Thermodynamic Class Note PDF

CHE 1201 – THERMODYNAMICS – LECTURE NOTES
COURSE OBJECTIVES
 To provide students with the basic principles of thermodynamics relevant to many
Engineering processes.
 To state and understand the laws of thermodynamics
 To apply the knowledge in the analysis of thermo systems.
CONTENT
 Basic concepts
 Equation of state and ideal gases
 Specific heat capacities and perfect gases
 Zeroth law of thermodynamics
 Temperature and its measurement
 Heat and work; determination of work for various paths/processes
 First law of thermodynamics as applied to closed systems
 First law of thermodynamics as applied to open systems
 Steady flow and the continuity equation
 Application of first law to common systems
 Steam tables and the working fluid
 Second law of thermodynamics and entropy
 Application of the second law to heat engines
 Refrigeration and heat pumps
 Otto, Dual, Atkinson, Joule and diesel cycles
 Gas turbines
 Combustion equations and chemical equilibrium
 Energy economy and alternative energy sources
LECTURER AND CONTACTS
Ssembatya Martin, Msc Sustainable Energy Engineering (KTH, Stockolm), BSc. Mechanical
Engineering (MUK)
Email: [email protected]
Mob: +256772194123
COURSE ASSESSMENT
Course work and take home tests: 20%
Continuous assessment tests: 20%
Final examination: 60%
REFERENCES
1. Thermodynamics an Engineering approach by Yunus A. Cenel and Michael A. Boles
2. Applied thermodynamics for engineering technologists by Eastop and McConkey
3. Engineering thermodynamics, work and heat transfer by GFC Rogers and YR Mayhew
Ndejje University Faculty of Engineering
Contents
1. INTRODUCTION ...............................................................................................................1
1.1 Thermodynamics ...............................................................................................................1
1.2 System...............................................................................................................................1
1.2.1 Closed system .............................................................................................................1
1.2.2 Open system ...............................................................................................................1
1.3 Property.............................................................................................................................1
1.3.1 Intensive properties .....................................................................................................1
1.3.2 Extensive properties ....................................................................................................1
1.4 Homogeneous substance ....................................................................................................2
1.5 Heat...................................................................................................................................2
1.5.1 Sensible heat ...............................................................................................................2
1.6 Work .................................................................................................................................2
1.7 Process ..............................................................................................................................2
1.7.1 A cyclic process ..........................................................................................................2
1.7.2 Quasi – static process ..................................................................................................2
1.8 Thermal equilibrium ..........................................................................................................2
1.9 Chemical equilibrium ........................................................................................................3
1.10 Mechanical equilibrium ...................................................................................................3
1.10.1 Steady flow ............................................................................................................3
1.10.2 Zeroth law..............................................................................................................3
1.11 Temperature and its measurement ....................................................................................3
2. REVERSIBLE PROCESSES ..................................................................................................4
2.1 Criteria of reversibility ......................................................................................................4
2.2 Equations of state ..............................................................................................................4
2.3 Determination of work during a volume change .................................................................4
2.3.1 Constant Volume process (Iso - volumetric)................................................................5
2.3.2 Constant pressure process ...........................................................................................5
2.3.3 A process with a hyperbolic equation ..........................................................................5
2.3.4 Polytropic processes ...................................................................................................6
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2.4 Specific heat capacities ......................................................................................................6

2.5 Internal energy ..................................................................................................................6
2.6 Enthalpy, H .......................................................................................................................7
2.7 Relationship between Cp and Cv .......................................................................................7
3. FIRST LAW OF THERMODYNAMICS ............................................................................8
3.1 Applied to cyclic processes ................................................................................................8
3.2 As applied to change of state processes for closed systems ................................................8
3.2.1 Analysis of some closed system processes using the first law of thermodynamics .......8
3.3 First law of thermodynamics as applied to open systems....................................................9
3.3.1 A working fluid......................................................................................................9
3.3.2 Steady - flow systems ............................................................................................... 12
3.3.3 Steady – flow process ............................................................................................... 12
3.3.4 Mass balance for a steady flow process ..................................................................... 12
3.3.5 Energy balance for steady – flow systems ............................................................ 12
3.3.6 Some examples of steady – flow Engineering devices ............................................... 13
4. SECOND LAW OF THERMODYNAMICS ..................................................................... 17
4.1 Heat engines .................................................................................................................... 17
4.2 Steam plant...................................................................................................................... 17
4.3 Open gas turbine plant ..................................................................................................... 18
4.4 Closed gas turbine system................................................................................................ 18
4.5 Heat engine performance............................................................................................. 19
4.5.1 Refrigeration plant performance................................................................................ 19
4.5.2 Heat pump performance ............................................................................................ 20
4.5.3 An ideal heat engine ................................................................................................. 20
4.5.4 Reversible heat engine .............................................................................................. 20
5. ENTROPY ........................................................................................................................ 21
5.1 Isentropic efficiency ........................................................................................................ 21
5.2 Determination of entropy ............................................................................................ 22
5.3 Evaluation of entropy change for common Engineering processes ................................... 23
5.3.1 Constant volume process .......................................................................................... 23
5.3.2 Constant pressure process ......................................................................................... 23
5.3.3 Constant temperature process.................................................................................... 23
6. POWER CYCLES ................................................................................................................ 25
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6.1 The Carnot cycles ............................................................................................................ 25

6.1.1 Carnot efficiency of refrigeration and heat pump plants ............................................ 26
6.2 Steam power plants.......................................................................................................... 27
6.2.1 The Carnot vapor cycle ............................................................................................. 27
6.2.2 The Rankine cycle: The ideal for vapor power cycles................................................ 28
6.2.3 Actual Rankine cycle ................................................................................................ 30
6.2.4 Ways of increasing the efficiency of steam power plants........................................... 33
6.3 Gas power cycles ............................................................................................................. 35
6.3.1 The Brayton cycle: The ideal for gas turbine engines ................................................ 35
6.3.2 Actual gas – turbine cycles ....................................................................................... 37
6.3.3 An overview of reciprocating engines .................................................................. 39
6.3.4 Otto cycle: The ideal cycle for Spark – ignition engines ............................................ 40
6.3.5 Causes of deviation of the actual Otto cycles from the ideal Otto cycle ..................... 42
6.3.6 The diesel cycle: The ideal cycle for compression – Ignition engines ........................ 42
6.3.7The dual – combustion cycle ...................................................................................... 44
7. COMBUSTION ................................................................................................................ 46
7.1 Terminology commonly used in combustion ................................................................... 46
7.1.1 Stoichiometry ........................................................................................................... 46
7.1.2 An atom .................................................................................................................... 46
7.1.3 Molecule ................................................................................................................... 46
7.1.4 Chemical element ..................................................................................................... 46
7.1.5 Atomic masses .......................................................................................................... 46
7.1.6 Relative molecular masses ........................................................................................ 46
7.1.7 Oxides ...................................................................................................................... 47
7.1.8 Fuels ......................................................................................................................... 47
7.2 Chemical reactions (chemical changes)............................................................................ 47
7.2.1 Combustion equations ............................................................................................... 47
7.2.2 Air composition ........................................................................................................ 48
7.2.3 Complete combustion ............................................................................................... 48
7.2.4 Incomplete combustion ............................................................................................. 48
7.3 Stoichiometric air – fuel ratio .......................................................................................... 49
7.4 Mixture strength .............................................................................................................. 50
7.5 Avogadro’s Hypothesis ................................................................................................... 50
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7.6 Wet and dry analysis ....................................................................................................... 50

7.7 First law of thermodynamics as applied to combustion processes..................................... 51
7.7.1 Enthalpy of formation ............................................................................................... 52
7.7.2 Higher heating values and lower heating values ........................................................ 52
7.7.3 Dissociation .............................................................................................................. 53
7.8 Energy economy and alternative energy sources .............................................................. 53
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1. INTRODUCTION
1.1 Thermodynamics
It is defined as the study of energy in its various forms and transformations and the interaction of
energy with matter. Thermodynamics is a subject concerned with interactions between the
influence of the system on its surroundings and vice versa.
Applied thermodynamics
This is defined as the science of the relationship between heat, work, and the properties of a
system. It provides the means by which heat energy from various sources is converted into
mechanical work.
1.2 System
A system is simply the collection of matter between prescribed and identifiable boundaries. A
system in thermodynamics refers to a definite quantity of matter bounded by some closed
surfaces. The closed surface is what is referred as the system boundary and anything outside of it
is referred to as the surrounding. This boundary may be real as in case of a tank enclosing a
fluid or it may be imaginary as in the case of a pipe where there is fluid flow.
1.2.1 Closed system

This is the one that doesn’t allow for mass flow across the system boundary.
1.2.2 Open system

This is the one that allows for mass flow across the system boundary. For the case of open
systems, the boundary is referred to as a control surface and the contents within the control
surface are referred to as the control volume.
1.3 Property
A property is any macroscopic observable characteristic of a system. The thermodynamics state
of a system is described by the specification of thermodynamic properties of the system. For any
given state of a substance, each of the thermodynamic properties has only one value.
1.3.1 Intensive properties

These are properties that are independent of the mass and are definable at a point in a substance.
If the substance under consideration is uniform and homogeneous, the value of the intensive
property will be the same for each point in the substance. Examples include; temperature,
density, pressure etc.
1.3.2 Extensive properties

These are properties of a system whose value for the entire system equals the sum of the values
for the component parts of the system or are properties that depend on the total mass of
substance under consideration. The ratio of the extensive property of the system to the total mass
of the substance is referred to as the specific property. Examples of extensive properties include
enthalpy, internal energy, volume etc.
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1.4 Homogeneous substance

A system is said to be homogeneous if the specific values of its properties are the same at all
points in the system.
1.5 Heat
Heat is a form of energy which can be transferred from one body to another of lower temperature
by virtue of the temperature difference between the bodies. It is a transient energy whose rate of
transfer is proportional to the temperature gradient and the constant of proportionality is called
the thermal conductivity.
1.5.1 Sensible heat

