus the expression for pressure as a function of temperature can be written as

P2 H  1 1 
ln    
P1 R  T1 T2 

b) Phase transition: The real gas behaves differently

from ideal gas when it approaches critical
temperature (below which gas changes to liquid
phase). The variation of Pressure with volume for such
a real gas is as shown in the adjacent figure. The
curves represent isotherms for different
temperatures. The shaded region indicates a region
where liquid and vapor coexist. To the left of this
region, substance exists as liquid and on the right of
region it is as a vapor. It can be observed that the
horizontal lines in the shaded region are the
vaporization lines representing equilibrium between
liquid and vapor. As temperature increases this line becomes shorter and finally vanishes at a
specific temperature called critical temperature (TC). The point that represents the limit of
vaporization is called critical point. The pressure and volume at this point are called Critical
pressure (PC) and Critical Volume (VC). Above the critical point, the isotherms are continuous
curves which are hyperbolas at higher temperatures similar to an ideal gas.
At critical point, there is no distinction between liquid and vapor and hence the meniscus
disappears. When critical point is approached the following observation can be made
Experiment 4 UP204 Thermal and Physics of Material

(i) The density of vapor and liquid are identical and hence there are completely mixed.
Befor the crtical point, liquid density is more and hence gravitate to the bottom with a
miniscus and the vapor is above it.
(ii) As the mixture approaches the critical point, the light scattering within the container
reaches an extremely high level. This phenomenon is called the critical opalescence,
and is caused by variations in density that increase significantly close to the critical
point because the compressibility is greater and the resistance to density changes is
low. Short-wavelength light is scattered, while long-wavelength light continues in it
path.

However, In case of water, the critical values are very high and hence it is difficult to observe it.
At ordinary temperature and pressure liquid and vapor co exists. In the experiment phase
transition at critical point for Sulfur Hexa fluoride is studied since its critical point can be easily
achieved. The critical values for SF6 are
Temperature: 318.7K; Pressure: 37.6 bar; Molar volume: 200cm3mol-1.
In the experimental demonstration some of these effects are can be observed.

Procedure:
(a) Clausius Clapeyron equation:
1) The experimental setup is as shown in the following figure below. A round bottom flask
containing distilled water is placed in a water bath with temperature regulator. The flask
is attached to a pressure sensor and a temperature sensor which can be interfaced to
the laptop.

Pressure sensor

Water bath

Round bottom flask

2) The volume of the flask and rubber tube (Vd) should be measured accurately. This can
be done by estimating the volume of water required to fill it up.
3) Fill the round bottom flask with distilled water to half its volume (Vw). Estimate the
volume available for water vapor and air (V0). Close the flask with glass tube which is
connected to a pressure sensor. Place the flask in the water bath as shown in the figure
Experiment 4 UP204 Thermal and Physics of Material

above. Close the tap of the glass connector. Place the temperature sensor in the water
bath.
4) The readings of the sensor can be read out and plotted using Data studio software.
5) Temperature of the water bath can be raised to a maximum temperature of 80 0C. Study
the variation of pressure with temperature between 800C to 00C. Use ice cubes to cool
the water bath below room temperature.
6) In order to verify Clausius Clapeyron equation, vapor pressure of water is required. The
pressure sensor gives the net pressure due to air and water vapor in the flask and the air
in the rubber tube. The pressure due to air in the flask and tube at a given temperature
can be estimated using ideal gas equations and pressure (P0) recorded at 00C. The
amount of vapor at 00C is negligible hence the pressure is only due to air. Let the volume
of the flask available for air and vapor be Va and that in the tube be Vd. If P0 is the
pressure at 273K , the pressure of air at other temperature can be obtained using

 Va V 
  d 
Pa  P0  273 300  .
 Va Vd 
  
 T 300 
Here the temperature of air in the tube is assumed to be at room temperature.
7) Estimate the vapor pressure at different temperature (P-Pa). Plot an appropriate graph
to verify Clausius Clapeyron equation and determine the latent heat of vaporization.

Phase transition:

1) The experimental set up is as shown in the figure below.

2) The temperature of the pressure chamber can be increased by
passing steam generated in the steam chamber.
3) The pressure chamber is provided with a glass window.
4) Liquefied SF6 filled in the pressure chamber is provided.
5) Place a thermometer in the hole provided for it. With the help of a
bright light source the liquid in the pressure chamber can be seen
directly or by projecting it on a screen.
6) As temperature increases observe the changes in liquid particularly
when the temperature reaches critical temperature.
7) Report your observations.
Experiment 4 UP204 Thermal and Physics of Material

Pre lab question:

1) Draw the Pressure as a function of temperature (Phase diagram) for water and SF6 indicating
triple point and critical point.
2) What happens to boiling point temperature of water when pressure increases?
3) What happens to melting point of ice when pressure increases?

Lab report should consists of

1) Answer to pre-lab questions.
2) Graph for net Pressure as a function of temperature.
3) Graph for Vapor Pressure as a function of temperature.
4) Appropriate graph to obtain molar latent heat of vaporization.
5) Uncertainty analysis 4) Results and discussions.