LECTURE NOTES

ON
THERMODYNAMICS

2019 – 2020

Dr. M. Vubangsi, Assistant Lecturer

Department of Fundamental Sciences

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UNIT.I

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 THEERMODYNAMICS
INTRODUCTION

Thermodynamics is the science that deals with heat and work and those properties of
substance that bear a relation to heat and work.

Thermodynamics is the study of the patterns of energy change. Most of this course will be
concerned with understanding the patterns of energy change.

More specifically, thermodynamics deals with (a) energy conversion and (b) the direction of
change.

Basis of thermodynamics is experimental observation. In that sense it is an empirical science.

The principles of thermodynamics are summarized in the form of four laws known as zeroth,
first, second, and the third laws of thermodynamics.
The zeroth law of thermodynamics deals with thermal equilibrium and provides a means of
measuring temperature.
The first law of thermodynamics deals with the conservation of energy and introduces the
concept of internal energy.
The second law of thermodynamics dictates the limits on the conversion of heat into work
and provides the yard stick to measure the performance of various processes. It also tells
whether a particular process is feasible or not and specifies the direction in which a process
will proceed. As a consequence it also introduces the concept of entropy.
The third law defines the absolute zero of entropy.

Macroscopic and Microscopic Approaches:

Microscopic approach uses the statistical considerations and probability theory, where we
deal with “average” for all particles under consideration. This is the approach used in the
disciplines known as kinetic theory and statistical mechanics.
In the macroscopic point of view, of classical thermodynamics, one is concerned with the
time-averaged influence of many molecules that can be perceived by the senses and measured
by the instruments.
The pressure exerted by a gas is an example of this. It results from the change in momentum
of the molecules, as they collide with the wall. Here we are not concerned with the actions of
individual molecules but with the time-averaged force on a given area that can be measured
by a pressure gage.

From the macroscopic point of view, we are always concerned with volumes that are very
large compared to molecular dimensions, and therefore a system (to be defined next) contains
many molecules, and this is called continuum. The concept of continuum loses validity when
the mean free path of molecules approaches the order of typical system dimensions

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System:

We introduce boundaries in our study called the system and surroundings.

The boundaries are set up in a way most conducive to understanding the energetics of what
we're studying.

Defining the system and surroundings is arbitrary, but it becomes important when we
consider the exchange of energy between the system and surroundings.

Two types of exchange can occur between system and surroundings: (1) energy exchange
(heat, work, friction, radiation, etc.) and (2) matter exchange (movement of molecules across
the boundary of the system and surroundings).

Based on the types of exchange which take place or don't take place, we will define three
types of systems:

• isolated systems: no exchange of matter or energy

• closed systems: no exchange of matter but some exchange of energy
• open systems: exchange of both matter and energy

Control Volume

• control volume is defined as a volume which encloses the matter and the device inside
a control surface.
• Every thing external to the control volume is the surroundings with the separation
given by the control surface.
• The surface may be open or closed to mass flows and it may have flows from energy
in terms of heat transfer and work across it.
• The boundaries may be moveable or stationary.
• In the case of a control surface that is closed to the mass flow, so that no mass can
enter or escape the control volume, it is called a control mass containing same
amount of matter at all times.

Property

• In thermodynamics a property is any characteristic of a system that is associated with

the energy and can be quantitatively evaluated.

• The property of a system should have a definite value when the system is in a
particular state.
• Thermodynamic property is a point function.

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 • Properties like volume of a system that depend on the mass of a system are called
extensive properties.
• Properties like pressure or temperature which do not depend on the system mass are
called intensive properties.
• The ratio of extensive property to the mass of the system are called specific properties
and therefore become intensive properties.
• Substance can be found in three states of physical aggregation namely, solid, liquid
and vapor which are called its phases.
• If the system consists of mixture of different phases, the phases are separated from
each other by phase boundary.
• The thermodynamic properties change abruptly at the phase boundary, even though the
intensive properties like temperature and pressure are identical.

Equilibrium

• When the property of a system is defined, it is understood that the system is in

equilibrium.
• If a system is in thermal equilibrium, the temperature will be same throughout the
system.
• If a system is in mechanical equilibrium, there is no tendency for the pressure to
change. In a single phase system, if the concentration is uniform and there is no
tendency for mass transfer or diffusion, the system is said to be in chemical
equilibrium.
• A system which is simultaneously in thermal, mechanical, and chemical equilibrium
is said to be in thermal equilibrium.

