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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
ME8391 ENGINEERING THERMODYNAMICS
L T P C
3 0 0 3
UNIT I BASIC CONCEPTS AND FIRST LAW 9
Basic concepts - concept of continuum, comparison of microscopic and macroscopic approach.
Path and point functions. Intensive and extensive, total and specific quantities. System and
their types. Thermodynamic Equilibrium State, path and process. Quasi-static, reversible and
irreversible processes. Heat and work transfer, definition and comparison, sign convention.
Displacement work and other modes of work .P-V diagram. Zeroth law of thermodynamics –
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concept of temperature and thermal equilibrium– relationship between temperature scales –
new temperature scales. First law of thermodynamics –application to closed and open systems
– steady and unsteady flow processes.
UNIT II
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SECOND LAW AND AVAILABILITY ANALYSIS 9
Heat Reservoir, source and sink. Heat Engine, Refrigerator, Heat pump. Statements of
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second law and its corollaries. Carnot cycle Reversed Carnot cycle, Performance. Clausius
inequality. Concept of entropy, T-s diagram, Tds Equations, entropy change for - pure
substance, ideal gases - different processes, principle of increase in entropy. Applications
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of II Law. High and low grade energy. Available and non-available energy of a source and
finite body. Energy and irreversibility. Expressions for the energy of a closed system and
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open systems. Energy balance and entropy generation. Irreversibility. I and II law
Efficiency.
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UNIT III PROPERTIES OF PURE SUBSTANCE AND STEAM POWER CYCLE 9
Formation of steam and its thermodynamic properties, p-v, p-T, T-v, T-s, h-s diagrams. p-v-T
surface. Use of Steam Table and Mollier Chart. Determination of dryness fraction.
Application of I and II law for pure substances. Ideal and actual Rankine cycles, Cycle
Improvement Methods - Reheat and Regenerative cycles, Economiser, preheater, Binary and
Combined cycles.
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UNIT IV IDEAL AND REAL GASES, THERMODYNAMIC RELATIONS 9
Properties of Ideal gas- Ideal and real gas comparison- Equations of state for ideal and real
gases- Reduced properties-.Compressibility factor-.Principle of Corresponding states. -
Generalised Compressibility Chart and its use-. Maxwell relations, Tds Equations, Difference
and ratio of heat capacities, Energy equation, Joule-Thomson Coefficient, Clausius
Clapeyron equation, Phase Change Processes. Simple Calculations.
UNIT V GAS MIXTURES AND PSYCHROMETRY 9
Mole and Mass fraction, Dalton‟s and Amagat‟s Law. Properties of gas mixture – Molar
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mass, gas constant, density, change in internal energy, enthalpy, entropy and Gibbs
function. Psychrometric properties, Psychrometric charts. Property calculations of air
heating .co
vapour mixtures by using chart and expressions. Psychrometric process
saturation, sensible and cooling,
evaporative cooling and adiabatic mixing. Simple Applications.
humidification,
–adiabatic
dehumidification,
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UNIT CONTENT PAGE
NO. NO.
1 BASIC CONCEPTS AND FIRST LAW
1.1 Statistical and Classical Thermodynamics 7
1.2 Types of Thermodynamics 8
1.3 Thermodynamic Properties 9
1.4 Thermodynamic State & Equilibrium 9
1.5 Processes and Cycles 10
1.6 Point and Path Functions 11
1.7 Temperature and Zeroth Law 13
1.8 Temperature Sclaes 14
1.9 Pure Substances 15
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1.10 Concept of Continuum 16
1.11 Work & Heat 16
1.12 Units of Work & Power 17
1.14 Displacement Work
1.15 Heat
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1.13 Sign convection of Work
1.16 Sensible Heat and Latent Heat
1.17 The first law of Thermodynamics
17
18
22
24
24
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1.18 Steady Flow Energy Equation 28
2 SECOND LAW OF THERMODYNAMICS
2.1 The Second law of Thermodynamics 40
2.2 Equivalence Kelvin-Planck & Clausius Statements 43
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2.3 Reversible Process 45
2.4 Entropy 50
2.5 Temperature Entropy Diagram 53
2.6 Change in Entropy 54
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2.7 Principle of Increase in Entropy 55
2.8 Solved Problems 56
2.9 Availability Energy, Availability & Irreversibility 62
2.10 Availability 65
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2.11 Irreversibility 67
3 PROPERTIES OF PURE SUBSTANCE AND STEAM POWER
CYCLE
3.1 Pure Substance 69
3.2 Formation of Steam & Properties 70
3.3 p-v, p-T, T-v, T-s, h-s Diagrams 71
3.4 Definitions and Applications 73
3.5 Solved Problems 73
3.6 The Measurements of Dryness Fraction 79
3.7 Regenerative Brayton Cycle 82
3.8 Intercooling and Reheating 84
3.9 Gas Power/ Air Standard Cycles 87
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3.10 Brayton Cycle 88
3.11 Combined Cycle 92
4 IDEAL AND REAL GASES, THERMODYNAMIC
RELATIONS
4.1 Ideal Gas 94
4.2 Real Gas 94
4.3 Vander waals Modelisation 95
4.4 Redlich-Kwong Modelisation 95
4.5 Thermodynamics Relations 96
4.6 The Joule-Thomson Coefficient of an Ideal Gas is Zero 101
4.7 Clausius – Claperyon Relation 102
4.8 Solved Problems 106
5 GAS MIXTURES AND PSYCHROMETRY
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5.1 Gas Mixtures 112
5.2 p-v-T Behavior of Gas Mixtures 114
5.3 Entropy 116
5.4 Psychrometry
5.5 Solved Problems
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122
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UNIT –I
BASIC CONCEPTS AND DEFINITIONS
Thermodynamics is the science of energy transfer which deals with the relations among heat, work
and properties of systems.
The name ‘thermodynamics’ is derived from the Greek words therme, meaning ‘heat’ and
dynamis meaning power. Thus, thermodynamics is basically the study of heat and power.
Application Area of Thermodynamics
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Energy transfer is present in almost all the engineering activities. Hence, the principles of
thermodynamics are playing vital role in designing all the engineering equipments such as internal
1.1 Statistical and Classical Thermodynamics
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combustion engines, rockets, jet engines, thermal and nuclear power plants, refrigerators etc.
Statistical Thermodynamics is microscopic approach in which, the matter is assumed to be made of
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numerous individual molecules. Hence, it can be regarded as a branch of statistical mechanics dealing
with the average behaviour of a large number of molecules.
Classical thermodynamics is macroscopic approach. Here, the matter is considered to be a
continuum without any concern to its atomic structure.
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Consider a gas in a container. Pressure exerted at the wall of the container is the average force per
unit area due to the collision of the gas molecules on the wall surface. To determine this pressure, we
need not know the behaviour of individual molecules of the gas. This approach is macroscropic approach.
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However, the results obtained from macroscopic and statistical study of matter.
Thermodynamic Systems and Surroundings
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A Thermodynamic system is defined as a quantity of matter or a region in space whose behaviour
is being investigated.
Everything external to the system is defined as surroundings. In its usual context the term
‘surroundings’ is restricted to the regions in the immediate vicinity which has a detectable influence
on the system.
Boundary is the surface which separates the system from its surroundings. It may be fixed or
moving and real or imaginary.
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Surroundings
System
Boundary
Fig.1.1 Thermodynamic System, boundary, surroundings
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1.2 Types of Thermodynamic Systems
There are three types of thermodynamic systems :
a)
b)
c)
Closed System
Open System and
Isolated System
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In closed system, attention is focused on a fixed mass. Energy in the form of heat and work (The terms
heat and work will be defined in the chapter 2.) can cross the boundary of the system. But there is no
mass flow across the boundary. Hence, the possibility of change in volume is always there in the closed
systems.
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Cylinder
Piston
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Fig.1.2 Closed system
In open system, both matter and energy can cross the boundary. Here, the behaviour of a fixed region in
space called control volume is investigated and hence, there is no change in volume. The surface of the
control volume is known as control surface.
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Water in
Control
surface
Water out
Fig.1.3 Open system
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A system that exchanges neither energy nor matter with its surroundings is known as an isolated system.
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vessel
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Fig.1.2 Isolated system
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1.3 Thermodynamic Properties
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In all thermodynamic problems energy transfer to or from the system is observed. To receive, store
and deliver energy a working substance is present within the system. The characteristics which can be
used to describe the condition of the system are known as properties.
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Thermodynamic properties are classified into two categories : intensive and extensive. Intensive
properties are independent of quantity of matter or mass whereas extensive properties are dependent on
mass
Consider a vessel containing air. If a membrane is assumed to be introduced into the vessel, such that it is
divided into two equal parts. The properties remaining unchanged such as pressure and temperature are
intensive properties. Volume of air will be reduced to half of its initial value. Hence, it is an extensive
property.
1.4 Thermodynamic State and Equilibrium
When a system does not undergo any change, all the properties have fixed values. This condition is
known as a thermodynamic state.
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The word equilibrium means balance. An equilibrium state of a thermodynamic system is a state
that can not be changed without any interaction with its surroundings. The factors that cause a change
without any interactions with its surroundings are:
1. Pressure difference
2. Temperature difference
3. Chemical reaction
If a system is balanced in all respects, it is in a state of thermodynamic equilibrium. Balanced in all
respects means :
There should not be any temperature difference within the system, so that the system is
thermally balanced.
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No pressure difference exists between any two points within the system (Neglecting
gravitational effects) and between the system and surroundings, so that it is mechanically
balanced.
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No chemical reaction is taking place, so that it is chemically balanced.
If two phases are involved, mass of each phase remains constant so that phase equilibrium
is achieved.
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Hence, for a system in a state of thermodynamic equilibrium, there is no change in any
macroscopic property.
1.5 Processes and Cycles
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When a system is taken from one equilibrium state to another, the change is known as process. The
series of intermediate states through which a system passes during a process is called the path of the
process. If all these intermediate states are equilibrium states, the process is known as quasi equilibrium
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or quasi-static process.
Consider a certain quantity of gas taken in a frictionless piston cylinder arrangement as shown in
Fig 1.5. The system is in thermodynamic equilibrium so that there is no unbalanced force acting on
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piston.
thgieW thgieW
Cylinder
Piston
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(a) (b)
Fig.1.5 Illustration for thermodynamic equilibrium
The moment the weight is removed from the piston, mechanical equilibrium does not exist and as a
result the piston is moved upward until mechanical equilibrium is restored again. Therefore the actual
process occurs only when equilibrium does not exist.
As shown in Fig.1.5.a, if the entire weight on the piston is removed at once, the deviation from the
equilibrium is high and the expansion is rapid. For such a process the intermediate states are not
equilibrium states and hence the process would be non-quasi-equilibrium.
If the weight is assumed to be made of a large number of small pieces as shown in Fig.1.5.b and
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taken off one by one, the deviation from equilibrium is less. The process could be considered quasi-
equilibrium.
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A thermodynamic system is said to undergo a cycle, if it is taken through a number of processes
such that, the final state of the last process is identical with the initial state of the first process in all
respects. For cycles net change in any property is zero.
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1.6 Point and Path Functions
Thermodynamic functions are classified into two categories namely point and path functions.
Point functions are those for which the change depends on only the end states and not on the path
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followed. Hence point functions are inexact differentials
Path functions are those for which the change depends not only on the end states but also on the path
followed. Hence path functions are exact differentials
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In can be observed the change in any property during a process depends only on end states.
Therefore all the properties are point functions.
.
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To demonstrate path and point functions, let us consider two stations A and B on a hill as shown in
the Fig.1.6. While moving from station A to station B, let the distance traveled and increase in height
from the mean sea level are observed. Distance traveled in path 1 is different from that in path 2. Hence it
may be regarded as path function. But the change in height is same in both path 1 and path 2, therefore it
is a point function.
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onoitatS A
A WeaP
A WeaP
onoitatS A
Fig.1.6 Illustration of point and path functions
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State Postulate and Property Diagrams
As mentioned earlier, properties are meant for describing the state of a system. To fix a state, all
properties automatically
This is known as state postulate.
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the properties need not be specified. If any two independent intensive properties are specified, rest of the
assumes certain values.
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1
1
p
p 2
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V
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Fig.1.7 property diagram of equilibrium and non equilibrium processes
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Consider pressure and specific volume (Volume per unit mass) are the two independent, intensive
properties, describing the state of a compressible system. On a p-V diagram the state will assume a point
as represented in the Fig.1.7(a). Let the system be taken to another state such that all the intermediate
states are equilibrium states. The curve connecting the initial state and final state, passing through all the
intermediate states is indicating the path of the process. In non-quasi-equilibrium process as the
intermediate status can not be defined, the path is denoted by dashed line as given in Fig.1.7(b)
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1 3
p
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Fig. 1.8 Thermodynamic cycle on a property diagram
Fig.1.8 indicates a system undergoing a cycle consisting of three quasi-equilibrium processes.
1.7 Temperature and Zeroth Law
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Maxwell defined the temperature of a system as its Thermal state considered with reference to its
ability to communicate heat to other bodies.
When a hot body is brought into contact with a cold body, the hot body becomes cooler and the
cold body becomes hotter. After sufficient time, the temperature of both the bodies will be equal. At that
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point, the two bodies are said to have reached thermal equilibrium.
Consider three bodies A, B and C. If the bodies A and B are in thermal equilibrium with C when
brought into contact separately, they are also in thermal equilibrium with each other. This concept is
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known as zeroth law of thermodynamics.
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A B
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Several properties of materials are found to be varying with temperature in a predictable way. This
variation is used to measure temperature. In mercury thermometers, expansion of mercury with
temperature is used for temperature measurement.
1.8 Temperature Scales
Freezing point of water known as ice point and boiling point of water known as steam point are
taken as the reference states for all types of temperature scales.
The various types as temperature scales in use are :
a) Celsius scale
b) Fahrenheit scale
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c) Kelvin scale
d) Rankine scale
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Boiling point of water at 1 atm.
Steam point
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Melting point/ Freezing point
Ice point
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Absolute zero
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Reference Celsius Kelvin Fahrenheit Rankine
state
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Steam point 100 373 212 672
Ice point 0 273 32 492
Absolute Zero -273 0 460 0
Homogeneous and Heterogeneous Systems
Matter can exist in any one of the three phases namely solid, liquid and gas. A system consisting of
a single phase is known as homogeneous systems. If the matter exists in more than one phase, the system
is known as heterogeneous system.
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1.9 Pure Substances
Substances of fixed chemical composition throughout are known as pure substances.
or phases in which they exist.
Example
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That is, pure substances have homogenous and invariable chemical composition irrespective of the phase
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a. Atmosphere air
b. Water
c. Nitrogen
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d. Water-steam mixture
e. Product of combustion.
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Though, mixture of water and steam is considered a pure substance, air and liquid air cannot be,
since, the chemical composition of liquid air differs from that of gaseous air.
