Topic 1: Relationship between pressure and temperature

(Clausius-Clapeyron Equation)

1.0 Introduction

The temperature, at which equilibrium occurs at a given pressure, is called the Saturation
Temperature. Saturation temperature means boiling point. The saturation temperature is the
temperature for a corresponding saturation pressure at which the liquid boils its vapour phase.
The liquid can be said to be saturated with thermal energy.

Atmospheric pressure is the pressure at any given point in the Earth’s atmosphere. Gauge
pressure is the pressure relative to the local atmospheric or ambient pressure.

The idea of ideal gas is purely hypothetical and such gas does not exist in the physical
universe. However, the concepts of ideal gas are a tool to calculate satisfactory approximate
solutions. The explanation for why it does not exist in the real world is in the definition itself.
The ideal gas composed of molecules with no size, it's not possible. Gas molecules are in
random motion and they will interact with each other. Similarly all the collisions are not
elastic collisions. There are in-elastic collisions and there by loss of energy. Hence in the real
world we are approximating real gases into a ideal gas to get satisfactory result. It is a
scientific way of approach to solve problems in a simple way. Therefore, a few modifications
on the ideal gas equation of state allow its application in the properties of real gas. Scientific

way of approach to solve problems in a simple way. Therefore, a few modifications on the
ideal gas equation of state allow its application in the properties of real gas.

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 liquid
vapour and solid- phase boundaries. It predicts the variation of pressure with temperature and
how the boiling temperature varies with pressure.

The Marcet Boiler is used to investigate the relationship between the pressure and
temperature of saturated steam in equilibrium with water at all temperature levels between
the atmospheric pressure and 10 bars. The experimental slope (dP/dT)SAT obtained is
compared to the theoretical value determined through calculation from the steam table.
Clausius-Clapeyron equation :

𝐷𝑃 𝑇𝑣𝑔
= ,
𝐷𝑇 ℎ𝑓𝑔

𝐷𝑃 ℎ𝑓 −ℎ𝑔
= ,
𝐷𝑇 𝑇(𝑉𝑓 −𝑉𝑔 )

𝐷𝑃 ℎ𝑓𝑔
=
𝐷𝑇 𝑇𝑣𝑔

∴ 𝑣𝑔 ≫ 𝑣𝑓

∴ ℎ𝑓 + ℎ𝑓𝑔 = ℎ𝑔 ,

Then, ℎ𝑓𝑔 = ℎ𝑔 − ℎ𝑓

∴ vf = specific volume of saturated liquid

vg = specific volume of saturated vapor
hf = enthalpy of saturated liquid
hg = enthalpy of saturated vapor
hfg = latent heat of vaporization

1.1 Problem Statement

People created the concept of an Ideal gas as an approximation that helps us model and
predict the behaviour of real gases. Therefore, there are some assumption:

1) Gases are made up of molecules which are in constant random motion in straight lines.

2) The molecules behave as rigid spheres.

3) Pressure is due to collisions between the molecules and the walls of the container.

4) All collisions, both between the molecules themselves, and between the molecules and the
walls of the container, are perfectly elastic. (That means that there is no loss of kinetic energy
during the collision.)

5) The temperature of the gas is proportional to the average kinetic energy of the molecules.

An ideal gas is a gas in which the molecules that make up the gas have no size, never collide
or otherwise interact with each other, and if they hit the walls of the container they're held
inside, they rebound off perfectly without having lost any of their speed or energy.
1.2 Objective

The main goal of this experiment is to obtain a balance relationship between temperature and
pressure of saturated steam for water at all pressure levels between atmospheric pressure and
6.0 bars (87.0226 lb/in2). Then, the experimental value for the slope of the graph (dP/dT)SAT
is compared to the theoretical value found in the steam table. Besides, learn how to use
Marcet Boiler.