Process

A process is path followed by a system in reaching a given final state of equilibrium state
starting from a specified initial state.

An actual process occurs only when the equilibrium state does not exist.

An ideal process can be defined in which the deviation from thermodynamic equilibrium is
infinitesimal.

All the states the system passes through during a quasi-equilibrium process may be
considered equilibrium states.

For non-equilibrium processes, we are limited to a description of the system before the
process occurs and after the equilibrium is restored.

Several processes are described by the fact that one property remains constant.

The prefix iso- is used to describe such processes.

A process is said to be reversible if both the system and its surroundings can be restored to
their respective initial states by reversing the direction of the process.

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 • reversible: if the process happens slow enough to be reversed.
• irreversible: if the process cannot be reversed (like most processes).

• isobaric: process done at constant pressure

• isochoric: process done at constant volume
• isothermal: process done at constant temperature
• adiabatic: process where q=0
• cyclic: process where initial state = final state

The basic units (SI Units)

Mass---------kg.
Mole------ The mole is the amount of substance that contains as many atoms (or molecules)
as there are atoms in 0.012 kg of carbon-12.
Length—m.
Time: second
SI unit of temperature is Kelvin (abbreviated as K). The Kelvin is defined as the fraction of
1/273.16 of the thermodynamic temperature of the triple point of water. The relation between
Kelvin and Celsius temperature is K = C + 273.15 (The triple point of water is at 0.01 C).
Derived units: Force: 1 N = 1 kg m/s, pressure 1 Pa = 1 N/m2, 1 bar = 10 Pa, 1 atm. = 101325
Pa. In thermodynamics we are concerned with absolute pressure. Gauge pressure = absolute
pressure – atmospheric pressure. Ordinary vacuum gauge pressure = atmospheric pressure –
absolute pressure.

Internal Energy

•The molecule as a whole can move in x, y and z directions with respective

components of velocities and hence possesses kinetic energy.
• There can be rotation of molecule about its center of mass and than the kinetic
energy associated with rotation is called rotational energy.
• In addition the bond length undergoes change and the energy associated with it is
called vibrational energy.
• The electron move around the nucleus and they possess a certain energy that is called
electron energy.
• The microscopic modes of energy are due to the internal structure of the matter and
hence sum of all microscopic modes of energy is called the internal energy.
Bulk kinetic energy (KE) and potential energy (PE) are considered separately and the other
energy of control mass as a single property (U).
The total energy possessed by the body is given by:
E = KE + PE + U

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Work

Whenever a system interacts with its surroundings, it can exchange energy in two ways-
work and heat.
In mechanics, work is defined as the product of the force and the displacement in the
direction of the force.

Work done when a spring is compressed or extended: According to Hooke's law

Spring force = - k (x – x0)

Where k is the spring constant, x0 is the equilibrium position, and x is the final position. The
negative sign shows that the direction of the spring force is opposite the direction of the
displacement from x0. The external force is equal in magnitude but opposite in sign to the
spring force, so

External force (force of your hands) = k (x –x0).

Now, we want to calculate the work done when we stretch the spring from position 1 to
position 2.

W = F dx = k (x – x0) d(x-x0) = 1/2 k [(x2-x0)2 - (x1-x0)2]

Work done when a volume is increased or decreased

Consider a gas in a container with a movable piston on top. If the gas expands, the piston
moves out and work is done by the system on the surroundings.

Alternatively, if the gas inside contracts, the piston moves in and work is done by the
surroundings on the system. Why would the gas inside contract or expand?

It would if the external pressure, Pex, and the internal pressure, Pin, were different. To
calculate the work done in moving the piston, we know that the force = pressure times area
and then work equals pressure times area times distance or work equals pressure times the
change in volume. So, W = the integral of (Pex) dV

The differential work done (dW) associated with a differential displacement (dl) is given by

dW = F dl
For a piston cylinder assembly,
dW = F dl = PA (dl) = P dV
If the gas is allowed to expand reversibly from the initial pressure P to final pressure P, then
the work done is given by
W = ∫ p dV

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 • The integral represents the area under the curve on a pressure versus volume diagram.
Therefore the work depends on the path followed and work is a path function and
hence not a property of the system.