Sensible heat refers to that heat that causes a temperature change within a system. Sensible heat
is often given as;
= ( − ) or = ( − )
Where Cp and Cv are heat capacities at constant pressure and constant volume respectively.
1.6 Work
Work is said to be done when the point of application of a force moves through a distance in the
direction of the force.
1.7 Process
Is a change in the state of a system or change in properties of a system. The word “iso” is
normally used to identify the property constant during a certain process. For example:
 Isothermal – constant temperature
 Isobaric – constant pressure
 Iso-volumetric – constant volume
 Isentropic – constant entropy
 Adiabatic – no heat exchange with surroundings
1.7.1 A cyclic process

This is a process that takes place in such a way that its initial and final states are the same.
1.7.2 Quasi – static process

If a process is carried out in such a way that at every instant the system departs, only
infinitesimally from an equilibrium state, the process is called quasi – static or quasi –
equilibrium
1.8 Thermal equilibrium

A system is said to be in thermal equilibrium if there is no temperature imbalance either within
the system or between the system and its surroundings.
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1.9 Chemical equilibrium

This is a state attained by a system in which all possible chemical reactions have ceased.
1.10 Mechanical equilibrium

This is means there are no unbalanced forces present either internal to the system or between the
system and its surroundings.
A system which is in mechanical, chemical and thermodynamic equilibrium is said to be in a
state of thermodynamic equilibrium. Thermodynamic equilibrium defines a state of the system
when all possible properties of the system are unchanging.
1.10.1 Steady flow

This is when the mass entering the system per unit time is equal to mass leaving the system per
unit time.
1.10.2 Zeroth law

When two bodies are in thermal equilibrium with the third body, then the two bodies are also in
thermal equilibrium with each other. This law forms the basis for the measurement of
temperature.
1.11 Temperature and its measurement

Temperature is a property by which we are able to tell how cold or hot the body is. The zeroth
law forms the basis for the measurement of temperature. In order to detect temperature, the
change of certain properties with temperature is used for example specific volume (for fluids and
liquids), resistance of metals, color of glowing filament etc.
Some of the common instruments for measuring temperature are liquid in glass thermometers,
constant volume gas thermometer, thermocouples, resistance thermometers, etc.
For a liquid in glass thermometer, with increase in temperature, the volume of the fluid increases
more rapidly than that of the glass container and thus the liquid level rises. To give the
thermometer a scale, two reference points are selected and arbitrary values of temperature are
assigned to them. The lower reference point is usually taken as the ice point and the upper one is
as the steam point of water with both taken at atmospheric pressure, the choice of the values of
the temperature at the two reference points will determine the magnitude of each division. For
the case of water, the ice point is taken as 00C and the steam point 1000C.
Since the zero point when using different substances is not the same, the values obtained are
gauge temperatures and will depend on the reference substances.
In order to obtained temperatures having the same absolute reference points, we make use of
what is referred to as constant volume gas thermometer. The reference point for the constant
volume gas thermometer is independent of the gas being used within the thermometer. This
thermometer is made of a constant volume vessel equipped with a gauge for measuring pressure.
When the vessel is subjected to varying external temperatures, the pressure within the vessel will
increase accordingly.
The absolute temperature scale is defined such that; =
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2. REVERSIBLE PROCESSES
A reversible process is one that can be reversed without leaving any resultant change in either the
system or the surroundings i.e. a reversible process is one that can be reversed without leaving
any resultant change in either the system or the surrounding. Thus, it is always possible to
change the direction of the process and restore both the system and surrounding to their original
state.
A reversible process is an idealization and all actual processes are irreversible and approach the
reversible process only in special cases. The main features of an irreversible process are the
dissipative effects which are not directly useful. These all tend to increase disorder within the
system. Among the dissipative effects include friction and/or viscosity.
2.1 Criteria of reversibility

1. The process must be frictionless
2. Difference in pressure between the fluid and its surroundings during the process must be
infinitely small
3. Difference in temperature between the fluid and its surroundings during the process must
be infinitely small.
Note: All reversible processes are quasi – static but the reverse is not true.
2.2 Equations of state

The equation of state of a perfect gas can be written as; = = , where P and T
are pressure and absolute temperature respectively. This equation can also be written as;
= , where n is the number of moles of the gas and is the universal gas constant, where
= 8.314 /
Note: = =
2.3 Determination of work during a volume change
Figure2.1 Work due to volumetric expansion

Consider a gas contained in a cylinder, during a given process the piston moves from point 1 to
point 2 resulting in the volume change from V1 to V2.
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If the distance moved is dl, and the force causing this expansion is F, then the small element of
work done dW is given as; =
If the cross section area of the piston is A, from the definition of pressure, P, then =
The elemental work done is therefore given as; = ……………………………(1)
Integrating on both sides of (1) and noting that = , gives;
2.3.1 Constant Volume process (Iso - volumetric)
Figure 2.1 Iso - volumetric process
From =∫ , but = 0 hence =0
2.3.2 Constant pressure process
Figure5.3 Isobaric process
= = ( − )
Therefore; = ( − )
2.3.3 A process with a hyperbolic equation

=
Therefore, =∫ =
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2.3.4 Polytropic processes

These obey the equation, = → =
Therefore, =∫ = ∫
1
= [ ] = −
1− 1−
Since = = , then;
1
= ( − )
1−
Note
With the use of the gas equation of state, = , the following respective expressions (a) and
(b) for the relationships between pressure and temperature and volume and temperature for a
polytropic process can be obtained:
= ................................................................................................................... (a)
= …………………………………………………………………………….. (b)
For an adiabatic process, = , where γ is the ratio of the specific heat capacity at constant
pressure to that at constant volume. Thus an adiabatic process has a general equation, = .
Using the gas equation of state gives the expressions similar to (a) and (b) with = for the
relationships between P and T and V and T respectively for an adiabatic process.
Therefore, for an adiabatic process; = ( − )
2.4 Specific heat capacities

Specific heat capacity at constant volume, Cv is the change in internal energy per degree
temperature change for a constant volume process.
2.5 Internal energy

This is the energy associated with the molecular motion of the substance. Internal energy differs
from heat and work in that heat and work are transient energies where as internal energy is a
property of a system. Although a system or a substance has kinetic energy and potential energy
associated with the motion of the system as a whole, systems also posess internal energy which
is due to the energies of the molecules that comprise the system. Even in cases where the vessel
containing the substance is stationary, the substance consists of a large number of molecules
moving constantly in random fashion throughout the vessel. These molecules have kinetic
energy due to their translation, rotational and vibratory motions and potential energy due to the
intermolecular forces of attraction.
The sum of these energies for all the molecules comprising the system is what is referred to as
internal energy, U, for the system.
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2.6 Enthalpy, H
Enthalpy is a property of the system defined by the equation; = + . It is designated as H
and specific enthalpy as, h.
Specific enthalpy is defined by the equation ℎ = + , where u is specific internal energy and
v is the specific volume of the system.
From the definition of specific heat capacity Cv, then; =
The values of Cv depend on temperature of the control volume. It is a specific property and
therefore its value on a mass basis is given as;
=
Specific heat capacity at constant pressure, Cp is defined as the change in enthalpy per degree
temperature change at constant pressure. Hence, = and =
Cp and Cv for an ideal gas are functions of only temperature and because of this;
= and ℎ = . For a real gas, Cp and Cv vary with temperature but for most
practical purposes, a suitable average may be used.
A perfect gas is an ideal gas whose values of Cp and Cv are constant for all pressures and
temperatures.
For a perfect gas,
= therefore, − = ( − )
ℎ= hence, ℎ − ℎ = ( − )
2.7 Relationship between Cp and Cv

From ℎ = + ,
ℎ= + ( ), and by use of the gas equation;
ℎ= + , hence;
= +
∴ = + , putting = ∴ = 1+
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3. FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics can be stated mathematically as; ∆ = ∆ + ∆ where ∆ is
the heat supplied to the system, ∆ is the resultant change in internal energy and ∆ the
boundary work done by the system.
3.1 Applied to cyclic processes

When a system undergoes a thermodynamic cycle, the net heat supplied to the system from its
surroundings is equal to net work done by the system on its surroundings. Work done by the
system on the surroundings is positive and work done by the surroundings on the system is
negative.
3.2 As applied to change of state processes for closed systems

For a closed system undergoing a thermodynamic process, there is a system property called
energy such that a change in its value is equal to the difference between heat supplied to the
system and work done by the system. The first law of thermodynamics as applied to closed
systems is mathematically written as:
− = ∆ ………………………..………………………………………………..( )
But, ∆ = ∆ +∆ + ∆ ………………………………………………………..( )
For closed systems, changes in kinetic and potential energies are negligible since they are usually
very small as compared to changes in internal energy. Therefore, they are usually neglected in
the first law expressions, i.e.
− = ∆ …………………………………………………………………………….( )
For a cyclic process, ∆ = 0, therefore, = or ∑ =∑
3.2.1 Analysis of some closed system processes using the first law of thermodynamics
In the following analysis, the processes are assumed to be reversible
1. Constant volume process
=
From − = ∆ and with = ∴ =0