1.3 Scope

Our scope for this experiment is to relate the pressure and temperature by using water for test.
When energy is added within water, the increasing of activities among the molecules caused
the increase in the number of molecule escape from the surface until an equilibrium state is
reached. The state of equilibrium depends on the pressure between the water surface and
steam. The lower the pressure, the easier the molecules leaving the water surface and thus
less energy is required to achieve the state of equilibrium (boiling point). The temperature
where equilibrium occurs at a given pressure level is called saturated temperature. The
pressure where equilibrium occurs at a given temperature is called saturated pressure.This
situation which relate to Clapeyron equation that involve the latent heat (heat of
transformation) of vaporization or condensation to the rate of change of vapour pressure with
temperature.The maximum pressure required for the experiment is 6.0 bar for the pressure
gauge meanwhile 7.0 bar for the absolute pressure and the minimum pressure required for the
experiment is 0.5 bar for pressure gauge and 1.0 for the absolute pressure.

1.4 Learning outcome

At the end of this experiment, students will be able to

1. Determine the temperature of the saturated steam at certain pressure.

2. Demonstrate the vapour pressure curve.

3. Prove the Clapeyron equation.

4. Understand the concept of Marcet boiler systems.

5. Produce good technical report according to the required standard.

2.0 Literature Review

Pure Substance

A substance that has a fixed chemical composition throughout is called a pure substance.
Water, nitrogen, helium, and a carbon dioxide, for example are all pure substance. A pure
substance does have to be at a single chemical element or compound,

The T-v Diagram

Figure 2.1 T-v diagram of pure substance

The phase change process of water at 1 atm pressure was describes in detail and plotted on a
T-v diagram.

The saturated liquid states can be connected by a line called the saturated liquid line and
saturated vapor states can be connected by another line called the saturated vapor line.

These two lines meet at the critical point, forming a dome as shown in figure 2.1, All the
compressed liquid state are located in the region to the left of the saturated liquid, called
compressed liquid region. All the superheated vapor region are located on the right side of
saturated vapor line, called superheated vapor region. In these two region, the substance exist
in a single phase, a liquid or a vapor .Meanwhile, there are a place where both liquid and
vapor coexist, it is located under the dome called saturated liquid vapor mixture region.
P-v Diagram

Figure 2.2 : P-v Diagram of pure substance

The general shape of P-v diagram of pure substance are similar to T-v diagram but T line in
on this diagram have a downward trend, as shown in Figure 2.2.

As the pressure decrease, the volume of water increase slightly. When the pressure reaches
the saturated pressure value at the specified temperature, the water starts to boil. During this
vaporization process, both temperature, th water starts to boils. During this vaporization
process, both temperature and the pressure remain constant, but the specific volume
increases. Once the last drop of liquid is vaporize, further reduction in pressure results in
further increase in specific volume.
Clausius Clapeyron Equation

The relationship between the temperature of a liquid and its vapor pressure is not a straight
line. Apparently the vapour pressure of the water increase more significantly than the
temperature of the system. This behavior can be explained with the Clausius-Clapeyron
equation which defines the slope of the vapour pressure curve :

𝑑𝑃 ℎ𝑓𝑔
= ---------------------------------------- ①
𝑑𝑇 𝑇𝑣𝑔

Where, dP / dT = the slope of the coexistence curve

ℎ𝑓𝑔 = latent heat enthalphy

T = Temperature

𝑣𝑔 = specific volume of saturated vapor

Assuming that,

𝑅𝑇
𝑣𝑔 = --------------------------------------- ②
𝑃

Equation ② into equation ①

If the corresponding temperature and pressure is known at two point, the enthalphy of
vaporization can also be determined from this equation.

𝑃 ℎ𝑓𝑔
𝐼𝑛 ( ) = 1 1 ---------------------- ③
𝑃𝑜 𝑅×[𝑇 −𝑇]
𝑜

Where R is a gas constant for water, R = 0.416 kJ/kg. Index “0” refer to the critical point of
water. This equation also will let us figure out the vapor pressure of a liquid at any
temperature if we know the enthalpy of vaporization.
 3.0 Methodology

Pressure Gauge

Thermometer Safety Valve

Discharge valve
Water Port Screw

Spanner Boiler

Details Specifications :

The Marcet Detail specification is it Design Pressure is 19.5 bar g while its Design
Temperature is about 214 degree celcius. The hydraulic Test Pressure for this test gives its
reading 29.25 bar g .It was tested on 4th Jun 2003. The Marcet boiler was manufactured on
28th May 2003 .Its serial number is P5700/216 .The voltage for this apparatus is 230V with
2kW Power.For additional description of the marcet boiler are the it consists of a stainless
steel pressure vessel fitted with a high pressure immersion electrical heater.The marcet boiler
also comes with a safety valve, glass thermometer and Bourdon type pressure gauge.
Water inlet valve and discharge valve are also installed.
Apparatus And Function