The Ideal Gas
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Based on the experimental work carried out by Boyle, Charles and Gay-Lussac, pressure,
temperature and specific volume of many gases at low pressure and moderate temperature are related by
the following equation.
pv = RT where R=
This equation is known as equation of state of an ideal gas. The term R is known as characteristic
gas constant and Ru universal gas constant. In SI unit Ru= 8.314 kJ/kgmol.K.
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1.10 Concept of continuum
In microscopic approach the substance is assumed to be continuously distributed, ignoring the
space between the molecules. This is known as continuum hypothesis.
Since the matter is treated as continuous, the density at a point can be defined as
lim m
v v, v
Where v’ is the smallest volume for which a definite value of the ratio exists. Below the limiting
value of v’ , the fluctuation in average density will be high and a definite value for the ratio becomes
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impossible, with the mean free path* of the molecules approaching the order of magnitude of the
dimension of the vessel
1.11 WORK AND HEAT
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In the previous chapter, the different thermodynamic systems and their characteristics were
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discussed. To undergo a change of state, the system has to interact with its surroundings. Work and heat
transfers across the boundaries cause these changes. In this chapter various forms of work and modes of
heat transfers are discussed.
Work as Defined in Mechanics
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work is done when the point of application of a force moves in the direction of the force. The
product of the force and the distance moved in the direction of the force is equal to the amount of the
work done.
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This simple definition of work confines only to the area of mechanics and can not be extended to
the more complex problems in thermodynamics. Hence a new definition should be introduced to cover
mechanical as well as the other forms of work.
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The Thermodynamic Definition of Work
Positive work is done by a system, during a given process, when sole effect external to the system
could be reduced to the lifting of a mass.
Consider a gas expanding in a piston cylinder arrangement as given in Figure 2.1. Here no mass is
actually lifted against gravity. But if the existing surroundings is fitted with an arrangement as given in
the Figure 2.2, there is a possibility of lifting the mass. Hence work is said to be done by the system.
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While exploring the possibility of lifting a mass the effects that are external to the system alone
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must be taken into account. For example, a lift with a person and a suitcase is considered as a system. If
the person lifts the suitcase, it should not be taken into account, because this event occurs within the
system.
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1.12 Units of Work and Power
In the international system (SI), the unit of force is Newton (N) and that of distance is metre (m).
Hence the unit of work is Nm which is also given a special name Joule. In most of the applications large
quantity of work is involved. Therefore kJ is commonly used.
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Rate of doing work is known as power. Hence its unit is Nm/S or J/S which is again given a
special name Watts(W).
1.13 Sign Convention of Work
Work done by the system on the surroundings is considered as positive work.
Work done on the system by the surroundings is taken as negative work.
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1.14 Displacement Work
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Consider a piston cylinder arrangement as given in the Figure 2.4. If the pressure of the fluid is
greater than that of the surroundings, there will be an unbalanced force on the face of the piston. Hence,
the piston will move towards right.
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Force acting on the piston Pressure Area
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pA
Work done Force distance
pA dx
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pdV
where dV - change in volume.
This work is known as displacement work or pdV work corresponding to the elemental
displacement dx. To obtain the total work done in a process, this elemental work must be added from the
initial state to the final state. Mathematically, .
Evaluation of Displacement Work
Constant Pressure Process
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Figure 2.5 shows a piston cylinder arrangement containing a fluid. Let the fluid expands such that
the pressure of the fluid remains constant throughout the process. Figure 2.6 shows the process in a p-V
diagram.
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The mathematical expression for displacement work can be obtained as follows:
p(V2 – V1)
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This expression shows that the area under a curve in a p-V diagram gives work done in the process.
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Constant volume process
Consider a gas contained in a rigid vessel being heated. Since there is no change in volume, the
displacement work .
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Hyperbolic process
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Let the product of pressure and volume remains constant at all the intermediate states of a process.
In the p-V diagram it will be a hyperbola as given in Figure 2.7.
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1
W2 = pdV
1
2
= CdV where C=pV
1
2
1
= C V dV
1
= C ln (V2/V1)
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1
w2 = p1V1ln(V2/V1) (or) p2V2ln (V2/V1) ...(2.2)
For Ideal gases when temperature remains constant, pV will be constant i.e., isothermal process are
hyperbolic processes for an ideal gas.
Polytropic Process .co
Any process can be represented by the general form pVn constant. Based on the valve of n, the
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process differs as given below;For other values of n, the process is known as polytropic process. Figure
2.8 shows the polytropic process of various possible polytropic index ‘n’ on p-V coordinates. Expression
for displacements work for a polytropic process can be obtained as follows :
pdV
da
1
W2
1
2
C
V dV where C = pVn
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n
1
2
C V n dV
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2
V n 1
C
n 1 1
2
CV2 n 1 CV1 n 1
n 1 1
p 2V2 nV2 n 1 p1V1 nV1 n 1
since C p1V1n p2Vn2
n 1
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p 2V2 p1V1
n 1
Work is a Path Function
Consider a working substance initially occupying 0.2 m3 at 1 bar as represented by state 1 in the
Figure 2.9. Let the system changes its state such that the final volume is 0.05m3 and pressure 2 bar. The
change of state may occur along the paths 1A2,1B2 or 1C2. As mentioned earlier, area under the curve
representing the process in a p-V diagram gives the work done in the process. Comparing the area under
the paths 1A2, 1B2 and 1C2, it is clear that the work done in these paths are different. Hence it can be
concluded that the amount of work done is not only a function of the end states of a process, but also the
path followed between the states. Therefore work is a path function.
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Additivity of Work Over Processes
work done in the individual processes.
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If a system is taken through two or more number of processes, the total work done is the sum of
Let a system executes three processes as shown in Figure 2.10. The total work done,
W4 1W2 2W3 3W4
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1
1.15 Heat
Heat is the interaction between systems which occurs by virtue of their temperature difference
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when they communicate.
If a system, at a given temperature is brought in contact with another system (or surroundings) at a
lower temperature, it can be observed that heat is transferred from the system at the higher temperature to
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the system at lower temperature. This heat transfer occurs solely because of the temperature difference
between the two systems. Another important aspect of the definition of heat is that a body never contains
heat. Rather, heat can be identified only as it crosses the boundary. Similar to work, heat is also a form of
energy transfer occurring at the boundary of the system and is a path function.
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Sign Convention of Heat
Heat given into a system is positive
Heat coming out of the system is negative
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Fig. 2.8 Sign convention of work
Modes of Heat Exchange
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Conduction, convection and radiation are the three possible modes of heat transfer between systems
and between system and its surroundings.
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Conduction occurs without bulk movement of molecules. Energy transfer in conduction is due to
lattice vibration and free electron movement. It is the predominant mode of heat transfer in solids.
Convection occurs with bulk movement of molecules and therefore, occurs in gases and liquids. If
the bulk movement or flow is due to an external device, it is known as forced convection. In the absence
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of an external device the flow is due to the difference in density caused by the temperature difference.
This mode is known as natural convection.
Bodies separated by a distance may exchange heat in the form of electromagnetic waves without
the participation of the intervening medium. It is known as radiation. It is generally a surface
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phenomenon. Sometimes as in the case of gas mixtures containing carbon dioxide and water vapour it is a
volume phenomenon.
1.16 Sensible and Latent Heat
vil
It is known that a substance can exists in three phases namely solid, liquid and gas. When a
substance is heated or cooled temperature of the substance increases or decreases respectively unless there
is any phase change. Quantity of heat added or removed to change the temperature by unit degree is
Ci
known as specific heat. For solids and liquids same quantity of heat is required to cause unit degree rise
for both constant pressure heating as well as constant volume heating as they are incompressible. But for
gases there is appreciable difference in the quantity of heat required to cause unit difference in
temperature between constant volume and constant pressure processes. Accordingly, they are known as
specific heat at constant volume (CV) and specific heat at constant pressure (CP). Thus to increase the
temperature of m kg of the given substance by T degree, amount of heat required is given by
Q mCVT at Constant Volume ...(2.5)
Q1 mCPT at Constant Pressure …(2.6)
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If a certain single component system is undergoing phase change at constant pressure, temperature
of the system remains constant during heating or cooling. Quantity of heat removed or added to cause the
change of phase of unit mass of the substance is known as latent heat. For example latent heat of fusion of
water is the amount of heat to be removed to solidify 1 kg of water into 1 kg of ice at a given temperature.
Let us consider a process of converting 1 kg of ice at 30C to system to steam at 250C at
atmospheric pressure. We know that ice melts at 0C and water evaporates at 100C at atmospheric
pressure.
For a constant rate of heating, if temperature at different instants are plotted we will get a graph as
shown in Figure 2.9.
m
.co
tas
da
Figure 2.9 Illustration for sensible and latent heat
vil
The total heat required can be obtained as follows:
Q Qab Qbc Qcd Qde Qef ...(2.7)
Ci
Qab mCice (tb tc) ...(2.8)
Qbc Latent heat of melting of ice at 0C
Qcd mCwater (td tc) ...(2.9)
Qde Latent heat of evaporation of water at 100C
Qef mCPSteam (tf - te) ...(2.10)
Where Cice Specific heat of ice
Cwater Specific heat of water
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CPSteam Specific heat of steam at constant pressure
Reversible Adiabatic Process
A reversible process during which, the system and the surroundings do not exchange any heat
across the boundary is known as reversible adiabatic process. For such a process, pressure and volume
variation is governed by the law :
pV constant . ..(2.11)
Where
Cp is the specific heat at constant pressure
m
CV is the specific heat at constant volume
Detailed discussion on these specific heats is presented in the next chapter.
.co
A wall which does not permit the heat flow across it is known as adiabatic wall, whereas the wall
that permits the heat is known as diathermic wall. In an adiabatic process the only possible energy
interaction across the boundary of the system is work transfer to or from the system.
Displacement work involved in a reversible adiabatic process can be expressed as
tas
p 2V2 p1V1
W= ...(2.12)
1
da
Comparison between work and heat
Both heat and work are boundary phenomena, that is, they occur only at the
boundary.
vil
The interaction due to the temperature difference is heat and all other
interactions are to be taken as work.
Ci
Both work and heat are path functions, that is, they are inexact differentials.
1.17 THE FIRST LAW OF THERMODYNAMICS
Energy interactions between a system and its surroundings across the boundary in the form of heat
and work have been discussed separately in the previous chapter.
So far, no attempt has been made to relate these interactions between themselves and with the energy
content of the system.
First law of thermodynamics, often called as law of conservation of energy, relating work, heat,
and energy content of the system will be discussed in detail in this chapter.
First Law of Thermodynamics
In its more general form, the first law may be stated as follows
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“When energy is either transferred or transformed, the final total energy present in all forms must
precisely equal the original total energy”.
It is based on the experimental observations and can not be proved mathematically. All the
observations made so far, confirm the correctness of this law.
First Law of Thermodynamics for a Closed System Undergoing a Process
First law can be written for a closed system in an equation form as
Energy entered Energy left Change in the energy
into the system the system content of the system
For a system of constant mass, energy can enter or leave the system only in two forms namely work
and heat.
m
Let a closed system of initial energy E1 receives Q units of net heat and gives out W units of work
during a process. If E2 is energy content at the end of the process as given in Figure 3.1, applying first
law we get
.co
tas
da
vil
Q W (E2 E1)
Where the total energy content
Ci
Internal Energy + Kinetic energy + Potential energy
1 mC 2
U + + mgz
2 gc
The term internal energy usually denoted by the letter U is the energy due to such factors as
electron spin and vibrations, molecular motion and chemical bond.
Kinetic energy term is due to the system movement with a velocity C. For stationary systems this
term will be zero. The term gc is a constant of value 1 in SI unit. It will be dropped here after since SI
unit is followed throughout the book.
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Potential energy term is due to the location of the system in the gravitational field. It remains
constant for a stationary system. The unit of energy in SI is kJ.
The Thermodynamic Property Enthalpy
Consider a stationary system of fixed mass undergoing a quasi-equilibrium constant pressure
process
Applying first law
Q12 1W2 E2 E1
where E2 E1 (U2 U1) + m(C22 C12) + mg(Z2 Z1)
m
U2 U1 since it is a stationary system.
also 1W2 p(V2 V1)
p2V2 p1V1
.co
tas
Q12 (p2V2 p1V1) + (U2 U1)
Q12 (U2 + p2V2) (U1 + p1V1)
da
The terms within brackets are all properties depending on the end states. This combination of
properties may be regarded as a single property known as enthalpy. It is usually denoted by the letter H.
vil
ie H U + pV
(or) h u + pv
Where h is specific enthalpy in kJ/kg
Ci
u is specific internal energy in kJ/kg and
v is specific volume in m3/kg
Flow Energy
Flow energy is defined as the energy required to move a mass into the a control volume against a
pressure. Consider a mass of volume V entering into a control volume as given in the Figure 3.2 against a
pressure p.
26 S.A.RAMESH – AP/MECH
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m
.co
The Flow energy Work done in moving the mass
tas
Force distance
pA dx
da
p (Adx)
pV
vil
Therefore, Enthalpy Internal energy + Flow energy
First Law of Thermodynamics for a Control Volume
Ci
Mass simultaneously entering and leaving the system is a very common phenomenon in most of the
engineering applications. Control volume concept is applied to these devices by assuming suitable
control surfaces.
To analyze these control volume problems, conservation of mass and energy concepts are to be
simultaneously considered.
Energy may cross the control surface not only in the form of heat and work but also by total energy
associated with the mass crossing the boundaries. Hence apart from kinetic, potential and internal
energies, flow energy should also be taken into account.
Conservation of mass
27 S.A.RAMESH – AP/MECH
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Total mass Total mass Net change in the
entering the leaving the mass content of the
control volume control volume control volume
Conservation of energy
Net energy crossing the Total energy Total energy Net change
boundary in the associated withthe associated withthe in theenrgy
form of heat mass entering mass leaving content of the
and work the control volume the control volume control volume
m
.
W
.co
tas
. Control .
min mout
Volume
da
Control Surface
.
Q
vil
Figure 3.3 First Law of Thermodynamics Applied to a control Volume
Ci
As a rate equation, it becomes
Q W m
in h
C2
Zg
m
out h
C2
Zg ECV
in 2 out 2
1.18 The Steady-state Flow Process
When a flow process is satisfying the following conditions, it is known as a steady flow process.
28 S.A.RAMESH – AP/MECH
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1. The mass and energy content of the control volume remains constant with time.
2. The state and energy of the fluid at inlet, at the exit and at every point within the control
volume are time independent.
3. The rate of energy transfer in the form of work and heat across the control surface is constant
with time.
Therefore for a steady flow process
m
in mout
also
ECV 0
m
Q W m
in
in h
C2
2
.co
out
Zg mout h
C2
2
Zg 0
tas
For problem of single inlet stream and single outlet stream
da
C 2 C1 2
Q W m (h 2 h1 ) 2 Z 2 Z1 g
2
vil
This equation is commonly known as steady flow energy equation (SFEE).