This implies, = ∆ = ( − )
2. Constant temperature process

Since ∆ = 0, then =
3. Constant pressure process

− = ∆ , but = ( − )
∴ − ( − )=∆
− + = ∆ , rearranging this gives;
=( + )−( + )= −
= ( − )= ( − )
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4. An adiabatic process
For an adiabatic process, =0
∴ = −∆ = −( − )
= −
Examples 3.1
1. A reciprocating compressor delivers 0.10kg/s of air at a pressure of 12 bar, the air enters
the compressor at 1 bar and 150C. Calculate the delivering temperature of the air and the
work transfer rate in the compression process, for:
.
(i) A reversible polytropic process, = (436 K, -21050 W)
(ii) A reversible adiabatic process
(iii)A reversible isothermal process. (288 K, -20550.2 W)
(Assume air is a perfect gas with = 1.005 and = 1.4)
2. A mass of gas occupying 0.008m3 at 6kN/m2 and 800C is expanded reversibly in a non
.
flow process according to the equation, = . The pressure at the end of the
2
expansion is 0.7kN/m . The gas is then heated at constant pressure back to the original
temperature, taking Cp and Cv as 1.005 and 0.74 kJ/kgK respectively; determine
(i) the work transfer in the expansion process (722.3 J)
(ii) The heat transfer in the expansion process (352.5 J)
(iii)The volume at the end of the heating process (0.668 m3)
(iv) The change in internal energy during the heating process. (369.63 J)
3.3 First law of thermodynamics as applied to open systems
3.3.1 The working fluid

A working fluid is the matter contained within the boundaries of a system. It can either be a
liquid, a vapor or a gas. Although all substances can exist in either one of these phases, we
usually identify a substance with the phase in which it is in equilibrium at atmospheric pressure
and temperature. Only the above three phases shall be considered since the solid phase is of little
importance in engineering thermodynamics. Most of the working fluids in engineering
thermodynamics are pure substances.
A pure substance is one that has a homogeneous and invariable composition e.g. water,
ammonia, etc.
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Figure3.1 Change of state of the working fluid as a result of heating

In the study of pure substances, water will be used as an example and the sequence of events
which occur when a unit mass of water is heated at constant pressure will be used to describe the
behavior of pure substances.
When one kilogram of water is heated at constant pressure, in a closed vessel as shown in
Figure3.1 above, its temperature rises with a decrease in specific volume until 40C. After this, the
volume begins to increase steadily. Water is said to have its highest density at 40C. The
temperature continues to rise until point C, and further addition of heat at this point will not bring
about further increase in temperature. At point C, water is said to be saturated and the
temperature at that point is called the saturation temperature. At atmospheric pressure, this is
1000C.
Between C and D, water boils at a constant temperature until all the water has been turned into
vapor at D. C to D is referred to as the mixed region and the substance at that point is a wet
vapor. D is called the saturation vapor point.
After the evaporation process, further heating results into rise in temperature and the vapor is
referred to as superheated. The difference between the saturation temperature and the
temperature of the superheated vapor is called the degree of superheat.
The relation between T and V can also be obtained for various values of pressure, P and the
relationship between P and V can be shown on a property diagram. As the pressure increases,
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saturation temperature rises and the transition region between liquid and vapor becomes
progressively shorter. Consider Figure 3.2 below, with pressures > >
Figure3.2 Temperature - volume relations for 3 different pressures
A line connecting various saturated liquid points is called the saturated liquid line and is always
given a suffix, f. The line connecting saturated vapor points is called the saturated vapor line and
is usually given a suffix, g. Between states, f and, g pressure and temperature are constant but the
water is partially vaporized and the properties are defined by what is known as the dryness
fraction, x.
The dryness fraction is the ratio of mass of dry saturated vapor to the total mass of vapor and
liquid i.e. a mixture in between the saturated vapor line and saturated liquid line has x parts of
dry vapor and (1 – x) parts of saturated liquid.
If the value of some property of the saturated liquid e.g. specific enthalpy is Pf and its value for
the saturated vapor is Pg for the same pressure and saturation temperature, the value of the
property, P of a mixture with dryness fraction, x at the same pressure is then given as;
= (1 − ) +
The above equation can be further written as; = + − .
The difference − is always quoted as for most properties in thermodynamic tables.
Specific enthalpy, specific internal energy, and specific volume can therefore, be determined
using the following respective equations, with the usual notations for the properties:
ℎ=ℎ + ℎ
= + and,
= +
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Examples 3.2
1. Find the dryness fraction, specific volume and specific internal energy of steam at 7 bar
and with specific enthalpy of 2600 kJkg -1.
2. What is the degree of superheat for steam at a pressure of 10 bar and with specific
enthalpy of 3000 kJ/kg?
3.3.2 Steady - flow systems

These include devices such as turbines, compressors and nozzles which operate for a long period
of time under the same conditions once the transient start – up period is completed and steady
operation reached.
3.3.3 Steady – flow process

This is a process during which a fluid flows through a control volume steadily i.e. properties can
change from point to point within a control volume but at any point they remain constant for the
entire process.
During a steady flow process, no intensive or extensive properties within the control volume
change with time. Therefore, the boundary work is zero during such processes. The fluid
properties at the exit and entrance remain constant during the process.
3.3.4 Mass balance for a steady flow process

Since there is no mass accumulation within the control volume, then; ̇ = ̇ (kg/s)
For multiple inlets and exits; ∑ ̇ = ∑ ̇
For single exit – single entrance devices like nozzles, diffusers, compressors and pumps;
̇ = ̇ ⇒ =
3.3.5 Energy balance for steady – flow systems

During a steady flow process, the energy content of the control volume remains constant, hence
the change in the total energy of the control volume is zero.
Therefore, − =∆ =0
∴ = …………………………………………………………………………(1)
Where is rate of net energy transfer in by heat, work and mass and;
is the rate of energy transfer out by heat, work and mass.
Equation (1) can be written more explicitly as;
̇ + ̇ +∑ ̇ = ̇ + ̇ +∑ ̇
This can be further written as;
1 1
̇ + ̇ + ̇ ℎ + + = ̇ + ̇ + ̇ ℎ + +
2 2
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Assuming that heat is transferred to the system at a rate ̇ and work is produced by the system at
a rate, ̇ , the above last expression can be written as;
1 1
̇− ̇ = ̇ ℎ + + − ̇ ℎ + +
2 2
For single stream devices, we can denote the entrance and exit states as 1 and 2 respectively.
The mass flow through the entire control volume is constant, therefore, ̇ = ̇ = ̇
Thus, for single stream steady flow systems, the energy balance becomes;
1
̇ − ̇ = ̇ ℎ −ℎ + − + ( − )
2
Dividing by ̇ , gives the energy balance on a unit mass basis;
1
− = ℎ −ℎ + − + ( − )
2
If the fluid experiences a negligible change in kinetic energy and potential energy as it flows
through the control volume, then;
− = ℎ −ℎ
h is the specific enthalpy of the fluid
̇ is the rate of heat transfer between the control volume and surroundings. When the control
volume is losing heat, ̇ is negative. If the control volume is well insulated (adiabatic), ̇ = 0
̇ is power, for steady – flow devices, the control volume is constant and hence no boundary
work is involved and hence, ̇ , represents the remaining forms of work done per unit time.
Many steady – flow devices such as turbines, compressors and pumps, transmit power through a
shaft, and ̇ simply becomes the shaft power.
3.3.6 Some examples of steady – flow Engineering devices

a) Nozzles and diffusers
Nozzles and diffusers are commonly applied in jet engines, rockets, and space craft and even
garden hoses.
A nozzle is a device that increases the velocity of a fluid at the expense of pressure.
A diffuser is a device that increases the pressure of a fluid by slowing it down.
Note
(i) The rate of heat transfer between the fluid and surrounding is usually very small since the
fluid is so fast and hence, = 0.
(ii) Nozzles and diffusers involve no power ̇ = 0 and any change in potential energy is
negligible (∆ = 0)
(iii)However, nozzles and diffusers involve high changes in kinetic energy and hence
∆ ≠0
(iv) (ℎ − ℎ ) is the change in specific enthalpy of the fluid which can be obtained from
thermodynamic tables or by use of ∆ℎ = ( − )
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Examples
1. Air at 100C and 80 kPa enters a diffuser of a jet engine steadily with a velocity of 300 ms-1.
The inlet area of the diffuser is 0.4 m2. The air leaves the diffuser with a velocity that is very
small compared with the inlet velocity. Determine:
(i) The mass flow rate of the air (Ans: 118.196 kg/s)
(ii) The temperature of the air leaving the diffuser (Ans: 54.80C)
(Take R = 0.287 kJ/kgK and γ = 1.4)
2. Air which may considered as a perfect gas enters an adiabatic nozzle with negligible
velocity. The entry temperature is 760 K. The flow throughout the nozzle is reversible and
the mass flow rate is 2kg/s. Calculate the exit velocity and exit diameter of the nozzle if the
inlet and exit pressures are 6 bar and 1 bar respectively. Take R = 0.287 kJ/kgK and γ = 1.4.
(Ans: 782.14 ms-1, 0.065 m)
b) Turbines and compressors

In steam, gas or hydroelectric power plants, the device that drives the electric generator is the
turbine. As the fluid passes the blades that are attached to the shaft, the shaft rotates
producing work (power). The work done in a turbine is positive since it is done by the fluid.
Compressors, as well as pumps and fans are devices used to increase the pressure of fluids.
Work is transferred to these devices from an external source through a shaft hence the
devices involve work inputs.
Distinction between fans, compressors and pumps
A fan increases the pressure of a gas slightly while a compressor is capable of compressing the
gas to very high pressures.
Pumps work very much like compressors except that they handle liquids instead of gases.
Note
(i) Turbines produce power output whereas compressors, pumps and fans require power
input.
(ii) Heat transfer from turbines is negligible. Heat transfer from compressors is also
negligible unless there is intentional cooling.
(iii)The velocity involved in these devices is negligible with exceptions of turbines and
fans, hence ∆ =0
(iv) The velocities encountered in most turbines are very high and the fluid experiences a
significant change in kinetic energy(∆ ≠ 0).
(v) Potential energy changes are negligible for all of these devices ∆ =0
Figure3.3 Turbine
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The first law of thermodynamics can be applied to an expansion device e.g. turbine as below;
− = (∆ℎ + ∆ +∆ ), with =∆ =∆ =0
− = ̇ (ℎ − ℎ ) ⇒ = ̇ (ℎ − ℎ ), where h1, h2 are the entrance and exit specific
enthalpies and ̇ is the fluid mass flow rate. Hence the amount of work produced by the turbine
is equal to the enthalpy change between the inlet and outlet.
The compressor has a similar analysis only that unlike the turbine, the compressor involves
energy addition to the fluid hence h2 is higher than h1 in its case.
Examples 3.3
1. Steam at a pressure of 60 bar and temperature 5000C, enters an adiabatic turbine with a
velocity of 20 ms-1 and expands to a pressure of 0.5 bar. At exit, the steam has a velocity 200
ms-1 a dryness fraction 0.98. If the turbine is required to produce 1 MW for a spinning plant,
determine the mass flow rate of steam required and the cross sectional area of flow at the
turbine exit. (Ans: 1.246 kg/s, 0.0198 m2)
2. Air at 100 kPa and 280 K is compressed steadily to 600 kPa and 400 K. The mass flow rate
of the air is 0.02 kg/s, and a heat loss of16 kJ/kg occurs during the process. Assuming the
change in kinetic and potential energies are negligible, determine the necessary power input.
(2.092 kW)
Boilers and condensers (heat exchangers)
Figure3.4 U - tube and Shell and Tube heat exchangers