• The above expression does not represent work in the case of an irreversible process.

• The thermodynamic definition of work is “ Work is said to be done by a system on

the surrounding if the sole effect external to the system could be reduced to the raising
of a mass through a distance”.

Heat:

Heat like work, is a form of energy.

The energy transfer between a system and its surroundings is called heat if it occurs by virtue
of the temperature difference across the boundary.
The two modes of energy transfer – work and heat- depend on the choice of the system.
Heat energy moves from a hotter body to a colder body upon contact of the two bodies.

If two bodies at different temperatures are allowed to remain in contact, the system of two
bodies will eventually reach a thermal equilibrium (they will have the same temperature).

A body never contains heat. Rather heat is a transient phenomenon and can be identified as it
crosses the boundary.

The State Postulate

The state of the system is described by its properties.

Once a sufficient number of properties are specified, the rest of the properties assume
some values automatically.
The number of properties required to fix a state of a system is given by the state
postulate:

The state of a simple compressible system is completely specified by two independent,

intensive properties.
The system is called a simple compressible system in the absence of electrical,
magnetic, gravitational, motion, and surface tension effects.

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The state postulate requires that the two properties specified be independent to fix the state.
Two properties are independent if one property can be varied while the other one is held
constant. Temperature and specific volume, for example, are always independent
properties, and together they can fix the state of a simple compressible system.Thus,
temperature and pressure are not sufficient to fix the state of a two-phase system.
Otherwise an additional property needs to be specified for each effect that is significant.
An additional property needs to be specified for each other effect that is significant.
Zeroth Law of Thermodynamics :
We cannot assign numerical values to temperatures
based on our sensations alone. Furthermore, our senses may be misleading.
Several properties of material changes with temperature in a repeatable and predictable way,
and this forms the basis of accurate temperature measurement.
The commonly used mercury-in-glass thermometer for example, is based on the expansion
of mercury with temperature.
Temperature is also measured by using several other temperature dependant properties.
Two bodies (eg. Two copper blocks) in contact attain thermal equilibrium when the heat
transfer between them stops. The equality of temperature is the only requirement for thermal
equilibrium.

The Zeroth Law of Thermodynamics

If two bodies are in thermal equilibrium with a third body, they are also in thermal
equilibrium with each other.

This obvious fact cannot be concluded from the other laws of thermodynamics, and it serves
as a basis of temperature measurement.

By replacing the third body with a thermometer, the zeroth law can be restated two bodies
are in thermal equilibrium if both have the same temperature reading even if they are not in
contact

The zeroth law was first formulated and labeled by R.H. Fowler in 1931.

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Temperature Scales:

All temperature scales are based on some easily reproducible states such as the freezing and
boiling point of water, which are also called the ice-point and the steam-point respectively.

A mixture of ice and water that is in equilibrium with air saturated with water vapour at 1atm
pressure is said to be at the ice-point, and a mixture of liquid water and water vapour (with no
air) in equilibrium at 1atm is said to be at the steam-point.

Celsius and Fahrenheit scales are based on these two points (although the value assigned to
these two values is different) and are referred as two-point scales.

In thermodynamics, it is very desirable to have a temperature scale that is independent of the

properties of the substance or substances.
Such a temperature scale is called a thermodynamic temperature scale.(Kelvin in SI)

Ideal gas temperature scale:

The temperatures on this scale are measured using a constant volume thermometer.
Based on the principle that at low pressure, the temperature of the gas is proportional to its
pressure at constant volume.
The relationship between the temperature and pressure of the gas in the vessel can be
expressed as T = a + b.P
Where the values of the constants a and b for a gas thermometer are determined
experimentally.
Once a and b are known, the temperature of a medium can be calculated from the relation
above by immersing the rigid vessel of the gas thermometer into the medium and measuring
the gas pressure.
Ideal gas temperature scale can be developed by measuring the pressures of the gas in the
vessel at two reproducible points (such as the ice and steam points) and assigning suitable
values to temperatures those two points.
Considering that only one straight line passes through two fixed points on a plane, these two
measurements are sufficient to determine the constants a and b in the above equation.
If the ice and the steam points are assigned the values 0 and 100 respectively, then the gas
temperature scale will be identical to the Celsius scale.
In this case, the value of the constant a (that corresponds to an absolute pressure of zero) is
determined to be –273.150C when extrapolated.
The equation reduces to T = bP, and thus we need to specify the temperature at only one
point to define an absolute gas temperature scale.