Application of SFEE
Ci
SFEE governs the working of a large number of components used in many engineering practices.
In this section a brief analysis of such components working under steady flow conditions are given and
the respective governing equations are obtained.
Turbines
Turbines are devices used in hydraulic, steam and gas turbine power plants. As the fluid
passesthrough the turbine, work is done on the blades of the turbine which are attached to a shaft. Due to
the work given to the blades, the turbine shaft rotates producing work.
29 S.A.RAMESH – AP/MECH
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Mass entering
Shaft work
m
Control
Mass leaving
Surface
.co
Figure 3.4 Schematic Representation of a Turbine
tas
General Assumptions
1. Changes in kinetic energy of the fluid are negligible
2. Changes in potential energy of the fluid are negligible.
da
Q W m (h
2 h1 )
vil
Compressors
Compressors (fans and blowers) are work consuming devices, where a low-pressure fluid is
compressed by utilising mechanical work. Blades attached to the shaft of the turbine imparts kinetic
Ci
energy to the fluid which is later converted into pressure energy.
30 S.A.RAMESH – AP/MECH
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Mass leaving
Shaft work
Control
m
Surface
Mass entering
General Assumptions
.co
Figure 3.5 Schematic Representation of a Compresso
tas
1. Changes in the kinetic energy of the fluid are negligible
2. Changes in the potential energy of the fluid are negligible
da
Governing Equation
Applying the above equations SFEE becomes
Q W m (h h1 )
vil
Pumps
Similar to compressors pumps are also work consuming devices. But pumps handle incompressible
Ci
fluids, whereas compressors deal with compressible fluids.
31 S.A.RAMESH – AP/MECH
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General Assumptions
1. No heat energy is gained or lost by the fluids;
2. Changes in kinetic energy of the fluid are negligible.
Governing Equation
W m (h
2 h1 ) Z 2 Z1 g ...(3.13)
As the fluid passes through a pump, enthalpy of the fluid increases, (internal energy of the fluid
m
remains constant) due to the increase in pv (flow energy). Increase in potential energy of fluid is the most
important change found in almost all pump applications.
Nozzles .co
Nozzles are devices which increase the velocity of a fluid at the expense of pressure. A typical
tas
nozzle used for fluid flow at subsonic* speeds is shown in Figure 3.7.
General Assumptions
1. In nozzles fluids flow at a speed which is high enough to neglect heat lost or gained
da
as it crosses the entire length of the nozzle. Therefore, flow through nozzles can be
regarded as adiabatic. That is 0.
2. There is no shaft or any other form of work transfer to the fluid or from the fluid; that is
vil
0.
3. Changes in the potential energy of the fluid are negligible.
Ci
Control Surface
In Out
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Governing Equation
C 2 2 C1 2
(h2 h1 ) 0
2
C 2 2 C1 2
(h1 h2 )
2
Diffusers
Diffusers are (reverse of nozzles) devices which increase the pressure of a fluid stream by reducing
m
its kinetic energy.
General Assumptions
1.
.co
Similar to nozzles, the following assumptions hold good for diffusers.
Heat lost or gained as it crosses the entire length of the nozzle. Therefore, flow through nozzles can
be regarded as adiabatic. That is Q 0
tas
2. There is no shaft or any other form of work transfer to the fluid or from the fluid; that is
0.
3. Changes in the potential energy of the fluid are negligible
da
Governing Equation
C2 2 C12
(h2 h1 ) 0
vil
2
C12 C2 2
(h2 h1 )
2
Ci
Heat Exchangers
Devices in which heat is transferred from a hot fluid stream to a cold fluid stream are known as
heat exchangers.
Throttling
A throttling process occurs when a fluid flowing in a line suddenly encounters a restriction in the flow
passage. It may be
a plate with a small hole as shown in Figure 3.10 (a)
a valve partially closed as shown in Figure 3.10 (b)
33 S.A.RAMESH – AP/MECH
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a capillary tube which is normally found in a refrigerator as shown in Figure 3.10 (c)
a porous plug as shown in Figure 3.10 (d)
m
First Law for a Cyclic Process
.co
tas
In a cyclic process the system is taken through a series of processes and finally returned to its
original state. The end state of a cyclic process is identical with the state of the system at the beginning of
the cycle. This is possible if the energy level at the beginning and end of the cyclic process are also the
same. In other words, the net energy change in a cyclic process is zero.
da
1
p
vil
Path A
Ci
Path B 2
V
Figure 3.11 First Law for a Cyclic Process
34 S.A.RAMESH – AP/MECH
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Consider a system undergoing a cycle consisting of two processes A & B as shown in Figure 3.11
Net energy change
EA +EB 0 ..(3.17)
(QA WA) + (QB WB) 0 ...(3.18)
ie QA QB WA WB ...(3.19)
(or) dQ dW ...(3.20)
Hence for a cyclic process algebraic sum of heat tranfers is equal to the algebraic sum of work
transfer.
m
This was first proved by Joule, based on the experiments he conducted between 1843 and 1858,
that were the first quantitative analysis of thermodynamic systems.
Energy is a property of a system
.co
Consider a system undergoing a process from state1 to state2 along path A as shown in Figure
3.12. Let the system be taken back to the initial state 1 along two possible paths B and C. Process A,
tas
combined separately with process B and C forms two possible cycles.
1
p
da
Path A
vil
Path C
Ci
Path B 2
V
Figure 3.12 Illustration to show that energy is property
35 S.A.RAMESH – AP/MECH
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Cycle 1A2B1
QA QB [WA WB]
QA WA [QB WB]
EA EB ...(3.21)
Cycle 1A2C1
QA QC [WA WC]
QA WA [QC WC]
m
EA EC ...(3.22)
From Equation (3.21) and (3.22) it can be concluded that energy change in path B and path C are
.co
equal and hence energy is a point function depending only on the end states.
It has been already shown that all the properties are point functions and hence energy is also a
property of the system.
tas
Specific Heat at Constant Volume and at Constant Pressure
Specific heat at constant volume of a substance is the amount of heat added to rise the temperature
of unit mass of the given substance by 1 degree at constant volume
da
From first law for a stationary closed system undergoing a process
vil
dQ pdV + dU or dq pdv + du
For a constant volume process
dQ dU or dq du
Ci
or du CvdT ...(3.23)
Similarly specific heat at constant pressure is the quantity of heat added to rise the temperature of unit
mass of the given substance by 1 degree at constant pressure
where dQ pdV + dU
dQ pdV + d(H PV)
36 S.A.RAMESH – AP/MECH
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dQ pdV + dH Vdp pdV
dQ dH Vdp
For a constant pressure process dp 0
Hence dQ dH or dq dh
or dh CpdT
The difference in specific heats Cp Cv R
The ratio of sp. heat Cp/Cv
m
Since h and u are properties of a system, dh CpdT and duCvdT, for all processes.
Work Interaction in a Reversible Steady Flow Process
.co
In a steady flow process the work interaction per unit mass between an open system and the
surroundings can be expressed in differential form as
tas
dq dw dh + CdC + gdz
dw dq (dh + CdC +gdz)
da
Also, dq du + pdv (or) dh vdp
Therefore, dw dh vdp (dh + CdC + gdz)
vil
vdp (CdC + gdz)
C 2 2 C1 2
Ci
For a stationary W vdp g ( z 2 z1 ) system
1 2
2
W vdp
1
3.26)
First law for an open system under unsteady flow conditions
37 S.A.RAMESH – AP/MECH
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Many processes of engineering interest involve unsteady flow, where energy and mass
content of the control volume increase or decrease.
Example for such conditions are:
1) Filling closed tanks with a gas or liquid.
2) Discharge from closed vessels.
3) Fluid flow in reciprocating equipments during an individual cycle.
To develop a mathematical model for the analysis of such systems the following assumptions are
made.
1) The control volume remains constant relative to the coordinate frame.
m
2) The state of the mass within the control volume may change with time, but at any
instant of time the state is uniform throughout the entire control volume.
.co
3) The state of the mass crossing each of the areas of flow on the control surface
is constant with time although the mass flow rates may be time varying.
Unlike in steady flow system, duration of observation t plays an important role in transient
analysis. Let mass of the working fluid within the control volume before and after the observation be m1
tas
and m2 respectively. Applying mass balance we get,
(m2 m1)CV mi m0 ...(3.27)
da
Where mi is the mass entered the control volume during the interval t seconds.
m0 is the mass left the control volume during the interval t seconds.
vil
By applying energy balance we get,
Qcv Wcv min h Zg mout h Zg Ecv
Ci
C2 C2
in 2 out 2
...(3.28)
Where ECV is the change in energy content of the control volume in t seconds.
QCV is the heat energy entered into the control volume in t seconds.
WCV is the work energy left the control volume in t seconds.
hi & h0 are specific enthalpy of the inlet and outlet streams respectively.
38 S.A.RAMESH – AP/MECH
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are the kinetic energy of the inlet and outlet streams
respectively.
Zig & Z0g are the potential energy of inlet and outlet streams
respectively.
Perpetual Motion Machine - I
An engine which could provide work transfer continuously without heat transfer is known as perpetual
motion machine of first kind. It is impossible to have such an engine as it violates first law of
thermodynamics.
m
.co
tas
da
vil
Ci
39 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
UNIT II
THE SECOND LAW OF THERMODYNAMICS
Limitations of First Law of Thermodynamics
If a well insulated tank of fluid is stirred by a rotating paddle wheel, the energy of the fluid
increases. If the stirrer is stopped, however the energy of the fluid will not decrease and cause the stirrer
to rotate in the opposite direction. The possibility of this process proceeding in the opposite direction is
not excluded by the first law of Thermodynamics. Hence first law of thermodynamics does not allow us to
predict whether a proposed conceived energy conversion is possible or not.
m
In all the internal combustion engines fuel and air mixture is supplied at room temperature. This
mixture undergoes combustion inside the engine and gives out work. Exhaust gases coming out of the
engine are always at higher temperature, indicating that some heat is taken away into atmosphere. Hence,
.co
in all the IC engines only a part of the heat is converted into work. From our experience we know that if
any attempt is made to convert all the heat into work, our effort will go in vain. This limitation in the
extent of energy conversion has also not been addressed in first law of thermodynamics.
tas
2.1 The Second law of Thermodynamics
Kelvin Planck’s statement : It is impossible to construct a device that, operating continuously, will
produce no effect other than transfer of heat from a single thermal
da
reservoir and performance of an equal amount of work.
The term thermal reservoir refers to a very large system in stable equilibrium, to which or from
which, any amount of heat can be transferred at constant temperature.
vil
A thermal reservoir supplying heat continuously at constant temperature is known as source.
(Example : Sun)
A thermal reservoir receiving heat continuously at constant temperature is known as sink.
Ci
(Examples : River, Sea)
From Kelvin-Planck statement it is clear that for any system to operate in a cycle and to give out
work continuously it should interact with a minimum of two reservoirs at different temperatures. The
system will receive heat from the high temperature reservoir and reject heat to the low temperature
reservoir. Such devices are known as heat engines. Performance (or) Efficiency of a heat engine can be
expressed as the ratio of desired output to the required input. In a heat engine the desired output is net
work output and the required input is total heat input
40 S.A.RAMESH – AP/MECH
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Source
Desired
Effect
Qin Heat
W
Required Engine
m
Effect
Qout
.co Sink
tas
Figure 4.1 Heat Engine
Wnet
Qin
da
From first law of thermodynamics
Q W
vil
Qin Qout Wnet
Clausius statement : Unaided by an external agency heat can not be transferred from a body at lower
temperature to a body at higher temperature.
Ci
Devices that are used to transfer heat from a body at lower temperature to a body at higher
temperature are known as refrigerators (or) heat pumps. If the high temperature side is atmosphere it is a
refrigerator. If the low temperature side is atmosphere it is known as a heat pump. The performance index
here is called coefficient of performance (COP). In refrigerator (and heat pumps) the performance is the
ratio of two independent parameters and hence the possibility of getting the value more than unity is
always there. But the term efficiency is restricted to a maximum of unity. Hence the term efficiency is not
used here.
Desired Effect
COP
Re quired Effect
Q
41 2
COPS.A.RAMESH – AP/MECH
W
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Taking work as external agency, for refrigerators (Figure 4.2)
From first law
Q W
Q1 Q2 W
Q2
COP
Q1 Q2
Sink
m
[Atmosphere]
Required
Effect
.co Q1
Refrige
tas
W rator
Desired
Q2
da
Effect
Source
vil
[conditioned Space]
Ci
Figure 4.2 Refrigerator
42 S.A.RAMESH – AP/MECH
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Sink
Desired [Conditioned Space]
Effect
Q1
Heat
W Pump
m
Required
Effect Q2
.co Source
tas
[Atmosphere]
da
Figure 4.3 Heat Pump
Similarly for a heat pumps (Figure 4.3)
vil
Desired Effect
COP
Re quired Effect
Ci
Q1
COP
W
Since , Q1 Q2 W
Q1
COP
Q1 Q2
2.2 Equivalence of Kelvin-Planck and Clausius Statements
The Clausius and Kelvin-Planck statements of the second law are entirely equivalent. This
equivalence can be demonstrated by showing that the violation of either statement can result in violation
of the other one.
43 S.A.RAMESH – AP/MECH
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Referring to Figure 4.4(a) the device marked Clausius violator is pumping Q1 amount of heat from
a low temperature reservoir at T1 to a high temperature reservoir at T2 without the aid of any external
agency. This is an impossible arrangement.
If such an arrangement is possible it would also violate Kelvin-Planck statement. Let a heat engine
operating between the same reservoirs at T2 and T1 take in Q2 as heat input at T2. It converts a part of this
heat into work and rejects heat Q3to the sink at T1. Since the Clausius violator is rejecting the same
quantity Q2at T2, it can be supplied directly into the heat engine so that the reservoir at T 2 can be
eliminated. This combination as shown in Figure 4.4 (b) is producing continuous work with a single
reservoir at T1. Hence it violates the Kelvin-Planck statement.
m
Reservoir
Reservoir
at T2 .co Q2
at T2
Q2
tas
W
Heat
Clausius
Engine
da
violator
Q3
vil
Q1
Reservoir at T1
Ci
(a)
44 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
Q2
Q2
W
Heat
Clausius
Engine
violator
Q1
m
Q3
Reservoir at T1
.co
tas
(b)
Figure 4.4 Illustration of the equivalence of Clausius and Kelvin-Planck’s statement
da
Referring to Figure 4.5 a Kelvin-planck violator is converting all heat QH taken from the reservoir
at TH into work. If such an impossible heat engine is assumed to exist it will violate the Clausius
vil
statement. Consider a refrigerator pumping QL heat from the low temperature reservoir at TL to the
reservoir at higher temperature TH. Combined with the Kelvin-Planck violator, the arrangement is
pumping QL heat from TL to TH, without any external agency. Hence it violate the Clausius statement.