Heat exchangers are used in condensers and evaporators for mainly refrigeration plants. One cold
fluid stream is heated up by a warm fluid stream.
Boilers are normally used to produce steam in many manufacturing firms e.g. textile firms, tea
production firms etc and steam cogeneration power plants.
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Figure3.5 Boiler
Applying the steady flow energy equation to any of these systems gives;
− = (∆ℎ + ∆ +∆ )
There is no work production and/or consumption in any of these devices hence, =0
There is also negligible potential and kinetic energy changes; hence ∆ =∆ =0
Then, = ̇ (ℎ − ℎ ).
Hence for a boiler or a heat exchanger, the amount of thermal energy added or extracted from the
fluid is equal to the enthalpy change for the fluid between inlet and outlet.
Throttling valve
Figure3.6 Throttling valve

The throttling valve is used to produce an isenthalpic expansion to a fluid in refrigeration and
steam power plants.
Applying the steady flow energy equation between the sections 1 and 2 shown in Figure 3.6;
− = (∆ℎ + ∆ +∆ )
For this system;
There is no heat extraction and/or addition hence Q = 0.
There is no displacement work, hence, W = 0
The entry and exit velocities are similar and the entry and outlet elevation are almost the same,
hence, ∆ =∆ =0
The equation reduces to; ̇ (ℎ − ℎ ) = 0 ⇒ ℎ = ℎ
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4. SECOND LAW OF THERMODYNAMICS

In power generating machines, the machine will accept a heat transfer and give a work transfer.
The second law states that it is impossible to convert all this heat energy into work. This law has
two forms:
i) Max Planck’s form of the second law as applied to direct engines
This states that it is impossible for a heat engine to produce net work in a complete cycle if it
exchanges heat only with bodies at a single fixed temperature or it is impossible cause an
engine to operate in a thermodynamic cycle in which the only interactions are the positive
work done on the surroundings and heat transfer from a system which remains at constant
temperature and finally, it is impossible to construct a machine which will give continuous
work positive transfer while exchanging heat with a single reservoir.
ii) Clausius’ statement of the second law as applied to reversed heat engines
It states that it is impossible to construct any device that operating in a cycle would produce
no other effect other than the transfer of heat from a cold body to a hot body.
4.1 Heat engines

A heat engine is a continuously operating thermodynamic system at a boundary of which there is
only heat and work interactions. Continuously operating means that the state of the system
exhibits only periodic changes i.e. although the working fluid changes state as it flows to and
from each component, its state at every point within the entire device or system remains the same
throughout the operation and therefore undergoes a cyclic process. The system considered in this
definition (heat engine) is that of a closed of system.
The devices that qualify to be called heat engines are:
a) Continuously operated
b) They are systems and not control volumes
c) Produce positive net work output by accepting a positive heat transfer of a high
temperature region and rejecting heat for a lower temperature region.
4.2 Steam plant
Figure 4.1 Schematic diagram of a steam plant
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In steam power plants, the working fluid flows steadily through all the components shown in
Figure 4.1 of the steam plant hence executing a cyclic process. According to the system
boundary, the only interactions between the system and the surrounding are the heat and work
transfers. A steam plant qualifies to be a heat engine because:
i) It is a closed system and not an open system
ii) The working fluid executes a cycle
iii) There is only heat and work transfers across the system boundary.
4.3 Open gas turbine plant
Figure 4.2 Schematic diagram of an open gas turbine plant

a) An open gas turbine engine on the other hand has a working fluid that does not execute a
cycle.
b) The working fluid crosses the system boundary.
c) There is no heat transfer across the system boundary.
4.4 Closed gas turbine system

This is similar in construction to the steam plant. However, the closed gas turbine plant uses a
gas instead of steam. It is cheaper to construct an open gas turbine engine than a closed gas
turbine engine because:
(i) The closed one requires a gas heater which is more expensive to make as compared to a
combustion chamber.
(ii) It is simpler to allow exhaust gases to flow to the atmosphere than to provide a cooler and
a coolant.
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4.5 Heat engine performance
Figure4.3 Second law of thermodynamics for heat engine and reversed engine
The measure of the success of the heat engine is the comparison of wok output, W with heat
transfer into the system QH. This comparison factor is referred to as thermal efficiency. It is the
measure of how much heat is converted into work and how much is wasted. In general,
efficiency, η is defined as:
=
For direct heat engines such as steam plants, and gas turbine engines, efficiency, η is defined by:
= =
Where, W = net work output

QH = Heat supplied from high temperature region.
From the definition of the first law of thermodynamics for a cyclic process, = −
Therefore, = =1−
By the second law of thermodynamics, there is always a heat rejection and therefore, QL can
never be equal to zero. Therefore, thermal efficiency can never be 100%.
For a reversed heat engine (heat pumps and refrigerators), comparison is given by what is
referred to as coefficient of performance (COP).
4.5.1 Refrigeration plant performance

The coefficient of performance of a refrigeration plant, COPref, is defined as; =
because, our desire is to draw heat from a low temperature region with the aid of power supply,
W.
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4.5.2 Heat pump performance

The desire of the heat pump is to supply heat to a high temperature region from a low
temperature reservoir with the aid of power supply, W.
The coefficient of performance of a heat pump, COPhp is thus given by; = =
Therefore, =1+ = 1+
4.5.3 An ideal heat engine

An ideal heat engine is one for which all processes are reversible and there are no losses such as
friction. Such an engine is the most efficient possible between two reservoirs. This is known as
the Carnot principle and the efficiency of the ideal heat engine is called the Carnot efficiency.
A reversible engine must have all its processes reversible but a number of practical processes
like friction, heat transfer and combustion are all irreversible. These processes can never be fully
eliminated from a heat engine and therefore an ideal heat engine is a theoretical one which can
never be used in practice but the ideal engine is used to determine the theoretical maximum
efficiency.
4.5.4 Reversible heat engine

A heat engine which engages in heat transfer with two systems at fixed but different
temperatures (thermal reservoirs) is said to be reversible if its efficiency when operating directly
is equal to the reciprocal of the coefficient of performance (COP) when it is acting as a heat
pump between the same temperatures.
1
=
Note
a) All reversible heat engines have the same efficiency when operating between two reservoirs
of fixed but different temperatures. The efficiency of a reversible heat engine does not
depend on the nature of the materials from which the engines are made or the working fluid
but only on the temperature of the reservoirs.
b) The efficiency of a reversible heat engine is the greatest that can be exhibited by any engine
operating between two systems having two constant different temperatures.
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5. ENTROPY
Entropy is a property of a system such that its increase, − as the system undergoes a change
from state 1 to state 2 is given by;
− = =
S = entropy
= Heat transfer to or from system during the process.
Entropy can also be defined as the measure of disorder in a system.
Reversible adiabatic process
For a reversible adiabatic process, = 0, therefore; − =0
All reversible adiabatic processes are isentropic and knowledge of this helps us fix the end states
of a reversible process.
5.1 Isentropic efficiency

Isentropic processes are used as standard of comparison usually, it is necessary to assess the
performance of an actual adiabatic machine by comparing it with its reversible adiabatic
counterpart. The result of comparison is usually expressed as isentropic efficiency.
The isentropic efficiency of a work producing machine is the ratio of the actual work output to
the work output of a reversible adiabatic machine taking in the fluid at the same initial state and
exhausting it at the same final pressure.
The isentropic efficiency of a work consuming machine is the ratio of the work input of a
reversible adiabatic machine to the actual input of the machine taking in the fluid at the same
initial state and exhausting it at the same pressure.
Figure5.1 Compression and expansion processes on a T - s diagram

Isentropic efficiency of a work consuming machine e.g. a compressor is the ratio of isentropic
work to actual work i.e. =
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The isentropic efficiency of a work producing machine e.g. a turbine is the ratio of actual work
output to the isentropic work out put i.e. =
Examples 5.1
1. Steam enters an adiabatic turbine at 60 bar, 6000C, and 80m/s and leaves at 0.5 bar, 1000C,
and 140 m/s. if the power output of the turbine is 8 MW, determine:
(i) The mass flow rate flowing through the turbine (8.27 kg/s)
(ii) The isentropic efficiency of the turbine (83.7%)
2. Air enters an adiabatic compressor at 100 kPa and 170C at a rate of 2.4 m3/s, and exits at
2570C. The compressor has an isentropic efficiency of 84%. Neglecting the changes in KE
and PE and taking R = 0.287 kJ/kgK and cp = 1.005 kJ/kgK, determine:
(i) The exit pressure of air (634.2 kPa)
(ii) The power required to drive the compressor (695.234 kW)
5.2 Determination of entropy