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 Absolute gas temperature is identical to thermodynamic temperature in the temperature
range in which the gas thermometer can be used.We can view that thermodynamic
temperature scale at this point as an absolute gas temperature scale that utilizes an ideal gas
that always acts as a low-pressure gas regardless of the temperature.
At the Tenth international conference on weights and measures in 1954, the Celsius scale has
been redefined in terms of a single fixed point and the absolute temperature scale.
The triple point occurs at a fixed temperature and pressure for a specified substance.
The selected single point is the triple point of water (the state in which all three phases of
water coexist in equilibrium), which is assigned the value 0.01 C. As before the boiling point
of water at 1 atm. Pressure is 100.0 C. Thus the new Celsius scale is essentially the same as
the old one.
On the Kelvin scale, the size of Kelvin unit is defined as “ the fraction of 1/273.16 of the
thermodynamic temperature of the triple point of water, which is assigned a value of
273.16K”. The ice point on Celsius and Kelvin are respectively 0 and 273.15 K.

Example 1. Consider as a system, the gas in the cylinder shown in the figure. The cylinder is
fitted with a piston on which number of small weights is placed. The initial pressure is 200
kPa, and the initial volume of the gas is 0.04 m2.

1. Let the gas in the cylinder be heated, and let the volume of the gas increase to 0.1 m3
while the pressure remains constant. Calculate the work done by the system during
this process.

2
W = ∫ P dV
1

Since the pressure is constant, we conclude

from the above equation that

2
W = P ∫ dV = P (V2 − V1 )
1

W = 200 kPa * (0.1 − 0.04 ) m 3 = 12 .0 kJ

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 2. Consider the same system and initial condition, but at the same time the cylinder is
being heated and the piston is rising, let the weights be removed from the piston at
such a rate that, during the process the temperature of the gas remains constant.

If we assume that the ideal-gas model is valid. We note that this is a polytropic process
(PVn=const.) with exponent n = 1. For such a process,

2 2
dV V
W = ∫ P dV = P1V1 ∫ = P1V1 ln 2
1 1
V V1
0.10
= 200 kPa * 0.04 m 3 * ln = 7.33kJ
0.04

3. For the same system, let the weights be removed at such a rate that the expression
PV1.3 = const. Again the final volume is 0.1 m3. Calculate the work.

cons tan t P1V n1 P2V n 2

P= = =
Vn Vn Vn
2
2 2
dV V − n +1

∫ PdV = cons tan t ∫
1 1
V n
= cons tan t 
 
 − n + 11
cons tan t 1− n 1− n P2V n 2V21− n − P1V n1V11− n
= (V2 − V1 ) =
1− n 1− n
P V − P1V1
= 2 2
1− n

1.3
 0.04 
P2 = 200   = 60 .77 kPa
 0 .1 
P V − P1V1 60 .77 * 0.1 − 200 * 0.04
W = 2 2 =
1 − 1 .3 1 − 1 .3
= 6.41kJ

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 4. Consider the system and initial state as before, but let the piston be held by a pin so
that the volume remains constant. In addition, let heat transfer take place from the
cylinder so that the pressure drops to 100kPa. Calculate the work.

Since dV = zero, the work is zero because there is no change in volume.

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Example 2. Consider a piston cylinder arrangement as shown. The piston is loaded with a
mass, mp, the outside atmospheric pressure P0, a linear spring and a single point force F1. The
piston is restricted in its motion by lower and upper stops trapping the gas with a pressure P.

For zero acceleration in a quasi-equilibrium process,

∑ F =∑ F↑ ↓

The forces when the piston is between the stops are

∑F ↑
=PA ∑F ↓
= m p g + P0 A + k ( x − x0 ) + F1
with the linear spring cons tan t k

The piston position for a relaxed spring is x0, which depends on how the spring is installed.