Ci
2.3 Reversible Process
A process is said to be reversible if it can be reversed without leaving any trace on the
surroundings.
For example, let a system be taken from state 1 to state 2 with a work transfer of +5 kJ and heat
transfer of 10 kJ. If the process is reversible, while taking the system from state 2 to state 1, the work
transfer must be 5 kJ and heat transfer must be +10 kJ. So that, both the system and surroundings are
returned to their initial states at the end of the process 2 to 1.
45 S.A.RAMESH – AP/MECH
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Irreversibility and Causes of Irreversibility
The factors that make a process irreversible are known as irreversibilities. Various forms of
irreversibilities are listed below.
a) Friction : Friction occurs at the interface of two bodies moving relative to each other. It
is the main cause of irreversibility in many processes. Energy spent in
overcoming friction is dissipated in the form of heat which can never be
restored.
b) Heat transfer: Once heat is transferred from a body at higher temperature to a body at lower
temperature, it can never be reversed without the aid of an external agency.
c) Unresisted expansion: Consider a vessel with two chambers as given in the arrangement as shown
m
in Fig. 4.6. If the members separating the gas from vacuum is removed, gas
will expand and occupy the entire space. Since the expansion has no influence
on the surroundings, there is no work output in this process. But to restore the
.co
initial arrangement, a definite work input is required.
d) Mixing of two gases: Consider a vessel with two chambers, one with O2 and the other with N2. When
the member separating O2 & N2 is removed, uniform mixing is taking place
without any work output. But such a process cannot be reversed without any
tas
work input.
e) Throttling: It is a totally irreversible process. Gas or vapour will expand through a
restricted passage with its pressure decreasing rapidly without any work output.
da
Such an expansion cannot be reversed.
Externally and internally reversible processes
As mentioned earlier if no irreversibilities occur outside the system boundaries during the process,
vil
it is known as externally reversible.
If no irreversibilities occur within the boundary of the system during a process, it is known as
internally reversible process. For such a process, the path of the reverse process will follow exactly that of
Ci
the forward process in any property diagram.
To be totally reversible or simply reversible both external and internal reversibilities must be
ensured.
The Carnot Cycle
In 1824, Nicholas Sadi Carnot proposed a classical ideal cycle consisting of four processes. All
processes are individually reversible and hence the cycle as a whole is a reversible cycle. The processes
that make up the Carnot cycle are :
46 S.A.RAMESH – AP/MECH
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Process 1-2
The working substance is taken in a piston cylinder arrangement as given in Figure 4.8(a). Heat is
added reversibly and isothermally from a high
m
.co
tas
temperature reservoir at TH. Since the process is to be reversible, the temperature TH of the reservoir
should be equal to or infinitesimally greater than that of the working substance.
da
vil
Ci
Process 2-3
The working substance is allowed to expand reversibly and adiabatically until its temperature falls
down to TL. The process is represented by Figure 4.8(b)
47 S.A.RAMESH – AP/MECH
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Process 3-4
Heat is rejected by the working substance to a low temperature reservoir kept T L or at temperature
infinitesimally smaller than TL.
Process 4-1
m
.co The working substance is then compressed
reversibly and adiabatically until its temperature becomes TH and the cycle continues.
tas
The cycle has been represented in a p-V diagram in Figure 4.9. The included area represents the net
work done in the cycle. From first law of thermodynamics net workdone is equal to net heat transfer in
the cycle. Since QH is the heat added to system and QL is the heat rejected by the system, the neat heat
da
transfer is QH QL.
vil
Isothermal heat addition Adiabatic compression
Ci
1 Effici
p Isothermal heat rejection
ency
2 of
Carno
t
Engin
e =
Adiabatic expansion 4 3
Wnet
Qin
v
48 S.A.RAMESH – AP/MECH
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QH QL
Qin
QL
= 1
Qin
Where
QL = 3W4 + U4 U3
Since the process is isothermal U4 U3
m
QL 3W4
P3 V3 ln
mRTL ln
p3
p4
p3
.co
tas
p4
p2
Similarly QH mRTH ln
p1
da
Process 2-3 is reversible adiabatic
1
vil
T2 p 2 TH
T3 p3 TL
Ci
Process 4-1 is also reversible adiabatic
1
T p TH
1 1
T4 p 4 TL
From the above two expressions,
p2 p
1
p3 p 4
p 2 p3
49
pS.A.RAMESH
1 p4 – AP/MECH
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Substituting the above condition we get
mRTL ln 3
p
Q
Carnot 1 L 1 p4
Qin mRTL ln p 2
p1
T
1 L
TH
It shows that efficiency of carnot engine is purely a function of TH and TL.
m
Since the carnot cycle being completely reversible, if carried out in reverse direction, the
magnitudes of all energy transfers remain the same but their sign change. This reversed carnot cycle can
cycle.
2.4 ENTROPY
.co
be applied for a refrigerator or a heat pump. Figure 4.10 shows the p-V diagram of a reversed carnot
tas
The first law of thermodynamics deals with the property energy and the conservation of energy.
The second law introduced in the previous chapter, leads to the definition of a new property called
entropy. Entropy is defined in terms of a calculus operation, and no direct physical picture of it can be
da
given. In this chapter, Clausius inequality, which forms the basis for the definition of entropy will be
discussed first. It will be followed by the discussion of entropy changes that take place during various
processes for different working fluids. Finally, the reversible steady-flow work and the isentropic
efficiencies of various engineering devices such as turbine and compressors will be discussed.
vil
The Clausius Inequality
Consider two heat engines operating between two reservoirs kept at temperature TH and TL as
Ci
shown in the Figure 5.1. Of the two heat engines, one is reversible and the other is irreversible.
50 S.A.RAMESH – AP/MECH
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For the reversible heat engine it has already been proved that
Q H TH
Q L TL
QH QL
0
TH TL
dQ
T 0
rev
m
As discussed earlier, the work output from the irreversible engine should be less than that of the
reversible engine for the same heat input QH. Therefore QL,Irrev will be greater than QL,Rev . Let us define
then
QL,Irrev QL,Rev dQ
.co
tas
dQ Q QL , Irev
T H
Irrev TH TL
Q QL ,rev dQ
H
da
TH TL TL
dQ
0
TL
vil
0
Ci
By combining this result with that of a reversible engine we get
dQ
T
Irrev
0
This is known as Clausius inequality.
Clausius inequality forms the basis for the definition of a new property known as entropy.
51 S.A.RAMESH – AP/MECH
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Consider a system taken from state 1 to state 2 along a reversible path A as shown in Figure 5.2.
Let the system be brought back to the
initial state 1 from state 2 along a
reversible path B. Now the system has
completed one cycle. Applying
Clausius inequality we get
m
dQ
0
2
T
dQ
1
dQ
1 T A 2 T B 0
.co
tas
...(5.2)
Instead of taking the system from state2 to state1 along B, consider another reversible path C. Then
da
for this cycle 1-A-2-C-1, applying Clausius inequality :
vil
dQ
T
0
...(5.3)
dQ dQ
2 1
1 T A 2 T C 0
Ci
Comparing 5.2 & 5.3
Hence, it can be concluded that the quantity is a point function, independent of the path followed.
Therefore it is a property of the system. Using the symbol S for entropy we can write
...(5.4)
upon integration we get
52 S.A.RAMESH – AP/MECH
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S2 S1 ... (5.5)
For a reversible process.
Entropy change for an irreversible process
The relationship between the entropy change and heat transfer across the boundary during an
irreversible processes can be illustrated with a simple cycle composed of two processes, one of which is
internally reversible and the other is irreversible, as shown in Figure 5.3. The Clausius inequality applied
to this irreversible cycle can be written as
Since the process B is internally reversible, this process can be reversed, and therefore
m
or
.co ...(5.6)
As defined in equation 5.5, since the process B being reversible the integral on the left hand side
can be expressed as
tas
...(5.7)
2.5 Temperature - Entropy diagram
da
In a T-s diagram consider a strip of thickness ds with mean height T as shown in Figure 5.4. Then
Tds gives the area of the strip.
vil
For a reversible process the elemental heat transfer
Ci
dQ Tds Area of the strip
To get the total heat transfer the above equation should be integrated between the limits 1 and 2, so
that, we get
...(5.8)
This is equivalent to the area under a curve representing the process in a T-S diagram as shown in
the Fig 5.4.
Note: For an isothermal process S2 S1 .
For reversible adiabatic process S2 S1 0.
53 S.A.RAMESH – AP/MECH
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2.6 Change in Entropy
a) Solids and Liquids
Change in entropy
Where dq du + pdv
For solids and liquids
pdv 0
m
Where c- is the specific heat
.co ...(5.9)
tas
b) For ideal gases change in entropy
da
Substituting
du CvdT
vil
We get ,Upon integration
Ci
Substituting dh CpdT
and
We get
Upon integration
54 S.A.RAMESH – AP/MECH
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2.7 Principle of Increase in Entropy
Applying Clausius inequality,
For an isolated system undergoing a process
Consider a system interacting with its surroundings. Let the system and its surroundings are
included in a boundary forming an isolated system. Since all the reactions are taking place within the
combined system, we can express
or
Whenever a process occurs entropy of the universe (System plus surroundings) will increase if it is
m
irreversible and remain constant if it is reversible. Since all the processes in practice are irreversible,
entropy of universe always increases
.co
This is known as principle of increase of entropy.
Adiabatic Efficiency of Compressors and Turbines
ie., (s)universe>0
tas
In steady flow compressors and turbines reversible adiabatic process is assumed to be the ideal
process. But due to the irreversibilities caused by friction between the flowing fluid and impellers, the
process is not reversible though it is adiabatic. Percentage deviation of this process from the ideal process
da
is expressed in terms of adiabatic efficiency.
(a) Compressors :
Since compressors are work consuming devices actual work required is more than ideal work.
vil
For compressors handling ideal gases
(b) Turbines :
In turbine due to irreversibilities the actual work output is less than the isentropic work.
Ci
55 S.A.RAMESH – AP/MECH
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2.8 Solved Problems
Prob : 5.1 A body at 200oC undergoes an reversible isothermal process. The heat energy removed
in the process is 7875 J. Determine the change in the entropy of the body.
System : Closed system
Known : T1 T2
200oC
473 K
Qrejected 7875 J
m
Process : Isothermal
To find : s
Analysis : S2 S1 for an isothermal process
16.65 J/K.
.co
tas
Comment : Entropy decreases as heat is removed from the system.
Prob : 5.2 A mass of 5 kg of liquid water is cooled from 100oC to 20oC. Determine the change in
entropy.
da
System : Closed system
Known : Mass of water 5kg
vil
T1 100 C 373 K
o
T2 20oC 293 K
Process : Constant pressure
Ci
To find : Change in entropy
Assumptions : 1) The process is reversible
2) The specific heat of liquid water is constant
Analysis : S2 S1 m
For this problem
p2 p1 & Cp 4.186
56 S.A.RAMESH – AP/MECH
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S2 S1 5
5.053
Comment : Entropy decreases as heat is removed from the system.
Prob : 5.3 Air is compressed isothermally from 100 kPa to 800 kPa. Determine the change in
specific entropy of the air.
System : Closed/Open
Known : p1 100 kPa
p2 800 kPa
m
To find : S - change in Specific entropy
Analysis : S R ln [Since the process is isothermal]
0.287 x ln
0.597 kJ/kgK.
.co
tas
o
Prob : 5.4 A mass of 5 kg of air is compressed from 90 kPa, 32 C to 600 kPa in a polytropic
process, pV1.3 constant. Determine the change entropy.
System : Closed / Open
da
Known : p1 90 kPa
T1 32oC 305 K
vil
p2 600 kPa
m 5 kg
Ci
Process : pV Constant
1.3
To find : S - Change in entropy
Analysis : S2 S1 m
Where T2 T1
305
473 K
57 S.A.RAMESH – AP/MECH
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S2 S1 5
0.517 kJ/K.
Comment : For air the ratio of Cp and Cv is equal to 1.4. Therefore the polytropic index n
1.3(<1.4) indicates that some heat is removed from the system resulting in
negative entropy.
Prob : 5.5 A rigid insulated container holds 5 kg of an ideal gas. The gas is stirred so that its state
changes from 5 kPa and 300 K to 15 kPa. Assuming Cp 1.0 kJ/kgK and 1.4,
determine the change of entropy of the system.
System : Closed
m
Process : Constant volume since the gas is stirred in an rigid container
Known : p1 5 kPa p2 15 kPa
m 5 kg
T1 300 K
To find :
1.4
.co
Cp 1.0 kJ/kgK
Change in entropy
tas
Analysis : S2 S1 m
By applying the state equation.
da
Since V2 V1
vil
Also R Cp Cv
Ci
0.286 kJ/kgK
Substituting these values we get
S2 S1 5
58 S.A.RAMESH – AP/MECH
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3.922 kJ/K
Comment : Though this process is adiabatic it is not isentropic since the process of stirring is an
irreversible process.
Prob : 5.6 An insulated rigid vessel is divided into two chambers of equal volumes. One chamber
contains air at 500 K and 2 MPa. The other chamber is evacuated. If the two chambers
are connected d, what would be the entropy change ?
System : Closed system
Process : Unresisted expansion
Known : T1 500 K
m
p1 2 10 kPa
3
To find : Entropy change
Diagrams :
Analysis : s2 s1
.co
tas
s2 s1
After expansion air will occupy the entire volume of the container.
V2 2V1
da
Also 1
W2 0 since it is an unresisted expansion
Q12 0 since the vessel is insulated
vil
Applying the first law of thermodynamics
Q12 U + 1W2
Ci
Therefore u 0
For air
mcv(T2 T1) 0
i.e. T2 T1
Hence s2 s1 Cvln + Rln
0.287 ln
59 S.A.RAMESH – AP/MECH
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0.199 kJ/kgK
Comment : Though the process is adiabatic entropy increases as the process involving
unresisted expansion is an irreversible process. It also proves the fact that
Prob : 5.7 An adiabatic chamber is partitioned into two equal compartments. On one side there is
o
oxygen at 860 kPa and 14 C. On the other side also, there is oxygen, but at 100 kPa and
14oC. The chamber is insulated and has a volume of 7500 cc. The partition is abruptly
removed. Determine the final pressure and the change in entropy of the universe.
System : Closed
m
Process : Adiabatic Mixing
Known :
Subsystem I
Fluid
Subsystem II
Oxygen
.co Oxygen
tas
Initial pressure 850 kPa 100 kPa
Initial Temperature 14oC 14oC
Initial volume
da
Diagrams :
Analysis : Here the energy interaction is taking place only between the two fluids and therefore the
vil
energy lost by one fluid should be equal to the energy gained by the other fluid. Taking t F
as the final temperature we get
Ci
Since the same fluid is stored in both the systems at the same temperature
C1 C2 and
t1 t2 14oC
Therefore the final temperature will also be 14oC
After removing partition total mass of oxygen is occupying the entire 7500cc at 14oC.