In determining entropy, a reversible process was used but most engineering processes are
irreversible. Therefore, in order to evaluate the entropy change for these irreversible processes,
we have to find properties which can be easily measured and relate them to entropy change. This
is done through what is referred to as the Tds relationships.
For an infinitely small process, undergone by a unit mass of a pure substance, in absence of
gravity, motion, electricity and magnetism, the first law of thermodynamics is given by the
expression;
− = = +
If the process is reversible, then; =
Therefore, = +
From the definition of entropy,
= → =
Substituting (2) into (1)

= + …………………………………………………………………………….(1)
But ℎ = +
ℎ= + +
Substituting for du into (3)
= + ℎ− −
∴ = ℎ− ………………………………………………………………………….(2)
Equation (1) and (2) are referred to as the relationships. The relations were arrived at
by using the idea of reversible processes but these relations are mainly concerned with
properties. Since we are dealing with properties, these relations can be used to evaluate entropy
change for both reversible and irreversible processes.
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For a perfect gas,

= + ……………………………………………………………………………...(a)
But = → =
From (a)
= + …………………………………………………………………………….......(b)
For a perfect gas, = ; substituting for du into (b)
= +
Integrating on both sides;
− = + ………………………………………………………………….*
Similarly from, (6)

ℎ
= − = −
∴ − = − ……………………………………………………………….**
5.3 Evaluation of entropy change for common Engineering processes

5.3.1 Constant volume process
From = + = +
= (since = 0)
=
∴ − = =
5.3.2 Constant pressure process

From (6), = =
− = =
5.3.3 Constant temperature process

From (3), = +
∴ − = = =
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Examples 5.2
1. 1 kg of air at 1.013 bar, 170C, is compressed according to the law PV1.3 = constant, until the
pressure is 5 bar. Calculate the change of entropy. (-0.0885 kJ/kg)
2. 1 kg of air at 1.02 bar, 200C undergoes a process in which the pressure is raised to 6.12 bar,
and the volume becomes 0.25 m3. Calculate the change of entropy. (0.083 kJ/kg)
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6. POWER CYCLES
6.1 The Carnot cycles
Figure 6.1 T - s and P - V diagrams for a Carnot cycle

The Carnot cycle regardless of the working fluid has four basic processes; two reversible
isothermal heat transfer processes and two adiabatic processes.
Based on Figure 6.1 above, process ab is a reversible isothermal process in which heat is
transferred to the working fluid at temperature, Tmax (TH) from a single fixed temperature
reservoir.
bc is a reversible adiabatic process in which there is an expansion of the working fluid and work
is done.
cd is a reversible isothermal process in which heat is transferred to the sink (reservoir at low
temperature) from the system at a temperature Tmin (TL).
da is a reservoir adiabatic compression process which returns the working fluid to its original
state.
Since all processes must be reversible, they must be performed infinitely slowly so that the
process proceeds in a series of equilibrium states.
From the definition of entropy;
= ( − ) and
= ( − ), but = = (isentropic processes)
( − )
∴ =1− = 1−
( − )
→ = 1−
Note
Because the efficiency of an ideal heat engine depends only on temperatures, Tmax and Tmin, for
the efficiency to increase, Tmax should be as high as possible and Tmin as low as possible. This is
valid whether the power producing cycle is ideal or not.
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6.1.1 Carnot efficiency of refrigeration and heat pump plants

Consider Figure 6.2 below,
Figure6.2 Schematic of a reversed heat engine

The Carnot efficiency of the refrigeration plant is given by;
= =
−
This can be written in terms of thermodynamic temperatures as;
1
= =
− / −1
For a heat pump (whose purpose is to produce heating from a low temperature source to a high
temperature sink with aid of some energy addition), the Carnot coefficient of performance is
given by;
1
= = = =
− − 1− /
Where QL and QH are the amount of heat absorbed from the low – temperature medium and
amount of heat rejected to the high temperature medium. TL and TH are the temperatures of the
low temperature medium and high temperature medium respectively.
Examples 6.1
1. A Carnot heat engine receives 500 kJ of heat per cycle from a high – temperature source at
6250C and rejects heat to a low – temperature sink at 300C. Determine:
a) The thermal efficiency of this Carnot engine. (67.2%)
b) The amount of heat rejected to the heat sink per cycle. (164 kJ)
2. An investor claims to have developed a refrigerator that maintains the refrigerated space at
350F while operating in a room where the temperature is 750F and has a COP of 13.5. is this
claim reasonable?
3. A heat pump maintains a house at a fixed temperature. The house is to be maintained at 210C
at all times. The house is estimated to be losing heat at a rate of 135,000 kJ/h when the
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outside temperature drops to -50C. Determine the minimum power required to drive this heat
pump. (3.32 kW)
4. A refrigerator removes heat from 230 grams of water at 00C until the water is turned into ice
at 00C. Heat from the system is rejected into the atmosphere at 250C. Latent heat of fusion of
water is 333.7 kJ/kg.
(i) What is the maximum coefficient of performance for this refrigeration process?
(ii) Determine the minimum amount of work required by the compressor motor of this
refrigerator.
(iii)What is the change in entropy of the air in the environment under the most ideal
conditions?
6.2 Steam power plants (Vapor cycles)
6.2.1 The Carnot vapor cycle
Figure 6.3 T - s diagram for a Carnot vapor cycle

Figure 6.3 shows the T – S diagram representation of the processes involved in the vapor power
cycle. As mentioned earlier, the Carnot cycle is the most efficient cycle operating between two
specific temperatures which is a reason for looking at the Carnot cycle first as a prospective ideal
cycle for steam power plants.
The Carnot vapor cycle has the following ideal processes:
 Process 1 – 2: Process in which the fluid is heated reversibly and isothermally in the
boiler.
 Process 2 – 3: The fluid is expanded isentropically in a turbine.
 Process 3 – 4: The fluid is condensed reversibly and isothermally in a condenser.
 Process 4 – 1: The fluid is compressed isentropically by a compressor to the initial state.
However, the following impracticalities (draw backs) are associated with the Carnot vapor cycle:
1. Limiting the heat addition process, 1 – 2 to the two phase region of the working fluid
severely limits the maximum temperature that can be attained by the cycle (i.e. it has to
remain under the critical temperature of 3740C). Limiting the maximum temperature in the
cycle limits the cycle’s thermal efficiency in turn. However, any attempt to raise the
maximum temperature results in heat addition in the single phase region, which is not easy to
accomplish isothermally.
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2. The turbine in this cycle handles steam of very low quality i.e. steam with high moisture
content. The impingement of liquid droplets on the turbine blades causes erosion, a major
cause of turbine blades wear.
3. The isentropic compression process, 4 – 1 involves the compression of a liquid – vapor
mixture to a saturated liquid. Two difficulties are associated with this process; it is not easy
to control the condensation process precisely so as to end with the desired steam quality at
state 4 and secondly it is impossible to design a compressor that handles the two phases.
Due to these impracticalities the Carnot cycle cannot be approximated in actual devices and is
not a realistic model for vapor power cycles.
6.2.2 The Rankine cycle: The ideal for vapor power cycles
Figure 6.4 Schematic and T - s diagram for a Rankine cycle

Many of the impracticalities in the Carnot cycle can be eliminated by superheating the steam in
the boiler and condensing it completed in the condenser by what is referred to as the Rankine
cycle which is the ideal cycle for vapor power plants. This is illustrated in the T – S diagram
above. The ideal Rankine cycle has the following reversible processes:
 1 – 2: Isentropic compression in a pump.
 2 – 3: Constant pressure heat addition in the boiler.
 3 – 4: Isentropic expansion in the turbine.
 4 – 1: Constant heat rejection in the condenser.
Analysis of the Rankine cycle
Usually in the calculation of Rankine efficiency, potential and kinetic energy changes in all
components are negligible.
Boiler
Water enters the boiler as a compressed liquid at state 2 and usually leaves the boiler as
superheated liquid at state 3. The boiler is basically a heat exchanger where the heat originating
from combustion gases, nuclear reactors or other sources is transferred to the water essentially at
constant pressure. The boiler, together with the region where the water is superheated (super
heater) is commonly referred to as the steam generator.
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Amount of heat transferred to water, Q23, in the boiler can be determined from the equation of
steady flow process, neglecting potential and kinetic energy changes.
= ̇ (ℎ − ℎ )
Turbine
Steam, usually superheated, enters the turbine at state 3, where it expands isentropically and
produces work by rotating the shaft connected to generator. The temperature and pressure drop
down to state 4, where the steam enters the condenser. Steam at this state is usually a saturated
liquid – vapor mixture of high steam quality.
Neglecting the potential and kinetic energy changes with = 0, work (power), WT, delivered by
the steam turbine can be obtained;
− = ̇ (ℎ − ℎ )
∴ = ̇ (ℎ − ℎ )
Condenser
Steam at state 4 enters the condenser where it is condensed at constant pressure. The condenser
is basically a large heat exchanger which rejects heat to a cooling medium such as a lake, river or
the atmosphere. Water leaves the condenser as a saturated liquid at state 1 where it enters the
pump for compression back to the boiler pressure. In areas where water is scarce, the power
plants are cooled by air instead of water by a method similar to that used in car engines. This
method of cooling is called dry cooling.
Similarly from the equation of steady flow processes with, = 0, ∆ =0&∆ = 0, the
rate of heat rejection from the condenser, Q41 can be obtained as:
= ̇ (ℎ − ℎ )
Pump
At state 1, saturated liquid enters a pump which raises the water’s pressure from the condenser
pressure to boiler pressure and the cycle is completed.
Power input to the pump, WP can be determined as;
− = ̇ (ℎ − ℎ )
∴ = ̇ (ℎ − ℎ )
The power input to the pump can also be obtained from; ℎ − ℎ = ( − ), with v1 the
specific volume at state 1.
Proof
For reversible processes, = + ……………………………………………………...(1)
Also ℎ = + ………………………………………………………………………………...(2)
ℎ= + +
∴ = ℎ− − …………………………………………………………………….(3)
Substituting for into (1), gives:
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= ℎ− − +
∴ = ℎ−
But for a pump, =0
ℎ= , and integrating on both sides;
ℎ −ℎ = ( − )
Note
The pump power input is normally very small compared to the power output from the turbine
and is usually neglected in comparison to the latter.
Rankine cycle thermal efficiency
The thermal efficiency for this cycle can be obtained from, =
Net work output is given by; = −