The force balance then gives the gas pressure by division with the area, A, as

[
P=P0 + mpg+k(x−x0) +F / A ]
To illustrate the process in a P-V diagram, the distance x is converted to volume by division
and multiplication with A:

mpg F1 k
P=P0 + + + 2 (V−V0) =C1 +C2V
A A A

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 This relation gives the pressure as a linear function of the volume with slope of
C2=k/A2

equilibrium process, is
The work in a quasi-equilibrium

2
W = ∫ P dV = Area under the curve
1

=
1 `
2
( )
P1 + P2` (V2 − V1 )

With P`1 = P1 and P'2 = P2 subject to the constraint that

Pmin ≤ P1`, P2` ≤ Pmax

An part of the process with a pressure smaller that Pmin or larger than Pmax does not involve
work.

CREC Department of Mechanical Engineering Page 15

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Example 3. Balloon initially collapsed and flat. Slowly filled with helium from a cylinder

Dia = 5 m.
Ambient pressure = 100 kPa
Temperature const. = 300 K

System: Helium contained in cylinder and balloon.

Filling process quasi-static process

Work done by Helium , W

2
= ∫ P dV = P (V 2 − V1 )
1

= PV 2
4π
= 100 *10 * (5 2) 3 = 6544 .98 kJ
3

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Ideal and Real Gases

Pure Substance:
A pure substance is one that has a homogeneous and invariable chemical composition. It
may exist in more than one phase but chemical composition is the same in all phases.

Some times the mixture of gases, such as air is considered a pure substance as long as
there is no change of phase. Further our emphasis will be on simple compressible substances

Early experiments on the variables of state (such as T, P, V, and n) showed that only two of
these variables of state need to be known to know the state of a sample of matter.

• Extensive variables: depend on the amount of substance present. Examples include

the volume, energy, enthalpy, and heat capacity.

• Intensive variables: do not depend on the amount of substance present. Examples

include the temperature and pressure.

Equations of State:
An equation of state is an equation which relates the variables of state (T, P, V, and n). It's
particularly useful when you want to know the effect of a change in one of the variables of
state

• Solids and Liquids:

• If the pressure on a solid or liquid is increased, the volume does not change much. If
the temperature is increased, the volume doesn't change much either. Therefore, an
appropriate equation of state describing such systems would be: V(T,P) = constant.

• Gases:
• In contrast, changing the pressure or temperature of a gas will have an easily
observable effect on the volume of that gas. For an ideal gas (no intermolecular
interactions and no molecular volume) n appropriate equation of state would be:
V(T,P,n) = (nRT)/P.
• There are many equations of state describing real gases. These equations take in
consideration molecular volume and interactions. The most well-known such
equations is probably the Van der Waals equation.

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Ideal and real gases:

An ideal gas is one which follows the ideal gas equation of state, namely
PV = (m/M) (MR) T = n Ru T

The universal gas constant has a value of 8.314 J/mol K or kJ/kmol K and is related to the
specific gas constant by the relation Ru = (R /M)

The ideal gas equation of state can be derived from the kinetic theory of gases where the
following assumptions are made:

1. The molecules are independent of each other. In other words, there are no attractive
forces between the molecules.
2. The molecules do not occupy any volume. That is the volume occupied by the
molecules is quite negligible compared to the volume available for motion of the
molecules.

The internal energy of an ideal gas is a function of temperature only and is independent of
pressure and volume. That is,
u= u(T)
(∂u/∂P)T =0, (∂u /∂v)T = 0

Enthalpy and specific heat:

h = u+ Pv
For an ideal gas u = u(T) only and PV = mRT and hence h = h(T) only.

The specific heat at constant volume is defined as the amount of energy transferred as heat at
constant volume, per unit mass of a system to raise its temperature by one degree. That is,

Cv = (dq/dT)v
The specific heat at constant pressure is defined as the energy transferred as heat at constant
pressure, per unit mass of a substance to raise its temperature by one degree. That is
Cp = (dq/dT)P

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For a constant pressure process dq = du + dw = du + Pdv = du+ Pdv +vdP(since dP=0 for a
constant pressure process)
Or dq= du+d(Pv) = d(U+ Pv) = dh
or dq=dh
CP = (∂h/∂T)P

The ratio of specific heat (γ) is given by

γ= C P/Cv

For mono-atomic ideal gases γ = 1.67 and for diatomic gases γ= 1.4.