Hence the final pressure can be computed as given below :
0.0427 kg
60 S.A.RAMESH – AP/MECH
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0.00503 kg
To find the final pressure
m1 m2
475 kPa
Ssystem S1 S2
Ssurroundings 0
Suniverse 8.596
m
Prob : 5.8 A closed system is taken through a cycle consisting of four reversible processes. Details
of the processes are listed below. Determine the power developed if the system is
executing 100 cycles per minutes.
Process Q (kJ) .co
Temperature (K)
Initial Final
tas
1-2 0 300 1000
2-3 +1000 1000 1000
3-4 0 1000 300
da
4-1 - 300 300
System : Closed
vil
Process : The system is executing cyclic process.
Known : Heat transfer in process 12, 23 and 34 and temperature change in all the process.
Ci
No of cycles per minute.
To find : Power developed.
Analysis : To find the power developed Wnet per cycle must be known.
From I Law Wnet Qnet which can be computed from the following table
Process Q (kJ) Temperature (K) S
Initial Final
1-2 0 300 1000 0
61 S.A.RAMESH – AP/MECH
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2-3 1000 1000 1000
3-4 0 1000 300 0
4-1 - 300 300 S41
For a cyclic process 0
where is any property
S 0
(i.e.,) S12 S23 S34 S41 0
m
0 1 0 S41 0
Since the process 4-1 is isothermal
1
.co
S41 1
tas
Q41 300 kJ
Therefore
da
Qnet Q12 Q23 Q34 Q41
0 1000 0 300
vil
700 kJ per cycle
Wnet Qnet 700 kJ
Ci
and power developed
700
1166.7 kW
2.9 AVAILABLE ENERGY, AVAILABILITY AND IRREVERSIBILITY
From second law of thermodynamics we found that complete conversion of heat into work is not
possible in a continuous process. Also it has been proved that the most efficient cycle to produce work is
a reversible power cycle (Carnot cycle). Even in carnot cycle, the efficiency of conversion can never be
62 S.A.RAMESH – AP/MECH
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unity and hence to establish a comparison of the work-energy conversion in actual processes, the
maximum theoretical work obtainable with respect to some datum must be determined. This chapter is
dedicated for this objective.
Available and Unavailable Energy
The energy content of a system can be divided into two parts
Available energy, which under ideal conditions may be completely converted into work
Unavailable energy which is usually rejected as waste.
Consider Q units of heat energy available at a temperature T. Available part of energy can be
obtained by assuming that the heat is supplied to a Carnot engine. Work obtained from the carnot engine
T To T
m
Q is the available part. The quantity o Q is the unavailable part. In a T-S diagram these
T T
quantities can be represented as shown in the fig 6.1. The term T 0 is the ambient temperature. Hence it
ambient conditions also.
Reversible Work In A Non-flow Process
.co
can be concluded that the available and unavailable part of energy content of a system depends on the
tas
From first law of thermodynamics
Qsys W=U2 U1 ...6.1
From second law of thermodynamics for a reversible process
da
(s)universe = (s)system + (s)surroundings
=0 ...6.2
vil
Where (s)system =S2- S1
Qsurr QSys
(s)surroundings=
Ci
TSurr To
where,
Qsystem = To(S2S1) ...6.3
substituting in 6.1 we get
To(S2S1) W=U2 U1
W= (U2 U1) (S1 S2)
since the process is reversible W can be represented Wrev
Wrev= (U1 U2) To(S1 S2) ...6.4
63 S.A.RAMESH – AP/MECH
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This is also the maximum work in the process.
For a closed system, when undergoing change in volume, the work done against the atmospheric
pressure:
Watm=po(V2 V1)
But this work is not an useful work and hence
Wmax,useful= Wmax Watm
= [(U1 U2) To(S1 S2)]po(V2V1)
m
= (U1 U2) Po(V1 V2)]To(S1S2) ...6.5
Reversible Work In A Steady-state Control Volume
Q Wrev m
out h
C2
.co
Steady flow energy equation for a constant volume is
gZ m
in h
C2
gZ
tas
out 2 in 2
for a single inlet and outlet
da
C22 C12
h2 h1
Q Wrev m g Z 2 Z1
vil
2
...6.6
Ci
From Second law of thermodynamics
suniverse= (s)cv + (s)surr
=0
where
s2 s1
sCV m
Q
sSur
To
64 S.A.RAMESH – AP/MECH
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Substituting these values we get
Q
s2 s1
m
To
s2 s1
Q To m
m
From eqn 6.6 neglecting kinetic and potential energy changes
h1 h2 To s1 s2
Wrev m
.co
In an open system a fixed volume in space known as control volume is taken for analysis. Hence
tas
the atmospheric work term po(V1-V2) should not be considered. Therefore
Wrev= Wmax,useful for an open system
da
2.10 Availability
The maximum useful work that can be obtained from the system such that the system comes to a
dead state, while exchanging heat only with the surroundings, is known as availability of the system. Here
vil
the term dead state means a state where the system is in thermal and mechanical equilibrium with the
surroundings.
Therefore for a closed system availability can be expressed as
Ci
U U o po V Vo To S So
similarly for an open system
H H o To S So
In steady flow systems the exit conditions are assumed to be in equilibrium with the surroundings.
The change in availability of a system when it moves from one state to another can be given as:
for a closed system
65 S.A.RAMESH – AP/MECH
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1 2 U1 U 2 po V1 V2 To S1 S 2
...6.10
for an open system
1 2 H1 H 2 To S1 S 2 . ...6.11
Availability Change Involving Heat Exchange with Reservoirs
Consider a system undergoing a change of state while interacting with a reservoir kept at T R and
atmosphere at pressure po and temperature To. Net heat transfer to the system
m
Reservoir at
.co
QR
TR
tas
System Qo Atmosphere
at To & Po
da
WRev
vil
Qnet= QR-QO.
Ci
From first law of thermodynamics
Qnet- Wrev=U2-U1 ...6.12
From second law of thermodynamics, assuming the process to be reversible
(s)Res+(s)atm+(s)sys=0
66 S.A.RAMESH – AP/MECH
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QR Qo
S 2 S1 0
TR To
The negative sign for QR shows that the heat is removed from the reservoir.
By rearranging We get
To
Q o QR To S1 S 2
TR
Net heat transferred
m
Qnet =QR-Qo
Qnet Q R QR
To
TR
To S1 S 2
Substituting 6.13 in 6.12 we get
.co ...6.13
tas
To S1 S 2 Wrev U 2 U1
To
Q R QR
TR
da
T
Wrev U1 U 2 To S1 S 2 QR 1 o ...6.14
TR
vil
T
Wmax,useful U1 U 2 po V1 V2 To S1 S 2 QR 1 o ...6.15
TR
2.11 Irreversibility
Ci
Work obtained in an irreversible process will always be less than that of a reversible process. This
difference is termed as irreversibility (i.e) the difference between the reversible work and the actual work
for a given change of state of a system is called irreversibility.
I=Wrev Wact
Let a stationary closed system receiving Q kJ of heat is giving out W act kJ of work. From first law of
thermodynamics.
Q - Wact = U2 U1
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Wact = U1 U2+Q
Wrev =(U1 U2) TO(S1 S2)
= (U1 U2) + T0(s)system
I = Wrev Wact
= (U1 U2) + T0(s)system (U1- U2) Q
= T0(s)systemQ Where Q = Qsurroundings = TO(s)surroundings
= T0(s)system+TO ssurroundings
m
=T0(s)universe
process and will never be negative.
I 0
Similarly for a steady flow system
.co
Since (s)universe will be positive for an irreversible flow, irreversibility will be zero for a reversible
tas
I=Wrev Wact
h1 h2 To s1 s2
Where
Wrev m
da
h1 h2 Qsys
-
Wact m
vil
Qsys= Qo= TO ssurroundings
Therefore I = T0 (S1 S2) + TO ssurroundings
Ci
= T0 [ssysssurroundings]
= T0 [suniverse]
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UNIT-III
PROPERTIES OF A PURE SUBSTANCE AND STEAM POWER
CYCLE
3.1 PURE SUBSTANCE
A pure substance is one that has homogeneous and invariable chemical
composition. It may exist in more than one phase, but chemical composition is
same for all the phases. Thus, water, mixture of water and ice and water and steam
are all examples of pure substance. Sometimes a mixture of gases e.g. air is
considered as pure substance.
We have seen that two independent properties are sufficient to determine
m
thermodynamic state of a fluid when it is in equilibrium. Any other thermodynamic
property is a function of the chosen pair of independent properties. We shall first
consider the relation between the primary properties p, v and T, the equation
equation .co
expressing this relation for any particular fluid being called the equation of state or
characteristic of the fluid.
tas
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Since we have three variables to consider, the obvious procedure is to measure the
variation of one with another while the third is kept constant and repeat this for a
range of values of the third variable.
3.2 FORMATION OF STEAM AND PROPERTIES
Imagine unit mass of ice below the freezing point, enclosed in a cylinder by
a piston under a constant load of 1 atmosphere (1 atm. = 1.01325 bar = 101.325
kPa). If heat is added to the cylinder while keeping the pressure constant, the
temperature rises and ice expands until a temperature of 273.15 K (00C) is reached
(AB) as shown in Fig. Further heating does not raise the temperature of ice but
causes a change to the liquid phase (BC). The change of phase occurs at a constant
temperature and by reduction of specific volume. The heat required for this process
m
is known as latent heat of fusion. Further heating results in a rise of temperature of
liquid and a further contraction in volume until the temperature is about 40C and
.co
subsequent expansion until a temperature of 373.15 K (1000C) is reached (point
D). At this point a second phase change occurs at constant temperature with a large
increase in volume until the liquid has been vaporised (point E). The heat required
in this case is called the latent heat of vaporisation. When vaporisation is
complete, the temperature rises again on heating (line EF). The heat transferred to
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a substance while the temperature changes is sometimes referred to as sensible
heat. This constant pressure lines are called isobars.
da
vil
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If the pressure is reduced, there is a slight rise in the melting point and also there is
a marked drop in the boiling point of water and a marked increase in the change in
volume, which accompanies evaporation. When the pressure is reduced to
0.006113 bar (0.6113 kPa), the melting point and boiling point temperatures
become equal and change of phase, ice-water-steam, are represented by a single
line. The temperature at which this occurs has been accepted internationally as a
fixed point for the absolute temperature scale and is by definition 273.16 K. Only
at this temperature and pressure of 0.6112 kPa, can ice, water and steam coexists in
thermodynamic equilibrium in a closed vessel and is known as triple point. If the
pressure is reduced further, the ice, instead of melting, sublimes directly into
steam.
m
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3.3 p-v, p-T, T-v, T-s, h-s DIAGRAMS
Consider now the behaviour at pressure above atmospheric. The shape of the
curve is similar to that of the atmospheric isobar, but there is a marked reduction in
the change in volume accompanying evaporation. At a sufficiently high pressure,
this change in volume falls to zero and the horizontal portion of the curve reduces
to a point of inflexion. This is referred to critical point. The values pressure and
temperature of water at which critical point reached are
pc = 221.2 bar = 22.12 MPa ; Tc = 647.3 K ; vc = 0.00317 m3/kg.
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m
.co
tas
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The pressure at which liquid vaporises or condenses is called saturation
pressure corresponding to a given temperature. Alternately, the temperature at
which this phenomena occur is called saturation temperature corresponding to the
given pressure. A vapour in a state lying along the saturated vapour line is also
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called dry saturated vapour and the vapour lying right of this line is called
superheated vapour.
3.4 DEFINITION AND APPLICATIONS
• Saturation temperature: Temperature at which a pure substance changes phase
at a
given pressure.
• Saturation pressure: Pressure at which a pure substance changes phase at a
given
temperature.
• Latent heat: The amount of energy absorbed or released during a phase-change.
m
� Melting/freezing: Latent heat of fusion.
� Evaporation/condensation: Latent heat of vaporization.
• Temperature at which water starts boiling depends on the pressure => if the
3.5 SLOVED PROBLEMS
.co
pressure is fixed, so is the boiling temperature.
tas
1. A vessel of volume 0.04 m3 contains a mixture of saturated water and steam at a
temperature of 250°C. The mass of the liquid present is 9 kg. Find the pressure, mass,
specific volume, enthalpy, entropy and internal energy. [April/May 2012,2015]
da
Given Data:
Volume, V = 0.04 m3
vil
Temperature, T = 250°C
Mass, m = 9 kg
To find:
Ci
1) p, 2) m, 3) v, 4) h, 5) S,6) ΔU
Solution:
From the Steam tables corresponding to 250°C,
vf = v1 = 0.001251 m3/kg
vg = vs = 0.050037 m3/kg
p = 39.776 bar
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Total volume occupied by the liquid,
V1 = m1 × v1
= 9 × 0.001251
= 0.0113 m3.
Total volume of the vessel,
V = Volume of liquid + Volume of steam
= V1 + VS
0.04 = 0.0113 + VS
m
VS = 0.0287 m3.
Mass of steam, ms = VS / vs
= 0.0287 / 0.050037
= 0.574 kg.
.co
tas
Mass of mixture of liquid and steam, m = m1 + ms
= 9 + 0.574
da
= 9.574 kg.
Total specific volume of the mixture,
vil
v=
= 0.04 / 9.574
= 0.00418 m3 / kg.
Ci
We know that,
v = vf + x vfg
0.00418 = 0.001251 + x (0.050037 – 0.001251)
x = 0.06
From Steam table corresponding to 250 °C,
hf = 1085.8 KJ / kg
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hfg = 1714.6 KJ / kg
sf = 2.794 KJ / kg K
sfg = 3.277 KJ / kg K.
Enthalpy of mixture,
h = hf + x hfg
= 1085.8 + 0.06 × 1714.6
= 1188.67 KJ / kg
Entropy of mixture,
m
s = sf + x sfg
= 2.794 + 0.06 × 3.277
= 2.99 kJ / kg K.
Internal energy, u = h – p v
.co
tas
= 1188.67 – 39.776×102 × 0.00418
= 1172 KJ / kg.
da
Result:
1) p = 39.776 bar
2) m = 9.574 kg
vil
3) v = 0.00418 m3 / kg
4) h = 1188.67 KJ / kg
5) S = 2.99 KJ /kg K
6) ΔU = 1172 KJ / kg.
Ci
2). A steam power plant uses steam at boiler pressure of 150 bar and temperature of
550°C with reheat at 40 bar and 550 °C at condenser pressure of 0.1 bar. Find the quality
of steam at turbine exhaust, cycle efficiency and the steam rate. [May/June 2014]
Given Data:
p1 = 150 bar
T1 = 550°C
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p2 = 40 bar
T3 = 550 °C
p3 = 0.1 bar
To find:
1. The quality of steam at turbine exhaust, (x4)
2. cycle efficiency and
3. The steam rate.
Solution:
m
1. The quality of steam at turbine exhaust, (x4):
Properties of steam from steam tables at 150 bar & 550°C
h1 = 3445.2 KJ/kg.