− (ℎ − ℎ ) − (ℎ − ℎ )
∴ = =
(ℎ − ℎ )
6.2.3 Actual Rankine cycle

Actual vapor power cycle differs from the ideal Rankine cycle, as illustrated in the Figure 6.5
below, as a result of irreversibilities in various components. Fluid friction and heat loss to the
surroundings are the two main sources of irreversibilities.
Figure6.5 Actual Rankine cycle T - s

Fluid friction causes pressure drops in the boiler, the condenser and the piping between various
components. As a result the steam leaves the boiler at somewhat lower pressure. To compensate
for these pressure drops the water has to be pumped to a higher pressure than the ideal cycle calls
for, this calls for a bigger pump and hence a higher power input.
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The other major source of irreversibilities is the heat lost from the steam to the surroundings as
the steam flows through various components. To maintain the same level of power output, more
heat has to be added to compensate for these heat losses hence lower efficiency for the cycle.
Analysis of the actual Rankine cycle
The pressure drops are always very small (always less than 3%) and they are usually neglected.
However, irreversibilities in the pump and turbine are usually very significant and they are
usually accounted for by what is referred to as the isentropic efficiency of the respective device.
Due to irreversibilities, the pump requires bigger power input than for isentropic case and the
turbine produces a smaller power output than it would produce if it were isentropic.
Consider the T – S diagram shown in Figure 6.6 below;
Figure 6.6 Effect of the isentropic efficiency on the Rankine cycle

The actual Rankine process consists of the following processes:
 1 – 2: The actual irreversible compression process in the pump.
 2 – 3: Heat addition process in the boiler ( that may be considered a constant pressure
process)
 3 – 4: The actual irreversible expansion process in the turbine.
 4 – 1: A heat rejection process in the condenser (may be considered constant pressure
process)
Processes 1 – 2s and 3 – 4s are ideal isentropic processes that are only used for comparison
with actual irreversible process using the isentropic efficiency of the corresponding
machines.
If the isentropic efficiency of the turbine and pump are, ηt and ηp respectively, then:
̇( )
= = = , and;
̇( )
̇( )
= = =
̇( )
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Other criteria used in comparing the operation of steam (vapor) plants

1. Efficiency ratio
This is the ratio of the actual cycle efficiency to Rankine efficiency. It should be as large as
possible and the closer it is to 1.0, the less is the energy wasted against irreversibilities.
2. Work ratio
This is defined as the ratio of net work to gross work. This indicates portion of work (energy)
produced by the turbine is used to drive the pump. The closer work ratio is to 1.0, the less
turbine work is used in driving the pump
−
=
3. Specific steam consumption (ssc)

3600
=
It is a measure that relates the plant output to the steam that is flowing through it. The
amount of steam flow also indicates the size of steam plant and its component parts that is it
is a measure of relative sizes of steam plants. ssc has units of kg/kWh
Examples 6.2
1. A steam power plant operates on a simple ideal Rankine cycle between pressure limits of
3 MPa and 50 kPa. The temperature of the steam at the turbine inlet is 4500C, and the
mass flow rate of steam through the cycle is 40 kg/s. Show the cycle on a T –s diagram
with respect to saturation lines, and determine:
(i) The thermal efficiency of the cycle (29.3%)
(ii) The net power output of the power plant. (35.17 MW)
2. A power plant which operates on a Rankine cycle with steam as the working fluid
operates at a boiler pressure of 40 bar and a condenser pressure of 0.1 bar. If the
temperature at the turbine inlet is 4000C, and the isentropic efficiencies of the turbine and
the pump are 80% and 90% respectively, find:
(i) The thermal efficiency (25.5%)
(ii) Work ratio of the plant (0.994)
3. A steam power plant operates between a boiler pressure of 50 bar and a condenser
pressure of 0.05 bar. Calculate for these limits the cycle efficiency, work ratio, and
specific steam consumption:
a) For a Carnot cycle. (43.02%, 0.724, 5.106 kg/kWh)
b) For a Rankine cycle with dry saturated steam at the entry to the turbine.
(36.6%, 0.995, 3.713 kg/kWh)
c) For a Rankine cycle with steam at a temperature of 3750C at the turbine entry.
(37.9%, 0.996, 3.181 kg/kWh)
d) For a Rankine cycle in c) above but with isentropic efficiency of the turbine is
85% and that of the pump is 88%. (32.1%, 0.994, 3.75 kg/kWh)
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6.2.4 Ways of increasing the efficiency of steam power plants

In order to increase the efficiency of a basic Rankine cycle, either we increase the temperature
and/or pressure at which heat is added to the working fluid or we can decrease the temperature at
which heat is rejected.
Increasing the boiler pressure
Figure6.7 Effect of increasing pressure on the Rankine cycle performance

If the condenser pressure and temperature and the boiler exit temperature are kept constant as
shown in Figure 6.7 above and the boiler pressure is increased from P1 to P2, then the cycle
1‫׀‬2‫׀‬344‫׀‬5‫׀‬1‫ ׀‬will be achieved. From the diagram it is evident that the average temperature at
which heat is supplied is greater for pressure P2 than it is at pressure P1
The efficiency of the cycle corresponding to higher boiler pressure is greater than that of lower
boiler pressure. The net work is approximately the same at both pressure levels but the heat input
is lower for higher boiler pressure cycle.
Although increase of the boiler pressure results in increase in efficiency, it has a disadvantage in
that the wetness of steam at the turbine exit is greater for higher pressure levels than for lower
boiler pressure levels. The wet moisture contains water droplets which at high rotational speeds
cause erosion of turbine blades. This results in shortening of the turbine lifetime. Usually it is
recommended that the steam quality at the turbine exit must not be greater than 0.9.
Since increase in boiler pressure results in a decrease in steam quality at the turbine exit, we use
what is referred to as a reheat cycle to obtain the advantage of high thermal efficiency associated
with increased boiler pressure maintaining the turbine exit steam quality at acceptable levels.
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Figure6.8 Improving the Rankine cycle performance by reheating

The least efficient part of the heat transfer in a steam power plant is the heating of the cold feed
water because it takes place temperatures well below the cycle maximum temperature. This is
overcome by the use of feed water heaters to raise the cycle efficiency through increasing the
average heat addition temperature. This process is known as regeneration.
Lowering the condenser pressure
Steam exits as a saturated liquid at the saturation temperature corresponding to the operating
pressure of the condenser. Therefore, lowering the condenser pressure automatically lowers the
temperature of the steam and hence lowers the temperature at which heat is rejected. Since the
steam power plants are closed systems, condenser pressures are lowered to pressures well below
the atmospheric pressure. However, there is a limit for the value the condenser pressure that can
be used; it cannot be lower than the saturation pressure corresponding to the temperature of the
cooling medium.
Super heating the steam to high temperatures
The average temperature at which heat is added can be increased without increasing the boiler
pressure by superheating the steam to high temperatures. However superheating increases both
the work output by the turbine and the heat input in the boiler but the increase in work output is
faster than the increase in heat input, the overall effect is the increase in thermal efficiency.
Super heating has another advantage of improving the steam quality at the turbine exit, which
greatly reduces the erosion effect of the steam moisture content to the turbine blades hence
improving the turbine life.
The temperature to which the steam can be super heated is limited by the metallurgical properties
of the turbine blades. Presently the highest steam temperature allowed at the turbine inlet is
6200C. Any increase in this value will depend on improving the present materials or inventing
new ones that can withstand higher temperatures.
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6.3 Gas power cycles

In gas power cycles, the working fluid remains a gas throughout the entire cycle. Spark – ignition
engines, diesel engines, and conventional gas turbines are examples of devices that operate on
gas cycles. In all these engines, heat is provided by burning a fuel within system boundaries.
That is, they are internal combustion engines. Because of this combustion process, the
composition of the working fluid changes from air and fuel to combustion products during the
course of the cycle. However, because air is predominantly nitrogen that undergoes hardly any
chemical reactions in the combustion chamber, the working fluid closely resembles air at all
times.
The actual gas power plants are rather complex. To simplify the analysis, we employ the
following assumptions, commonly known as the air – standard assumptions.
1. The working fluid is air, which continuously circulates in a closed loop and always
behaves as an ideal gas.
2. All processes that make up the cycle are internally reversible.
3. The combustion process is replaceable by a heat addition process from an external source
4. The exhaust process is replaced by a heat rejection process that restores the working fluid
to the initial state.
6.3.1 The Brayton cycle: The ideal for gas turbine engines
Figure6.9 Open and closed cycle gas - turbine engine
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Figure 6.10 P - V and T - S diagrams for the Brayton cycle

The cycle on which a gas turbine heat engine operates is referred to as the Brayton cycle or Joule
cycle. Gas turbines normally operate on open gas turbine power plants. Fresh air from the
atmosphere is drawn into the compressor where its pressure and temperature are raised. The high
pressure air proceeds to the combustion chamber, where the fuel is burned at constant pressure.
The resulting high – temperature gases then enter the turbine, where they expand to atmospheric
pressure thus producing power. The exhaust gases are thrown out to the atmosphere and not re –
circulated hence the cycle referred to as open cycle.
The open gas – turbine cycle can be modeled as a closed cycle by utilizing the air standard
assumptions. Here the compression and expansion remain the same but the combustion process
is replaced by a constant – pressure heat addition process and the exhaust process is replaced by
a constant pressure heat rejection process to the ambient air.
The ideal cycle that the working fluid under goes in this closed loop is the Brayton cycle and is
made of the following four processes:
1 – 2: Isentropic compression in a compressor
2 – 3: Constant – pressure heat addition
3 – 4: Isentropic expansion in a turbine
4 – 1: Constant pressure heat rejection
Analysis
Heat addition, , during combustion and heat rejection, in the exhaust process are given
by:
=ℎ −ℎ = ( − )
= ℎ −ℎ = ( − )
Since processes 1 – 2 and 3 – 4 are isentropic, and = and = , then:
( )⁄ ( )⁄
= = =
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= is normally referred to as the compressor pressure ratio, .
Net work (power) from the plant