Relation between two specific heats:

The two specific heats are related to each other.

h= u + Pv or dh = du + d(Pv)
For an ideal gas, the above equation reduces to
dh = du + d(RT) = du + RdT or
dh/dT = du/dT+R or CP = Cv+ R
or CP –Cv = R for an ideal gas.
γ= CP /Cv or CP = R/(γ-1) and Cv = Rγ /(γ-1)

Real gases:

The ideal gas law is only an approximation to the actual behavior of gases.

At high densities, that is at high pressures and low temperatures, the behavior of actual or
real gases deviate from that predicted by the ideal gas law. In general, at sufficiently low
pressures or at low densities all gases behave like ideal gases.

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Van der Waals Equation of State:

An equation of state taking account the volume occupied by the molecules and the attractive
forces between them.
(P+a/v2 )(v-b) = RT
where a and b are van der Waals constants.

The equation is cubic in volume and in general there will be three values of v for given
values of T and P.
However in some range of values of P and T there is only one real value v.
For T >Tc (critical temperature) there will be only one real value of v and for T< Tc there
will be three real values.
In Figure, the solid curve represents the value predicted by the van der Waals equation of
state and the points represent the experimentally determined values.
It can be observed that at temperatures greater than critical, there is only one real value of
volume for a given P and T.

However at temperatures less than the critical, there are three real values of volume for a
given value of P and T.

The experimental values differ from those predicted by van der Waals equation of state in
region 2345 if T<Tc.

One can use the criterion that the critical isotherm (isotherm passing through the critical
point) shows a point of inflexion. Stated mathematically

(∂P/∂v)T=Tc= 0 and (∂2P/∂v2)T=Tc = 0

(∂P/∂v)T=Tc = -RTc/(vc –b)2 + 2a/vc3 = 0

or
RTc/(vc –b)2 = 2a/vc3
(∂2P/∂v2)T=Tc = 2RTc/(vc-b)3 -6a/vc4 = 0

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 or

2RTc/(vc-b)3 = 6a/vc4
Therefore
2/(vc –b) = 3/vc or vc = 3b

At the critical point, the van der Waal’s equation is given by

Pc = RTc/(vc – b) – a/vc2
From these equations,
a = 27R2Tc2/64 Pc and b = RTc/8Pc

Compressibility Factor:

The deviation from ideal behavior of a gas is expressed in terms of the compressibility factor
Z, which is defined as the ratio of the actual volume to the volume predicted by the ideal gas
law.

Z = Actual volume/volume predicted by ideal gas law = v/RT/P = Pv/RT

For an ideal gas Pv = RT and hence Z = 1 at all temperatures and pressures.
The experimental P-v-T data is used to prepare the compressibility chart.

Reduced pressure, PR = P/Pc,

Reduced temperature, TR = T/Tc
Reduced volume, vR = v/vc

Where Pc, Tc and vc denote the critical pressure, temperature and volume respectively.

These equations state that the reduced property for a given state is the value of this property
in this state divided by the value of this same property by at the critical point.

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 The striking fact is that when such Z versus Pr diagrams are prepared for a number of
different substances, all of them very nearly coincide, especially when the substances have
simple, essentially spherical molecules.
We need to know only critical temperature and critical pressure to use this basic generalized
chart.

In general it can be noted that idealized gas behavior for very low pressures as compared to
critical) regardless of temperature. Furthermore, at high temperatures (greater than twice Tc),
the ideal-gas model can be assumed to good accuracy to pressures as high as 4-5 times Pc.

GRAPHICAL REPRESENTATION OF DATA

1. Pressure versus temperature (P-T)

2. Pressure vs. volume (P-v)

3. Temperature vs. volume (T-v)

4. Temperature vs. entropy (T-s)

5. Enthalpy vs. entropy (h-s)

6. Pressure vs. enthalpy (P-h)

The term saturation temperature designates the temperature at which vaporization takes
place.
For water at 99.6 C the saturation pressure is 0.1 M Pa, and for water at 0.1 Mpa, the
saturation temperature is 99.6 C.
If a substance exists as liquid at the saturation temperature and pressure it is called
saturated liquid.
If the temperature is of the liquid is lower than saturation temperature at the existing
pressure it is called sub-cooled liquid or compressed liquid.
1. When a substance exists as part liquid and part vapor at the saturation temperature,
its quality is defined as the ratio of the mass of vapor to the total mass.
2. If a substance exists as vapor at the saturation temperature, it is called a saturated
vapor.