No Name Functions

1 Pressure Gauge Showing the pressure value of fluid inside boiler

2 Thermometer Indicating the value of water temperature inside the boiler

3 Discharge Valve To remove the excess water and air trapped inside the boiler

4 Water Jug To fill up the water inside the boiler

5 Spanner To tighten or loosen the water port screw

6 Water Port Screw To fill up required water inside the boiler

7 Boiler Heat up the water

8 Safety Valve To relieve excessive pressure inside boiler

3.1 Experimental Procedure

1 Open the feed water port screw by using spanner provided by lab assistant for fill up
the water.
2 Open the discharge valve slowly and make sure put any beaker or jar at the below of
the valve to avoid water drops on the table.
3 Fill up slowly the boiler with water to the marked level until the water drips through
the opened discharge valve.
4 Close water port screw tightly by using the spanner provided. Make sure it is properly
closed.
5 Switch on the electrical switch for the boiler and the water start to heat up.
6 By using the hand gloves, close back the discharge valve when you notice steam
starts to come out from the boiler. (This is to ensure that there is no more air traps
inside the water).
7 Record the temperature reading for each 0.5 bar increment of pressure until it reaches
6 bar which shows in gauge pressure attached on top of Marcet Boiler pressure
gauge.
8 Switch off the boiler’s power supply after reached 6 bar at the pressure gauge to stop
the heating process.
9 Record again the temperature reading when the pressure drops. The measurement
taken for every decreasing of 0.5 bars.
10 Tabulate and calculate the result.

3.2 Safety Precaution

1. Gloves is needed to wear on at all time when handling the Marcet Boiler.

2. All operating instructions supplied with the unit must be carefully read and understood
before attempting to operate the unit.

3. Check and rectify any leaks before start boiling the water.

4. Do not open the valves on the level sight tube when the vessel is in operation.

5. It is not necessary to drain the water from the boiler as there is no rusting component in the
boiler. In case of draining is necessary, incline the bench to a side and open the heater flange
slowly. Be extremely careful when draining, never allow water to contact with the heater
terminals.

6. Always make sure that the Marcet Boiler is filled with sufficient water to cover the heater
element by adding the water until water drip from the open valve. Water level at half of the
boiler’s height is sufficient to cover the heating element.

7. Do not touch the hot components of the unit. Be extremely careful when handling liquid at
high temperature.

8. It is not recommended to boil the water to a very high pressure (exceed 8 bar) and
temperature.

9. Restore the system to operating conditions after any repair job. Replace a new seal if
necessary.
4.0 Result

Pressure,P (bar) Temperature,T Measured Calculated

Gauge Absolute Increase Decrease Average, Average Slope, Slope,

(˚C ) (˚C ) (˚C ) (K) dP/dT hfg/Tvg

0.5 1.5

1.0 2.0

1.5 2.5

2.0 3.0

2.5 3.5

3.0 4.0

3.5 4.5

4.0 5.0

4.5 5.5
 5.0 6.0

5.5 6.5

6.0 7.0

Slope dP/dT = (P2-P1)abs / (T2-T1)

Slope hfg/Tvg = Refer to Properties Tables

5.0 Reference

1. Yunus A. Cengel, Michael A. Boles, Thermodynamics, An Engineering Approach Eighth

Edition, (2015) Published by McGraw-Hill Education, 2 Penn Plaza, New York, NY 10121.

2. Cengel, Y. A. (2015). Thermodynamics: An Engineering Approach. New York: McGraw-

Hill Education.

3. Zairul, E. (2017, October 05). Youtube. Retrieved March 08, 2018, from Marcet Boiler
Experiment Demostration: https://www.youtube.com/watch?v=hy9AYUCQIAw

4. Tecquipment Academia. (n.d.). Retrieved March 08, 2018, from SATURATED STEAM -
THE MARCET BOILER: https://www.tecquipment.com/saturated-steam-the-marcetboiler