= −
= ( − )− ( − )
If the mass flow rate of the working fluid (air) is ̇ , then the total net power output is given by:
= ̇ [( − )−( − )]
Thermal efficiency
( − ) −
= = 1− = 1−
( − ) −
( )⁄ ( )⁄
But = and =
( − ) 1
∴ =1− ( )⁄
= 1− ( )⁄
( − )
Therefore, for a constant pressure cycle (ideal Brayton cycle), the efficiency is dependant only
on the compressor pressure ratio. The equation for thermal efficiency shows that the higher the
pressure ratio, the higher the efficiency, but in practice, the value of r p is limited by other factors
and one of the main factors is the maximum temperature T3 at which the turbine blades can
operate. T3 is limited by the metallurgical considerations of the turbine blades.
Work ratio
( − )− ( − )
= =
( − )
=1−
But = and =
−1
∴ =1−
1
1− ( )⁄
= 1−
6.3.2 Actual gas – turbine cycles

The actual gas – turbine cycle differs from the ideal Brayton cycle on several accounts. First of
all there is some pressure drop during the heat addition and heat rejection processes. More
importantly, the actual work input to the compressor is more and the actual work output from the
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turbine is less than the ideal case because of the irreversibilities. The deviation of the actual work
input and work output for the compressor and turbine respectively can be accounted for by the
use of the concept of the isentropic efficiency.
The pressure drops are very small because of the better designs that have been developed
recently and can thus be neglected.
Figure6.11 Effect of isentropic efficiencies on the Brayton cycle

Compressor
If the compressor isentropic efficiency is, , the actual enthalpy, h2 and/or temperature, T2 at the
compressor exit can be obtained from:
ℎ −ℎ ( − )
= = =
ℎ −ℎ ( − )
Turbine
If the isentropic efficiency of the turbine is, , the actual enthalpy, h4 and/or temperature, T4 at
the exit of the turbine can be obtained from;
ℎ −ℎ ( − )
= = =
ℎ −ℎ ( − )
Note
The values of cp and γ are temperature dependant and therefore their values are different for the
combustion and expansion processes and the compression process.
Examples 6.3
For the following examples take the values of cp and γ as 1.005 kJ/kgK and 1.4 for air and 1.15 kJ/kgK
and 1.333 for combustion and expansion processes.
1. a) A stationary power plant operating on an ideal Brayton cycle has a pressure ratio of 8. The
air temperature is 250C at the compressor inlet and 9270C at the turbine inlet. Determine
i) the gas temperature at the exits of compressor and the turbine
ii) the work ratio
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iii) the thermal efficiency

b) If the compressor isentropic efficiency is 80% and the turbine efficiency is 85%,
determine:
i) the work ratio
ii) the thermal efficiency
iii) the turbine exit temperature.
2. A gas – turbine power plant operates on a simple Brayton cycle with air as the working fluid
and delivers 15MW of power. The minimum and maximum temperatures in the cycle are 310
K and 900 K, and the compressor pressure ratio is 8. Assuming an isentropic efficiency of
80% for the compressor and 86% for the turbine, determine the mass flow rate of the air
through the cycle and the cycle efficiency.
3. Air enters the compressor of a gas – turbine engine at 270C and 100 kPa, where it is
compressed to 700 kPa and 3070C. Heat is supplied to air in the amount of 950 kJ/kg before
it enters the turbine. For a turbine efficiency of 86%, determine:
i) The fraction of the turbine work output that is used to drive the compressor
ii) The thermal efficiency
6.3.3 An overview of reciprocating engines
Figure6.12 Reciprocating engines terminology

The basic components of a reciprocating engine are illustrated in Figure 6.12 above. The piston
reciprocates between two positions called the top dead centre (TDC) – which is the position of
the piston when it forms the smallest volume in the cylinder and bottom dead centre (BDC) – the
position of the piston when it forms the biggest volume in the cylinder.
The distance between the TDC and BDC is the longest distance the piston can travel in the
cylinder and is called the stroke of the engine.
The diameter of the engine’s cylinder is called the bore of engine cylinder.
The air (in case of diesel engine) or air – fuel mixture (in case of petrol engine) is drawn into the
cylinder through the intake valve, and the combustion products are drawn out of the cylinder
through the exhaust valve.
The volume displacement as the piston moves from BDC to TDC is called the displacement
volume or swept volume.
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The ratio of maximum volume formed in the cylinder to minimum volume or clearance volume
is called the compression ratio, rv of the engine:
+
= = =
Note compression ratio is a volume ratio and should not be confused with the pressure ratio.
Mean effective pressure – This is the pressure that if acted on the piston during the entire stroke,
would produce the same amount of work as that produced during the entire power stroke.
= × × = ×
Or = = =
6.3.4 Otto cycle: The ideal cycle for Spark – ignition engines
Petrol engines operate on what is referred to as the Otto cycle. The air fuel mixture from the
carburetor or from the EFI is injected into the cylinder during the induction stroke. During this
process, the inlet valve is open and the piston moves downwards and the pressure is maintained
constant within the cylinder while the volume available for the mixture increases. At the BDC,
the inlet valve closes and the mixture is compressed on the upward motion of the piston until it
reaches the TDC. A spark is given off by the spark plug at TDC causing ignition and combustion
of the mixture. Ideally, the combustion of the mixture and the resultant heat release occur
instantaneously raising the temperature and pressure of the combustion gases. The gases at high
temperatures and pressure then push the piston down in what is referred as the power stroke. As
a result, this work is transferred to crankshaft, a component responsible for converting the
translational motion of the piston into rotary motion.
When the piston reaches BDC, the exhaust valve is opened thereby reducing the pressure and
expelling the combustion gases in what is called the exhaust stroke. During this stroke, pressure
is reducing because the combustion gases are being expelled out, but the volume remains
constant.
Figure6.13 Otto cycle
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Process 1 – 2 is a reversible adiabatic compression, from the general equation of steady flow
processes with negligible changes in kinetic and potential energies and = 0, gives
− = − = ( − )
Process 2 – 3 is heat addition to the system i.e. a reversible constant volume heating process:
= − = ( − )
Process 3 – 4 is a reversible adiabatic expansion process;
= − = ( − )
Heat rejected in the process 4 – 1 is also given by:
= − = ( − )
Otto cycle thermal efficiency
The thermal efficiency of the Otto cycle is given by:
= but = −
∴ = − = ( − )− ( − )
( − )− ( − ) ( − )
∴ = = 1−
( − ) ( − )
For the adiabatic processes 1 – 2 and 3 – 4
= =( ) =
∴ = ( ) and = ( )
( − ) 1
⇒ =1− =1−
( − )( ) ( )
Examples 6.4
1. Calculate the ideal air standard cycle efficiency based on the Otto cycle for a petrol engine
with a cylinder bore of 50 mm, a stroke of 75 mm and a clearance volume of 21.3 cm3.
(Ans: 56.3%)
2. An ideal Otto cycle has a compression ratio of 8.0. At the beginning of the of the
compression process, air is at 100 kPa and 170C, and 800 kJ/kg of heat is transferred to air
during the constant volume heat – addition process. Taking the respective values of cv and γ
as 0.718 kJ/kgK and 1.4 for the compression process and 0.823 kJ/kgK and 1.333 for the heat
– addition, expansion and heat rejection processes, determine:
(i) The maximum temperature and pressure that occur during the cycle
(ii) The net work output
(iii)The thermal efficiency
(iv) The mean effective pressure
3. The compression ratio of an airs - standard Otto cycle is 9.5. Prior to the isentropic
compression process, the air is at 100 kPa, 170C, and 600 cm3. The temperature at the end of
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the isentropic expansion process is 800 K. Using specific heat values at room temperature,
determine
i) the highest temperature and pressure in the cycle. (1969 K, 6449 kPa)
ii) the amount of heat transferred (0.65 kJ)
iii) the thermal efficiency, and (59.4%)
iv) the mean effective pressure (719 kPa)
6.3.5 Causes of deviation of the actual Otto cycles from the ideal Otto cycle
1. Air is not the working fluid throughout the cycle (the gaseous products of combustion differ
from air)
2. Some of the energy released during combustion goes into dissociation of molecules and
therefore not available for useful work.
3. There is heat loss through the cylinder walls
4. There are friction losses between the piston and the cylinder
5. There is a finite time required for the spark flame to propagate through the entire mass of gas.
When all of these are put into consideration, the actual thermal efficiencies of Otto cycle engines
are less than those of the ideal Otto cycle.
6.3.6 The diesel cycle: The ideal cycle for compression – Ignition engines
For diesel cycle, unlike the Otto cycle, fuel is sprayed into the cylinder after the compression
process and is burnt while the piston is moved down the cylinder. This gives rise to the constant
pressure combustion.
Figure6.14: Diesel cycle