S1= 6.5125 KJ/kg K
.co
At 40 bar & 550°C
tas
h3 = 3558.9 KJ/kg.
S3= 7.2295 KJ/kg K
da
At 40 bar
Tsat = 250.3°C = 523.3 K
vil
hf =1087.4 KJ/kg. hfg = 1712.9 KJ/kg.
Sf= 2.797 KJ/kg K Sfg= 3.272 KJ/kg K
Ci
At 0.1 bar
hf =191.8 KJ/kg. hfg = 2392.9 KJ/kg.
Sf= 0.649 KJ/kg K Sfg= 7.502 KJ/kg K
1-2 = isentropic
S1 = S = 6.5125 KJ/kg K
S2 = Sg at 40 bar
Therefore,
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Exit of HP turbine is superheat
Tsup = 332°C
h2 = 3047.18 KJ/kg
S3 = Sg at 0.1 bar
Steam is at wet condition.
S4 = S3 = 7.2295 KJ/kg K
S4 = Sf4 + x4 Sfg4
7.2295 = 0.649 + x4 × 7.502
m
x4 = 0.877
h4 = hf4 + x4 hfg4
= 191.8 + 0.877 × 2392.9
h4 = 2290.37 KJ/kg K
.co
tas
2) Cycle efficiency:
(h1 – h2) + (h3 – h4)
Ŋ=
(h1 – hf4) + (h3 – h2)
da
(3445.2 – 3047.15) + (3558.9 – 2290.37)
=
(3445.2 – 191.8) + (3558.9 – 3047.18)
vil
= 0.4426 × 100
= 44.26%
Ci
3) Steam rate:
= 3600
(h1 – h2) + (h3 – h4)
3600
= (3445.2 – 3047.15) + (3558.9 – 2290.37)
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= 2.16 kg/Kw–hr.
Result:
1. The quality of steam at turbine exhaust, (x4) = 0.877
2. cycle efficiency = 44.26%
3. The steam rate = 2.16 kg/Kw–hr.
3). Ten kg of water 45 °C is heated at a constant pressure of 10 bar until it becomes
superheated vapour at 300°C. Find the change in volume, enthalpy, internal energy and
entropy.
m
Given Data:
m= 10 kg
p1 = p2 = 10 bar
T2 = 300°C
To find:
.co
tas
1) Change in volume,
2) Change in Enthalpy,
3) Change in Internal energy,
4) Change in Entropy.
da
Solution:
From steam tables, corresponding to 45°C,
vil
v1=vf1=0.001010 m3 / kg; h1 = hf1 = 188.4 KJ/kg;
s1 = sf1 = 0.638 KJ/kg K
Ci
From steam tables, corresponding to 10 bar and 300°C,
h2 = 3052.1 KJ/kg; s2 = 7.125 KJ/kg K;
v2 = 0.258 m3 /kg;
Change in Volume, Δ V = m (v2 – v1)
= 10 (0.258 – 0.001010)
= 2.5699 m3.
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Change in Enthalpy, Δ h = m (h2 – h1)
= 10 (3052.1 – 188.4)
= 28637 KJ.
Change in Entropy, Δ S = m (s2 – s1)
= 10 (7.125 – 0.638)
= 64.87 KJ/K.
m
Change in Internal energy, Δ U = m (u2 – u1)
.co
= m [(h2 - h1) – (p2v2 – p1v1)]
= m [(h2 - h1) – p1 (v2 – v1)
= 10 [(3052.1 – 188.4) – 1000 (0.258 – 0.001010)]
tas
= 26067.1 KJ.
Result:
Change in volume, ΔV = 2.5699 m3.
da
1)
2) Change in Enthalpy, Δ h = 28637 KJ.
3) Change in Internal energy, ΔU = 26067.1 KJ.
4) Change in Entropy, ΔS = 64.87 KJ/K.
vil
3.6 THE MEASUREMENTS OF DRYNESS FRACTION
Dryness fraction of wet steam, representing the fraction of steam in the mixture of water
Ci
and steam can be measured by using (i) Throttling calorimeter and (ii) Separating and Throttling
calorimeter.
(i) Throttling calorimeter:
Let us consider a wet steam as represented by state 1 in the h-s diagram. When it
undergoes a throttling process to state 2, it enters into the superheated region. By measuring the
temperature and pressure after throttling the specific enthalpy can be obtained. As mentioned
earlier during throttling enthalpy remains constant. Therefore the initial state can be completely
fixed since the pressure before throttling and the corresponding specific enthalpy are known.
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m
Fig. h-s diagram
.co
Steam from the main is extracted through a perforated tube projecting into it as shown in
the Figure. Pressure of the steam is measured. It is then throttled into a chamber where the
tas
necessary pressure and temperature measurements are made. From the chamber the expanded
steam is then condensed by circulating cooling water and discharged.
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vil
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Fig . Throttling Calorimeter
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(ii) Separating and Throttling calorimeter:
When the dryness fraction of the steam is very low, it becomes superheated vapour only at
very low end pressure on throttling. In general, the pressure after throttling for dryness fraction
measurement is preferred to be above atmospheric. In such applications, separating and throttling
calorimeters are used for dryness fraction measurement.
Wet steam, when subjected to sudden change in the direction of flow, a portion of the
liquid falls due to gravity and gets separated from the main stream. Thus the remaining steam
becomes rich in vapour, which upon throttling will become superheated vapour even at a
pressure higher than atmospheric pressure. This principle is employed in the separating and
throttling calorimeter.
m
The wet steam from the steam main is extracted through a perforated tube and sent to the
.co
separator where a portion of the liquid is separated due to sudden change in the direction. The
remaining steam is throttled into a chamber where the required pressure and temperature
measurements are made. Mass flow rate of liquid separated in the separator is collected and
measured. Mass of the remaining steam is also measured by condensing the throttled steam and
collecting it. Let be the mass of liquid separated in the separator and be the mass of steam
tas
throttled.
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Fig. Separating and Throttling calorimeter
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3.7 REGENERATIVE BRAYTON CYCLE
The temperature of the exhaust gases of simple gas turbine is higher than the
temperature of air after compression. If the heat energy in the exhaust gases instead
of getting dissipated in the atmosphere is used in heating air after compression, it
will reduce the energy requirement from the fuel, thereby increasing the efficiency
of the cycle
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.
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Air is drawn from the atmosphere into compressor and compressed isentropically
to state 2. It is then heated at constant pressure in the regenerator to state x by hot
burnt gases from the turbine. Since the temperature of air is increased before it
reaches the combustion chamber, less amount of fuel will be required to attain the
designed turbine inlet temperature of the products of combustion. After the
combustion at constant pressure in the combustion chamber, the gas enters the
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turbine at state 3 and expands to state 4 isentropically. It then enters the counter-
flow regenerator, where it gives up a portion of its heat energy to the compressed
air from the compressor and leaves the regenerator at state y.
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3.8 INTERCOOLING AND REHEATING
The addition of regenerator improves the ideal efficiency but does not
improve the work ratio. The latter may be reduced by reducing the compressor
work or increasing the
turbine work.
m
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tas
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Consider the compressor work first. The curvature of the constant pressure lines on
T-s diagram is such that the vertical distance between them reduces as we go
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towards the left (shown by the arrow). Therefore, further to the left the
compression process 1-2 takes place, smaller is the work required to drive the
compressor. State 1 is determined by the atmospheric pressure and temperature.
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But if the compression is carried out in two stages, 1-3 and 4-5 with the air is being
cooled at constant intermediate pressure pi between the stages; some reduction of
compression work can be achieved. The sum of temperature rises (T3 – T1) and
(T5 – T4) will be clearly less than (T2 – T1). Ideally, it is possible to cool the air to
atmospheric condition i.e. T4 = T1, and in this case Intercooling is complete.
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4). A steam boiler generates steam at 30 bar, 300 °C at the rate of 2 kg/s. This steam is
expanded isentropically in a turbine to a condenser pressure of 0.05 bar, condensed at
constant pressure and pumped back to boiler.
a) Find the heat supplied in the boiler per hour.
b) Determine the quality of steam after expansion.
c) What is the power generated by the turbine?
d) Estimate the Ranking efficiency considering pump work.
Given Data:
p1 = 30 bar
m
p2 = 0.05 bar
T1 = 300°C
m = 2 kg / s
To find:
1.
.co
Find the heat supplied in the boiler per hour (QS)
tas
2. Determine the quality of steam after expansion (x2)
3. What is the power generated by the turbine (WT)
4. Estimate the Ranking efficiency considering pump work ( Ŋ)
da
Solution:
vil
1. Heat supplied in the boiler per hour (QS):
Properties of steam from the steam table
At 30 bar & 300°C
Ci
h1 = 2995.1 KJ/kg; S1 = 6.542 KJ/kg K;
At 0.05 bar
hf2 = 137.8 KJ/kg; hfg2 = 2423.8 KJ/kg;
Sf2 = 0.476 KJ/kg K; Sfg2 = 7.920 KJ/kg K;
Vf2 = 0.001005 m3/kg.
1-2 = Isentropic expansion in the turbine
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S1 = S2 = 6.542 KJ/ kg K
S2 = Sf2 + x2 ×Sfg2
6.542 = 0.476 + x2 × 7.92
= 0.766
Therefore, Quality of steam after expansion = 0.766 dry.
h2 = hf2 + x2 ×hfg 2
= 137.81 + 0.766 × 2423.8
m
= 1994.43 KJ/kg.
h3 = hfg2 = 137.8 KJ/kg.
.co
Considering the pump work, h4 – h3 = vf2 (p1 – p2)
h4 = h3 + vf2 (p1 – p2)
= 137.8 + 0.001005 × (30 - 0.05) × 102
tas
= 140.81 KJ/kg.
Heat supplied in the boiler:
da
QS = m × (h1 – h4)
= 2 × (2995.1 – 140.81)
vil
= 5708.58 KJ/s
= 20.55 × 106 KJ /hr.
Power generated by the turbine:
Ci
WT = m × (h1 – h2)
= 2 × (2995.1 – 1994.43)
= 2001.34 KW.
Rankine efficiency by the plant:
(h1 – h2) - (h4 – h3)
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(h1 – h4)
=
= (2995.1 – 1994.43) - (140.81 – 137.8)
(2995.1 – 140.81)
= 35 %
Result:
1. Find the heat supplied in the boiler per hour (QS) = 20.55 × 106 KJ /hr
m
2. Determine the quality of steam after expansion (x2) = 0.766 dry
3. What is the power generated by the turbine (WT) = 2001.34 KW.
4.
3.9 GAS POWER / AIR STANDARD CYCLES. .co
Estimate the Ranking efficiency considering pump work ( Ŋ) = 35%
For small power plants, gas is ideally preferred as the working fluid. The
gasoline engines, diesel engines and gas turbines are common examples. The
tas
analysis of the air-standard cycle is based on the assumptions that are far from real.
In actual internal combustion (IC) engines, chemical reaction occurs inside the
engine cylinder as a result of combustion of air-fuel mixture and. The IC engines
are actually operated on Open cycles in which the working fluid does not go
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through a cycle. The accurate analysis of IC engine is very complicated. However,
it is advantageous to analyse the performance of an ideal closed cycle that closely
approximates the real cycle. One such approach is air-standard cycle, which is
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based on certain assumptions. The assumptions for idealized air-standard cycles
are:
1) The working fluid, air, is assumed to be an ideal gas. The equation of state is
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given by the equation pv = RT and the specific heats are assumed to be constant.
2) All processes that constitute the cycle are reversible.
3) No chemical reaction occurs during the cycle. Heat is supplied from a high
temperature reservoir (instead of chemical reaction) and some heat is rejected to
the low temperature reservoir during the cycle.
4) The mass of air within the system remains constant throughout the cycle.
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5) Heat losses from the system to the atmosphere are assumed to be zero. In this
we shall discuss about the Brayton cycle, Otto cycle and Diesel cycle.
3.10 BRAYTON CYCLE
The Brayton cycle is widely used as the basis for the operation of Gas
turbine. A schematic diagram of a simple gas turbine (open cycle) and the
corresponding p-v and T-s diagrams are shown below. Air is drawn from he
atmosphere into compressor, where it is compressed reversibly and adiabatically.
The relative high pressure air is then used in burning the fuel in the combustion
chamber. The air-fuel ratio quite high (about 60:1) to limit the temperature burnt
gases entering the turbine. The gases then expand isentropically in the turbine. A
m
portion of the work obtained from the turbine is utilised to drive the compressor
and the auxiliary drive and the rest of the power output is the net power of the gas
turbine plant.
.co
tas
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Simple gas turbine Brayton cycle with closed cycle consists of
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3.11 COMBINED CYCLE
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Thermal Efficiency is given by
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OTTO CYCLE
The air standard Otto Cycle is an idealised cycle which closely approximates
the operation of Spark Ignition (SI) Engine.
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Process 1-2 is reversible adiabatic (isentropic) compression of air when the piston
.co
moves from crank-end dead centre (BDC) to cylinder head dead centre (TDC).
During the process 2-3, heat is transferred reversibly to the system at constant
volume (this process corresponds to the spark ignition of the actual engine). The
curve 3-4 represents the reversible adiabatic expansion process when piston moves
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from TDC to BDC and the curve 4-1 represents the heat rejected by the system
reversibly at constant volume.
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UNIT IV
IDEAL AND REAL GASES, THERMODYNAMIC RELATIONS
4.1 IDEAL GAS
An ideal gas is a theoretical gas composed of a set of randomly-moving
point particles that interact only through elastic collisions. The ideal gas concept is
useful because it obeys the ideal gas law, a simplified equation of state, and is
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amenable to analysis under statistical mechanics.
At normal ambient conditions such as standard temperature and pressure,
most real gases behave qualitatively like an ideal gas. Generally, deviation from an
.co
ideal gas tends to decrease with higher temperature and lower density, as the work
performed by intermolecular forces becomes less significant compared with the
particles' kinetic energy, and the size of the molecules becomes less significant
compared to the empty space between them.
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EQUATION TABLE FOR AN IDEAL GAS
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4.2 REAL GAS
Real gas, as opposed to a Perfect or Ideal Gas, effects refers to an
assumption base where the following are taken into account:
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• Compressibility effects
• Variable heat capacity
• Van der Waals forces
• Non-equilibrium thermodynamic effects
• Issues with molecular dissociation and elementary reactions with variable
composition.
For most applications, such a detailed analysis is "over-kill" and the ideal gas
approximation is used. Real-gas models have to be used near condensation point of
gases, near critical point, at very high pressures, and in several other less usual
cases.