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 3. When the vapor is at a temperature greater than the saturation temperature, it is said
to exist as superheated vapor.
4. At the critical point, the saturated liquid and saturated vapor state are identical.
5. At supercritical pressures, the substance is simply termed fluid rather than liquid or
vapor.
6. If the initial pressure at –200C is 0.260 kPa, heat transfer results in increase of
temperature to –100C. Ice passes directly from the solid phase to vapor phase.
7. At the triple point (0.6113 kPa) and a temperature of –200C, let heat transfer increase the
temperature until it reaches 0.010C. At this point, further heat transfer may cause some ice
to become vapor and some to become liquid. The three phases may be present
simultaneously in equilibrium.

Tables of Thermodynamic Properties

Tables of thermodynamic properties of many substances are available, and in general, all
these have same form.

Steam tables are selected because steam is used extensively in power plants and industrial
processes.
The steam tables provide the data of useful thermodynamic properties like T, P, v, u, h and s
for saturated liquid, saturated vapor and superheated vapor.
Since the properties like internal energy, enthalpy and entropy of a system cannot be directly
measured; they are related to change in the energy of the system.
Hence one can determine ∆u, ∆h, ∆s, but not the absolute values of these properties.
Therefore it is necessary to choose a reference state to which these properties are arbitrarily
assigned some numerical values.

For water, the triple point (T = 0.01o C and P = 0.6113 kPa) is selected as the reference state,
where the internal energy and entropy of saturated liquid are assigned a zero value.
In the saturated steam tables, the properties of saturated liquid that is in equilibrium with
saturated vapor are presented.
During phase transition, the pressure and temperature are not independent of each other. If
the temperature is specified, the pressure at which both phases coexist in equilibrium is equal
to the saturation pressure.
Hence, it is possible to choose either temperature or pressure as the independent variable, to
specify the state of two-phase system.
Depending on whether the temperature or pressure is used as the independent variable, the
tables are called temperature or pressure tables.
The two phases- liquid and vapor can coexist in a state of equilibrium only up to the critical
point.

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 Therefore the listing of the thermodynamic properties of steam in the saturated steam tables
ends at the critical point (374.15o C and 212.2 bar).
If the steam exists in only one phase (superheated steam), it is necessary to specify two
independent variables, pressure and temperature, for the complete specification of the state.
In the superheated steam tables, the properties- v, u, h, and s- are tabulated from the
saturation temperature to some temperature for a given pressure.
The thermodynamic properties of a liquid and vapor mixture can be evaluated in terms of its
quality. In particular, the specific volume, specific internal energy, specific enthalpy and
specific entropy of a mixture of quality X are given by
v = (1-X)vf + Xvg, u = (1-X)uf + Xug, h = (1-X)hf + Xhg = hf + Xhfg, s = (1-X)sf + Xhg
where hfg = hg - hf = latent hat of vaporization.

Temperature-volume diagram:
The locus of all the saturated states gives the saturated liquid curve AC and the locus of all
the saturated vapor states gives the saturated vapor states gives the saturated vapor states
gives the saturated vapor curve BC.
The point C represents the critical point. The difference between vg and vf reduces as the
pressure is increased, and at the critical point vg = vf .
At the critical point, the two phases-liquid and vapor- are indistinguishable.

Pressure-volume diagram

The pressure-volume (P-V) diagram for a pure substance is shown in Figure. The curves AC
and BC represent the saturated liquid curve and saturated vapor curve, respectively, and C is
critical point.

The area under the curve represents the two-phase region. Any point M in this region is a
mixture of saturated liquid (shown as f) and saturated vapor (g).

Mollier (h-s) Diagram

The h-s diagram was introduced by Richard Mollier and was named after him.
It consists of a family of constant pressure lines, constant temperature lines and constant
volume lines plotted on enthalpy versus entropy coordinates.
In the two-phase region, the constant pressure and constant temperature lines coincide.

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