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4.3 VAN DER WAALS MODELISATION
Real gases are often modeled by taking into account their molar weight and
molar volume
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Where P is the pressure, T is the temperature, R the ideal gas constant, and Vm the
molar volume. a and b are parameters that are determined empirically for each gas,
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but are sometimes estimated from their critical temperature (Tc) and critical
pressure (Pc) using these relations:
da
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4.4 REDLICH–KWONG MODELISATION
The Redlich–Kwong equation is another two-parameters equation that is
used to modelize real gases. It is almost always more accurate than the Van der
Ci
Waals equation, and often more accurate than some equation with more than two
parameters. The equation is
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4.5 THERMODYNAMICS RELATIONS
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Maxwell relations.
The Maxwell’s equations relate entropy to the three directly measurable
properties p,v and T for pure simple compressible substances.
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From first law of thermodynamics,
Q=W+ U
Rearranging the parameters
Q= U+W since [ds = , W = pdv ]
`` Tds = du +pdv
du = Tds – pdv ----------- (1)
We know that, h = u + pv
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dh = du + d(pv)
= du + vdp + pdv
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Substituting the value du in equation (2),
----------- (2)
dh = Tds + pdv + vdp – pdv
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dh = Tds + vdp ----------- (3)
By Helmotz’s function,
da
a = u – Ts
da = du – d(Ts)
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= du – Tds – sdT ----------- (4)
Substituting the values of du in equation (4),
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da = Tds – pdv – Tds – sdT
T = – pdv – sdT ----------- (5)
By Gibbs functions,
G = h – Ts
dg = dh – d(Ts)
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dg = dh – Tds – sdT ----------- (6)
Substituting the value of dh in equation (6),
So, dg becomes
dg = Tds + vdp – Tds – sdT
dg = vdp – sdT ----------- (7)
By inverse exact differential we can write equation (1) as,
du = Tds – pdv
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----------- (8)
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Similarly, equation (3) can be written as,
dh = Tds + vdp
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----------- (9)
Similarly, equation (5) can be written as,
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----------- (10)
Similarly, equation (7) can be written as,
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dg = vdp – sdT
----------- (11)
These equations 8, 9, 10 and 11 are Maxwell’s equation.
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Tds relations in terms of temperature and pressure changes and temperature
and volume changes.
The entropy (s) of pure substance can be expressed as a function of
temperature (T) and pressure (p).
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s = f(T,p)
We know that,
ds = and
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From Maxwell equation, we know that
Substituting in ds equation,
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ds = dT dp
Multiplying by T on both sides of the equation,
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Tds = dT dp
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This is known as the first form of entropy equation or the first Tds equation.
By considering the entropy of a pure substance as a function of temperature
and specific volume,
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i.e. s = f(T,v)
ds = and
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From the Maxwell Equations, we know that
Substituting in ds Equation,
ds = dT + dv
Multiplying by T,
Tds = dT + T dv
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This is known as the second form of entropy equation or the second Tds
equation
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4.6 THE JOULE-THOMSON COEFFICIENT OF AN IDEAL GAS IS ZERO
The Joule-Thomson coefficient is defined as the change in temperature with change in
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pressure, keeping the enthalpy remains constant. It is denoted by,
µ= =
da
We know that the equation of state as,
pV=RT
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Differentiating the above equation of state with respect to T by keeping pressure, p
constant.
= =
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µ=
µ = 0.
It implies that the Joule-Thomson coefficient is zero for ideal gas.
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4.7 CLAUSIUS–CLAPEYRON RELATION
The Clausius–Clapeyron relation, named after Rudolf Clausius and Émile
Clapeyron, who defined it sometime after 1834, is a way of characterizing the
phase transition between two phases of matter, such as solid and liquid. On a
pressure– temperature (P–T) diagram, the line separating the two phases is known
as the coexistence curve. The Clausius–Clapeyron relation gives the slope of this
curve. Mathematically,
where dP / dT is the slope of the coexistence curve, L is the latent heat, T is the
temperature, and ΔV is the volume change of the phase transition.
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Pressure Temperature Relations
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A typical phase diagram. The dotted line gives the anomalous behavior of water.
The Clausius–Clapeyron relation can be used to (numerically) find the
relationships between pressure and temperature for the phase change boundaries.
Entropy and volume changes (due to phase change) are orthogonal to the plane of
this drawing
Derivation
Using the state postulate, take the specific entropy, s, for a homogeneous
substance to be a function of specific volume, v, and temperature, T.
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During a phase change, the temperature is constant, so
Using the appropriate Maxwell relation gives
Since temperature and pressure are constant during a phase change, the derivative
of pressure with respect to temperature is not a function of the specific volume.
Thus the partial derivative may be changed into a total derivative and be factored
out when taking an integral from one phase to another,
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Δ is used as an operator to represent the change in the variable that follows it—
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final (2) minus initial (1) For a closed system undergoing an internally reversible
process, the first law is
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This leads to a version of the Clausius–Clapeyron equation that is simpler to
integrate:
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C is a constant of integration
These last equations are useful because they relate saturation pressure and
saturation temperature to the enthalpy of phase change, without requiring specific
volume data. Note that in this last equation, the subscripts 1 and 2 correspond to
different locations on the pressure versus temperature phase lines. In earlier
equations, they corresponded to different specific volumes and entropies at the
same saturation pressure and temperature.
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The Joule–Thomson (Kelvin) coefficient
The rate of change of temperature T with respect to pressure P in a Joule–
Thomson process (that is, at constant enthalpy H) is the Joule–Thomson (Kelvin)
coefficient μJT. This coefficient can be expressed in terms of the gas's volume V,
its heat capacity at constant pressure Cp, and its coefficient of thermal expansion α
as
See the Appendix for the proof of this relation. The value of μJT is typically
expressed in °C/bar (SI units: K/Pa) and depends on the type of gas and on the
temperature and pressure of the gas before expansion.
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All real gases have an inversion point at which the value of μJT changes
sign. The temperature of this point, the Joule–Thomson inversion temperature,
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depends on the pressure of the gas before expansion. In a gas expansion the
pressure decreases, so the sign of is always negative. With that in mind, the
following table explains when the Joule–Thomson effect cools or warms a real gas:
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Helium and hydrogen are two gases whose Joule–Thomson inversion temperatures
at a pressure of one atmosphere are very low (e.g., about 51 K (−222 °C) for
helium). Thus, helium and hydrogen warm up when expanded at constant enthalpy
at typical room temperatures. On the other hand nitrogen and oxygen, the two most
abundant gases in air, have inversion temperatures of 621 K (348 °C) and 764 K
(491 °C) respectively: these gases can be cooled from room temperature by the
Joule– Thomson effect.
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Derivation of the Joule–Thomson (Kelvin) coefficent
A derivation of the formula
for the Joule–Thomson (Kelvin) coefficient.
The partial derivative of T with respect to P at constant H can be computed by
expressing the differential of the enthalpy dH in terms of dT and dP, and equating
the resulting expression to zero and solving for the ratio of dT and dP. It follows
from the fundamental thermodynamic relation that the differential of the enthalpy
is given by:
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4.8 SOLVED PROBLEMS
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1. A mixture of ideal gases consists of 7kg of
and a temperature of 27°C. Determine:
and 2kg of at a pressure of 4bar
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i. Mole fraction of each constituent,
ii. Equivalent molecular weight of the mixture,
iii. Equivalent gas constant of the mixture,
iv. The partial pressure and partial volumes,
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v. The volume and density of the mixture
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Given data:
= 7kg
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= 2kg
p = 4bar
T = 27°C
Solution:
i. Mole fraction of ,
= 0.8
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Mole fraction of ,
= 0.2
ii. Equivalent molecular weight of the mixture,
M= +
= (0.8×28) + (0.2×32) = 28.8kg/kg mol
Total mass, m = + = 7 + 2 = 9kg
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iii. Equivalent gas constant of the mixture,
R=
= .co
= 0.2886kJ/kgK
iv. The partial pressure and partial volumes,
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= = 1.558
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= = 0.389
v. The volume and density of the mixture,
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Density of = = = 4.492kg/
Density of = = = 5.141kg/
Describe Joule Kelvin effect with the help of T-p diagram
The Joule Kelvin effect or Joule Thomson effect is an efficient way of cooling gases. In
this, a gas is made to undergo a continuous throttling process. A constant pressure is
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maintained at one side of a porous plug and a constant lower pressure at the other side. The
apparatus is thermally insulated so that the heat loss can be measured.
Joule – Thomson co – efficient is defined as the change in temperature with change in
pressure, keeping the enthalpy remains constant. It is denoted by,
µ=
Throttling process:
It is defined as the fluid expansion through a minute orifice or slightly opened valve.
During this process, pressure and velocity are reduced. But there is no heat transfer and no work
done by the system. In this process enthalpy remains constant.
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Joule Thomson Experiment:
stream of gas at a pressure
temperature .
and temperature
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The figure shows the arrangement of porous plug experiment. In this experiment, a
is allowed to flow continuously through a
porous pig. The gas comes out from the other side of the porous pig at a pressure and
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The whole apparatus is insulated. Therefore no heat transfer takes place. Q = 0.
The system does not exchange work with the surroundings.
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So, W=0 from steady flow energy equation we know that
g + +( + )+Q=g + +( + )+W
Since there is no considerable change velocity, and , Q=0,W=0, are applied in steady
flow energy equation. Therefore,
It indicates that the enthalpy is constant for throttling process.
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initial pressure
(
and temperature
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It is assumed that a series of experiments performed on a real gas keeping the
constant with various down steam pressures
). It is found that the down steam temperature also changes. The results from
these experiments can be plotted as enthalpy curve on T-p plane.
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The slope of a constant enthalpy is known as Joule Thomson Coefficient. It is denoted by
µ.
µ=
da
For real gas, µ may be either positive or negative depending upon the thermodynamic
state of the gas.
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2. A mixture of 2kg oxygen and 2kg Argon is in an insulated piston cylinder
arrangement at 100kPa, 300K. The piston now compresses the mixture to half its
initial volume. Molecular weight of oxygen is 40. Ratio of specific heats for oxygen is
1.39 and for argon is 1.667.[Nov 2004]
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Given data:
=2kg
=2kg
= 100kPa
= 300K
= 32
= 40
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=1.39
=1.667
Solution:
Mass fraction, = = 0.56
= = 556kPa
Similarly,
m
= = 0.44
= = 44.4kPa
From equation of state,
= =
.co = 2.804
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= = = 2.81
da
Volume of mixture before expansion,
= = 5.61
Volume after expansion,
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= = 2.807
Ratio of specified heat of mixture,
= + = 1.513
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Insulated process refers reversible adiabatic process
=
= = 100 = 285.4kPa
Similarly,
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Piston work,
W= = = -1000.23kJ
W = -1MJ
(Negative sign indicates the work input to piston)
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UNIT V
GAS MIXTURES AND PSYCHROMETRY
5.1 GAS MIXTURES
Pure substance is defined as a substance which means that it is homogeneous and
unchanging in chemical composition.
COMPOSITION OF A GAS MIXTURE:
MASS AND MOLE FRACTIONS
To determine the properties of a mixture, we need to know the composition of the
mixture as well as the properties of the individual components. There are two ways
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to describe the composition of a mixture: either by specifying the number of moles
of each component, called molar analysis, or by specifying the mass of each
component, called gravimetric analysis.
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Consider a gas mixture composed of k components. The mass of the mixture mm is
the sum of the masses of the individual components, and the mole number of the
mixture Nm is the sum of the mole numbers of the individual components.
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The ratio of the mass of a component to the mass of the mixture is called the mass
fraction mf, and the ratio of the mole number of a component to the mole number
of the mixture is called the mole fraction
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Dividing (1) by mm or (2) by Nm, we can easily show that the sum of the mass
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fractions or mole fractions for a mixture is equal to 1
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The mass of a substance can be expressed in terms of the mole number N and
molar mass M of the substance as m _ NM. Then the apparent (oraverage) molar
mass and the gas constant of a mixture can be expressed as
The molar mass of a mixture can also be expressed as
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Mass and mole fractions of a mixture are related by
m
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5.2 P-v-T BEHAVIOR OF GAS MIXTURES:
IDEAL AND REAL GASES
An ideal gas is defined as a gas whose molecules are spaced far apart so that the
behavior of a molecule is not influenced by the presence of other molecules—a
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situation encountered at low densities. We also mentioned that real gases
approximate this behavior closely when they are at a low pressure or high
temperature relative to their critical-point values. The P-v-T behavior of an ideal
gas is expressed by the simple relation Pv _ RT, which is called the ideal-gas
equation of state. The P-v-T behavior of real gases is expressed by more complex
equations of state or by Pv _ ZRT, where Z is the compressibility factor.
When two or more ideal gases are mixed, the behavior of a molecule
normally is not influenced by the presence of other similar or dissimilar molecules,
and therefore a nonreacting mixture of ideal gases also behaves as an ideal gas.
Air, for example, is conveniently treated as an ideal gas in the range where
nitrogen and oxygen behave as ideal gases. When a gas mixture consists of real
(nonideal) gases, however, the prediction of the P-v-T behavior of the mixture
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becomes rather involved.
The prediction of the P-v-T behavior of gas mixtures is usually based on two
models: Dalton’s law of additive pressures and Amagat’s law of additive volumes.
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Both models are described and discussed below.
Dalton’s law of additive pressures:
Dalton's law (also called Dalton's law of partial pressures) states that the total
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pressure exerted by a gaseous mixture is equal to the sum of the partial pressures of
each individual component in a gas mixture. This empirical law was observed by
John Dalton in 1801 and is related to the ideal gas laws. Mathematically, the
pressure of a mixture of gases can be defined as the summation
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Amagat’s law of additive volumes:
Amagat's law or the Law of Partial Volumes of 1880 describes the behavior and
properties of mixtures of ideal (as well as some cases of non-ideal) gases. Of use in
chemistry and thermodynamics, Amagat's law states that the volume Vm of a gas
mixture is equal to the sum of volumes Vi of the K component gases, if the
temperature T and the pressure p remain the same:
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This is the experimental expression of volume as an extensive quantity. It is
named after Emile Amagat. Both Amagat's and Dalton's Law predict the properties
of gas mixtures. Their predictions are the same for ideal gases. However, for real
(non-ideal) gases, the results differ. Dalton's Law of Partial Pressures assumes that
the gases in the mixture are non-interacting (with each other) and each gas
independently applies its own pressure, the sum of which is the total pressure.
Amagat's Law assumes that the volumes of each component gas (same temperature
and pressure) are additive; the interactions of the different gases are the same as
the average interactions of the components.
Heat capacity
The heat capacity at constant volume of an ideal gas is:
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It is seen that the constant is just the dimensionless heat capacity at constant
volume. It is equal to half the number of degrees of freedom per particle. For
moderate temperatures, the constant for a monoatomic gas is while for
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a diatomic gas it is . It is seen that macroscopic measurements on heat
capacity provide information on the microscopic structure of the molecules .
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where H = U + pV is the enthalpy of the gas. It is seen that is also a constant and
that the dimensionless heat capacities are related by:
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5.3 ENTROPY
Using the results of thermodynamics only, we can go a long way in
determining the expression for the entropy of an ideal gas. This is an important
step since, according to the theory of thermodynamic potentials, of which the
internal energy U is one, if we can express the entropy as a function of U and the
volume V, then we will have a complete statement of the thermodynamic behavior
of the ideal gas. We will be able to derive both the ideal gas law and the expression
for internal energy from it. Since the entropy is an exact differential, using the
chain rule, the change in entropy when going from a reference state 0 to some
other state with entropy S may be written as ΔS where:
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This is about as far as we can go using thermodynamics alone. Note that the above
equation is flawed — as the temperature approaches zero, the entropy approaches
negative infinity, in contradiction to the third law of thermodynamics. In the above
"ideal" development, there is a critical point, not at absolute zero, at which the
argument of the logarithm becomes unity, and the entropy becomes zero.
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5.4 PSYCHROMETRY
psychrometry is a term used to describe the field of engineering concerned with
the determination of physical and thermodynamic properties of gas-vapor
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mixtures. The term derives from the Greek psuchron meaning "cold" and metron
meaning "means of measurement"
Common applications
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The principles of psychrometry apply to any physical system consisting of
gasvapor mixtures. The most common system of interest, however, are mixtures of
water vapor and air because of its application in heating, ventilating, and air-
conditioning and meteorology.
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Psychrometric ratio
The psychrometric ratio is the ratio of the heat transfer coefficient to the product
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of mass transfer coefficient and humid heat at a wetted surface. It may be evaluated
with the following equation
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where:
• r = Psychrometric ratio, dimensionless
• hc = convective heat transfer coefficient, W m-2 K-1
• ky = convective mass transfer coefficient, kg m-2 s-1
• cs = humid heat, J kg-1 K-1
Humid heat is the constant-pressure specific heat of moist air, per unit mass of dry
air.
The psychrometric ratio is an important property in the area of psychrometrics as it
relates the absolute humidity and saturation humidity to the difference between the
117 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
dry bulb temperature and the adiabatic saturation temperature. Mixtures of air and
water vapor are the most common systems encountered in psychrometry. The
psychrometric ratio of air-water vapor mixtures is approximately unity which
implies that the difference between the adiabatic saturation temperature and wet
bulb temperature of air-water vapor mixtures is small. This property of air-water
vapor systems simplifies drying and cooling calculations often performed using
psychrometic relationships.
PSYCHROMETRIC CHART
m
.co
tas
da
vil
Ci
A psychrometric chart is a graph of the physical properties of moist air at a
constant pressure (often equated to an elevation relative to sea level). The chart
graphically expresses how various properties relate to each other, and is thus a
graphical equation of state. The thermophysical properties found on most
psychrometric charts are:
• Dry-bulb temperature (DBT) is that of an air sample, as determined by an
ordinary thermometer, the thermometer's bulb being dry. It is typically the x-axis,
118 S.A.RAMESH – AP/MECH
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the horizontal axis, of the graph. The SI units for temperature are Kelvin; other
units are Fahrenheit.
• Wet-bulb temperature (WBT) is that of an air sample after it has passed through
a constant-pressure, ideal, adiabatic saturation process, that is, after the air has
passed over a large surface of liquid water in an insulated channel. In practice, this
is the reading of a thermometer whose sensing bulb is covered with a wet sock
evaporating into a rapid stream of the sample air. The WBT is the same as the DBT
when the air sample is saturated with water. The slope of the line of constant WBT
reflects the heat of vaporization of the water required to saturate the air of a given
relative humidity.
m
• Dew point temperature (DPT) is that temperature at which a moist air sample at
the same pressure would reach water vapor saturation. At this saturation point,
.co
water vapor would begin to condense into liquid water fog or (if below freezing)
solid hoarfrost, as heat is removed. The dewpoint temperature is measured easily
and provides useful information, but is normally not considered an independent
property. It duplicates information available via other humidity properties and the
saturation curve.
tas
• Relative humidity (RH) is the ratio of the mole fraction of water vapor to the
mole fraction of saturated moist air at the same temperature and pressure. RH is
dimensionless, and is usually expressed as a percentage. Lines of constant RH
da
reflect the physics of air and water: they are determined via experimental
measurement. Note: the notion that air "holds" moisture, or that moisture dissolves
in dry air and saturates the solution at some proportion, is an erroneous (albeit
vil
widespread) concept (see relative humidity for further details).
• Humidity ratio (also known as moisture content, mixing ratio, or specific
humidity) is the proportion of mass of water vapor per unit mass of dry air at the
given conditions (DBT, WBT, DPT, RH, etc.). It is typically the y-axis, the vertical
Ci
axis, of the graph. For a given DBT there will be a particular humidity ratio for
which the air sample is at 100% relative humidity: the relationship reflects the
physics of water and air and must be measured. Humidity ratio is dimensionless,
but is sometimes expressed as grams of water per kilogram of dry air or grains of
water per pound of air.
• Specific enthalpy symbolized by h, also called heat content per unit mass, is the
sum of the internal (heat) energy of the moist air in question, including the heat of
the air and water vapor within. In the approximation of ideal gases, lines of
119 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
constant enthalpy are parallel to lines of constant WBT. Enthalpy is given in (SI)
joules per kilogram of air or BTU per pound of dry air.
• Specific volume, also called inverse density, is the volume per unit mass of the
air sample. The SI units are cubic meters per kilogram of dry air; other units are
cubic feet per pound of dry air.
Specific humidity
Specific humidity is the ratio of water vapor to air (including water vapor and dry
air) in a particular mass. Specific humidity ratio is expressed as a ratio of
kilograms of water vapor, mw, per kilogram of air (including water vapor), mt .
m
Relative Humidity
.co
tas
The relative humidity of an air-water mixture is defined as the ratio of the partial
pressure of water vapor in the mixture to the saturated vapor pressure of water at a
prescribed temperature. Relative humidity is normally expressed as a percentage
and is defined in the following manner
da
vil
is the relative humidity of the mixture being considered;
is the partial pressure of water vapor in the mixture; and
is the saturated vapor pressure of water at the temperature of the mixture.
Ci
The international symbols U and Uw, expressed in per cent, are gaining
recognition.
120 S.A.RAMESH – AP/MECH
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m
.co
tas
da
vil
Ci
121 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
5.5 SOLVED PROBLEMS
1. Atmospheric air at 1.0132bar has a DBT of 30°C and a WBT of 25°C. Compute
i. The partial pressure of water vapour,
ii. The specific humidity,
iii. The dew point temperature,
iv. The relative humidity,
v. The degree of saturation,
vi. The density of air in the mixture,
vii. The density of vapour in the mixture and
viii. The enthalpy of the mixture. Use thermodynamic table. [April/May -
2015]
m
Given data:
Dry bulb temperature, ( ) = 30°C
Wet bulb temperature, (
Atmospheric pressure, (
Solution:
.co
) = 25°C
) = 1.0132bar
tas
1. Humidity ratio, = 0.622
Partial pressure vapour, = -
da
Where,
- saturation pressure corresponding to WBT
- barometric pressure = 1bar
vil
- Dry bulb temperature
- Wet bulb temperature
From steam table, for 25°C WBT, corresponding pressure is 0.03166bar
Ci
i.e. = 0.03166bar
= 0.0336 –
Partial pressure of vapour,
= 0.0296bar
Substituting and value in equation ,
= 0.622×
122 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
Specific humidity, of air
2. Dew point temperature ( )
From steam table, we find that partial vapour pressure, = 0.03bar,
corresponding temperature is 24.1°C.
So, the dew point temperature = 24.1°C
3. Relative humidity
Where, – Saturation pressure corresponding DBT
m
From steam table,
.co
For 30°C DBT, corresponding pressure is 0.04242bar
i.e.
tas
4. Degree of saturation,
da
vil
0.6886
5. Specific volume ( ) of air:
From gas law,
Ci
Where,
Gas constant, R = 0.287kJ/kg
0.0296
0.9834bar
= = 88.428
Density of air,
= = 0.011kg/
123 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
6. Density of water vapour ( )
From steam table, corresponding to 30°C DBT, specific volume ( ) is
32.929
= = 0.0303kg/
Vapour density of relative humidity,
Vapour density, = 0.0303×0.6977
= 0.0211 kg/
7. Total enthalpy
Enthalpy, h =
Where, - Specific heat = 1.005kJ/kgK
m
- Specific enthalpy of air corresponding DBT
From steam table,
For 30°C DBT, corresponding specific enthalpy is 2430.7kJ/kg
h=
h = 76.09 kJ/kg .co
tas
2. Air at 20°C, 40% relative humidity is missed adiabatically with air at 40°C, 40%
RH in the ratio of 1kg of former with 2kg of latter (on dry basis). Find the final
condition (humidity and enthalpy) of air. [May/June - 2012]
Given data:
da
Dry bulb temperature, = 20°C
Relative humidity, = 40%
Dry bulb temperature, = 40°C
vil
Relative humidity, = 40%
=
Ci
Solution:
We know that mass balance,
------------ (1)
------------ (2)
By energy balance,
------------ (3)
124 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
Substituting the value of in equation (2),
------------- (4)
From psychrometry chart,
m
of dry air
of dry air
.co of dry air
tas
Similarly,
da
------------ (5)
vil
From psychrometry,
Ci
= 71.67kJ/kg.
3. An air conditioning system is to take in outdoor air at 283K and 30percent
relative humidity at a steady rate of 45 /min and to condition it to 298K and
60% relative humidity. The outdoor air is first heated to 295K in the heating
section and then humidified by the injection of hot steam in the humidifying
125 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
section. Assuming the entire process takes place at a pressure of 100kPa,
determine (i) the rate of heat supply in the heating section and (ii) the mass flow
rate of the steam required in the humidifying section. [Nov/Dec 2009]
Given data:
= 10°C
= 30%
= 25°C
= 60%
= 22°C
= 45 /min
= 100kPa
m
Solution:
Step 1:
.co
The dry of air i.e 10°C of dry bulb temperature and 30% relative humidity is marked
on the psychrometric chart at point
tas
1. The horizontal line is drawn up to 22°C to obtain point
2. The dry of air i.e. 25°C dry bulb temperature and 60% relative humidity is
marked on the psychrometric chart at point
3.
da
vil
Ci
Step 2:
126 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
Draw an inclined line from point 1 to 2. Read enthalpies and specific humidity
values at point 1,2 and 3 from psychrometric chart.
At point 1, enthalpy = 16.5kJ/kg
At point 2, enthalpy = 28kJ/kg
Mass of air, =
= = 0.923kg/s
Heated added,
Q = m( )
= 0.923 (28 – 16.5)
m
= 10.615kJ
Specific humidity,
.co
= 0.003kg/kg of dry air
= 0.012kg/kg of dry air
Moisture added,
tas
= 0.012 – 0.003 = 0.009kg/kg of dry air
We know that,
Specific humidity,
da
vil
Mass of steam = 0.0083kg/s
4. (i) What is the lowest temperature that air can attain in an evaporative cooler, if it
enters at 1atm, 302K and 40% relative humidity? [Nov/Dec 2008]
Ci
Given data:
p = 1bar
T = 302K
= 40%
Solution:
From steam table, corresponding to dry bulb temperature 29°C, saturation
pressure is 4.004kPa
Relative humidity,
127 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
0.4 =
= 1.601kPa
Lowest temperature that air attain in an evaporative cooler = 113.6°C
which is corresponding to = 1.601kPa.
(ii) Consider a room that contains air at 1atm, 308K and 40% relative humidity.
Using the psychrometric chart, determine: the specific humidity, the enthalpy, the wet
bulb temperature, the dew point temperature and the specific volume of air.
Given data:
Pressure, p = 1atm
m
Relative humidity, = 40%
Temperature, T = 308K = 35°C
Solution:
Specific humidity,
.co
From the point 1, draw a horizontal line with respect to
temperature and relative humidity. At this point specific humidity
is 0.0138kJ/kg. i.e. = 0.0138kJ/kg
tas
da
vil
Ci
Enthalpy, h and Wet bulb temperature,
From the point 1, draw a inclined line along the constant wet bulb
temperature line till it cuts enthalpy line. At this point, enthalpy is
52.5kJ/kg and wet bulb temperature is 23.9°C. i.e. h = 52.5kJ/kg and
= 23.9°C
128 S.A.RAMESH – AP/MECH
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m
.co
tas
da
vil
Ci
129 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
Dew point temperature, and specific volume, v
m
Mark point 1 on the psychrometric chart by given dry bulb temperature
.co
(35°C) and relative humidity 40%.
From point 1, draw a horizontal line to the left till it cuts saturation curve.
At that point, temperature is 20°C and specific volume is 0.89
= 20°C and v = 0.89 .
. i.e.
tas
5. 30 /min of moist air at 15°C DBT and 13°C WBT are mixed with 12 /min of
moist air at 25°C DBT and 18°C WBT. Determine DBT and WBT of the mixture
da
assuming barometric pressure is one atmosphere. [Nov/Dec 2008]
Given data:
vil
First steam of air,
Dry bulb temperature, = 15°C
Wet bulb temperature, = 13°C
Flow rate, = 30 /min
Ci
Second steam of air,
Dry bulb temperature, = 25°C
Wet bulb temperature, = 18°C
Flow rate, = 12 /min
Solution:
Step 1:
The first steam of air 15°C DBT and 13°C WBT is marked on the
psychrometric chart at point 1.
Step 2:
130 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
The second stream of air 25°C DBT and 18°C WBT is marked on the
psychrometric chart at point 2.
Join the points 1 and 2 from psychrometric chart.
Step 3:
m
We know that,
.co
Specific humidity of first steam of air,
= 0.007kg/kg of dry air
Specific humidity of second steam of air,
tas
= 0.014kg/kg of dry air
Step 4:
First steam flow rate,
da
= = 0.5 /s
From psychrometric chart we specific volume = 0.835 /kg passing
through point 1.
vil
Mass, = = 0.6kg/s
Second stream flow rate,
Ci
= = 0.2 /s
From psychrometric chart we specific volume = 0.845 /kg passing
through point 2.
Mass, = = 0.24kg/s
We know that,
Substituting and values,
131 S.A.RAMESH – AP/MECH
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ME8391- ENGINEERING THERMODYNAMICS II/III MECHANICAL ENGINEERING
= 0.00943kg/kg of dry air
Specific humidity after mixing,
= 0.00943kg/kg of dry air
Step 5:
Draw a horizontal line from = 0.00943 till it cuts 1 – 2 line.
Name the point 3.
From psychrometric chart, at point 3
Dry bulb temperature, = 24.02°C
Wet bulb temperature, = 18.2°C
m
.co
tas
da
vil
Ci
132 S.A.RAMESH – AP/MECH
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