Thermal efficiency
But = − ,∴ = 1−
= ( − )=( − )+ ( − ) and
= ( − )=( − )
( − )
⇒ =1−
( − )
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2 – 3 is a constant pressure process, therefore =
The ratio; is referred to as the cut off ratio, β.
∴ = ⇒ = − = ( − 1)
1 – 2 is an adiabatic – isentropic process;
= , is the compression ratio,
∴ =( ) ⇒ =
( )
3 – 4 is also an adiabatic process, therefore:
= = ⇒ =
∴ = = ⇒ =
But = ⇒ = =
− = − = ( − 1)
( ) ( − 1)
− 1
∴ =1− =1−
( − ) ( − 1)
1 −1
=1−
−1
Looking at the last expression for the efficiency of a diesel engine, one can notice that the diesel
engine thermal efficiency differs from the Otto by the quantity in brackets, and this quantity is
always greater than 1.0. Therefore, for the same compression ratio rv for cold air – assumptions,
the engine based on the diesel cycle is less efficient than the other based on the Otto cycle i.e.
> .
Examples 6.5
1. A diesel engine has an inlet temperature and pressure of 150C and 1 bar respectively. The
compression ratio is 12/1 and the maximum cycle temperature is 11000C. Calculate the
air standard thermal efficiency based on the diesel cycle. Take cp = 1.005 kJ/kgK and γ =
1.4 for all processes (56.3%)
2. An air – standard diesel cycle has a compression ratio of 16 and a cut off ratio 2. At the
beginning of the compression process, air is at 95 kPa and 270C. Taking the respective
values of cp and γ as 1..005 kJ/kgK and 1.4 for the compression process and 1.111 kJ/kgK
43 SM
and 1.333 for the heat – addition and expansion processes, and the value of R as 0.287
kJ/kgK, determine:
(i) The temperature after the heat – addition process

(ii) The thermal efficiency
(iii)The mean effective pressure
6.3.7The dual – combustion cycle

Modern oil engines, although still called diesel engines use solid injection of the fuel. The fuel is
injected by a spring loaded injector, the fuel pump being operated by a cam driven from the
engine crankshaft. The ideal cycle used as a basis for comparison is called the dual – combustion
cycle or mixed cycle shown in the p – v figure below:
Figure4.15 The dual - combustion cycle

The processes that make the dual – combustion cycle include;
1 – 2: isentropic compression
2 – 3: Reversible constant volume heating
3 – 4: Reversible constant pressure heating
4 – 5: Isentropic expansion
5 – 1: Reversible constant volume cooling
The heat is supplied in two parts; the first part at constant volume and the remainder at constant
pressure, hence the name dual – combustion. In order to fix the thermal efficiency completely,
three factors are necessary; the compression ratio, = , the ratio of pressures, =
and the ratio of volumes, = .
It can then be shown that, the thermal efficiency is given by:

−1
1−
[( − 1) + ( − 1)]
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Note
 When, k = 1 (i.e. P3 = P2) the equation reduces the thermal efficiency of a diesel cycle.
 The total heat input is given by: = ( − )+ ( − )
 Heat rejected during process 5 – 1 is given by: = ( − )
Therefore, thermal efficiency can be given by:
( − )
=1−
( − )+ ( − )
Examples 6.6
1. An oil engine takes in air at 1.01 bar, 200C and the maximum cycle pressure is 69 bar.
The compressor ratio is 18. Calculate the air standard thermal efficiency based on the
dual – combustion cycle and the mean effective pressure of the cycle. Assume that the
heat added at constant volume is equal to the heat added at constant pressure. Take cp =
1.005 kJ/kgK and γ = 1.4 for all processes. (68.2%, 2.25 bar)
2. An air standard dual – combustion cycle has a mean effective pressure of 10 bar. The
minimum pressure and temperature are 1 bar and 170C respectively, and the compression
ratio is 16. Calculate the maximum cycle temperature when the cycle efficiency is 60 %.
The maximum cycle pressure is 60 bar. (19590C)
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7. COMBUSTION
Combustion can be precisely defined as the oxidation of a fuel accompanied by heat release.
7.1 Terminology commonly used in combustion

7.1.1 Stoichiometry
This is the section of thermodynamics that deals with the relationship between the composition
of the reactants and that of the products in a chemical reaction.
7.1.2 An atom
This is the simplest particle which can take part in a chemical reaction
7.1.3 Molecule
This is a unit comprising of atoms held together by strong inter – atomic forces. Molecules may
either have atoms of the same element like oxygen (O2), Hydrogen (H2), Nitrogen (N2) etc, or
atoms of different elements e.g. water (H2O), sulphurdioxide (SO2), Nitrogen monoxide (NO),
ammonia (NH3), etc.
7.1.4 Chemical element

These are substances that that makeup matter. Common elements in combustion are Carbon,
Hydrogen, Oxygen, Nitrogen, and Sulphur. The inter atomic forces which bind atoms together in
a molecule can cause an appreciable effect for only very small distances and that is why most
molecules consist of a small number of atoms. When the number of atoms is high, the atoms will
be bound weakly and therefore easily decomposed. Carbon and Oxygen are the only exceptions
to this rule.
7.1.5 Atomic masses

Different elements have different masses and these values are important when a quantitative
analysis is required. The actual masses of atoms are very small hence ratios of masses of atoms
are used. These ratios are given by relative atomic masses.
The relative atomic mass of a substance is the mass a single entity of the substance relative to a
single entity of a carbon – 12. Table 7.1 below shows the relative atomic masses of the common
elements in combustion of fuels.
Table7.1 Relative atomic masses of common elements in combustion
Element Chemical symbol Relative atomic mass
Carbon C 12
Nitrogen N 14
Oxygen O 16
Sulphur S 32
Hydrogen H 1
7.1.6 Relative molecular masses

Relative molecular masses are based on the relative atomic masses of the elements that make up
a molecule and the number of the atoms of each element in the molecule.
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It is important to note that the relative molecular mass of a molecule represent the mass of one
kmole of a substance in kg.
Table 7.2 below shows the relative molecular masses of common molecules (compounds) that
may be met in the field of combustion of fuels.
Table7.2 Relative molecular masses for common compounds in combustion
Compound Chemical formula Relative molecular mass
Water, steam H2O (2 × 1) + (1 × 16) = 18
Carbon monoxide CO (1 × 12) + (1 × 16) = 28
Carbon dioxide CO2 (1 × 12) + (2 × 16) = 44
Sulphur dioxide SO2 (1 × 32) + (2 × 16) = 64
Methane CH4 (1 × 12) + (4 × 1) = 16
Ethane C2H6 (2 × 12) + (6 × 1) = 30
Propane C3H8 (3 × 12) + (8 × 1) = 44
n – Butane C4H10 (4 × 12) + (10 × 1) = 58
Ethylene C2H4 (2 × 12) + (4 × 1) = 28
Propylene C3H6 (3 × 12) + (6 × 1) = 42
n – pentane C5H12 (5 × 12) + (12 × 1) = 72
Benzene C6H6 (6 × 12) + (6 × 1) = 78
Ethanol C2H5OH (2 × 12) + (6 × 1) + (1 × 16) = 46
n – Octane C8H18 (8 × 12) + (18 × 1) = 114
7.1.7 Oxides
These are molecules (products) formed after the reaction of Oxygen with atoms of other
elements.
7.1.8 Fuels
The most important elements in a fuel are Carbon and Hydrogen. The fuels may also consist
other elements such as Sulphur and quantities of incombustibles like ash, Nitrogen, Oxygen, and
water.
Unless at very high temperatures (30000F and above), Nitrogen is relatively inactive and does
not take part in combustion reactions. However, it becomes one of the constituents of the
products of combustion.
7.2 Chemical reactions (chemical changes)

A chemical reaction is a process in which the inter – atomic bonds in the reactant molecules are
broken followed by the re – arrangement of atoms thus set free.
A chemical reaction is not an interaction between systems such as heat and work but it is a
change within a system.
7.2.1 Combustion equations

Using the conservation of mass principle, during combustion, total mass of products should be
equal to total mass of reactants.
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The composition of a fuel expressed in percentage of masses of the chemical composition of the
fuel is known as the mass analysis of the fuel. This is most useful in the case of solid fuels. For
liquid hydrocarbon fuels, it is also sufficiently accurate to use the mass analysis.
The total mass of atoms of each element involved in the reaction remains the same but atoms are
rearranged into groups (molecules) having different chemical properties.
7.2.2 Air composition

Air is taken to approximately contain mainly Oxygen and Nitrogen with the volume and mass
analysis shown in the table below:
Table7.3 Air mass and volume analysis
Volume analysis Mass analysis
Nitrogen (N2) 79% 76.7%
Oxygen (O2) 21% 23.3%
For combustion processes, Oxygen supplied is usually supplied from the atmospheric air. Since
in atmospheric air, oxygen is accompanied by nitrogen, then this nitrogen should also be
included in the equation. Since Nitrogen is almost inert as far as combustion chemical reactions
are concerned, then it appears on both sides of the equation.
Since by volume, there is 21% Oxygen and 79% Nitrogen, then using Avogadro’s Hypothesis;
one mole of Oxygen in air comes along with moles of Nitrogen.
7.2.3 Complete combustion

This is a form of combustion that normally occurs when air is supplied in excess of the required
stoichiometric amount. The products of combustion normally consist of CO2 as the major
constituent with water vapor as the other constituent in case of hydrocarbon fuels. Examples of
equations for fuels undergoing complete combustion include:
79 79
+ + → +
21 21
79 79
3 +5 +5× →3 +4 +5×
21 21 2
79 79
50 +2 +2× → +3 +2× 2
21 21
7.2.4 Incomplete combustion
This form of combustion occurs when there is limited supply of air to the fuel during combustion
(i.e. when the air supplied is less than the stoichiometric amount required). Normally CO is
formed as one of the major constituents in the products of the combustion reaction. Some of the
examples of chemical equations for incomplete combustion processes include:
1 1 79 1 79
+ + × → + ×
2 2 21 2 21
79 79
3 8+2 2+2× →3 +4 2 +2× 2
21 21
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Note
Many fuels contain some sulphur (S) as one of the combustible constituents. However, even
though S contributes to the energy output of the fuel during combustion, it also contributes
towards formation of sulphur - oxides, SOx which lead to formation of acid – rain, a main cause
of corrosion of many metallic products and a cause of deaths of different fauna and flora.
Sulphur mainly undergoes a chemical reaction represented by the equation below:
79 79
+ 2 + → + 2
21 21
7.3 Stoichiometric air – fuel ratio
A stoichiometric mixture of air and fuel is the one that contains just sufficient Oxygen for
complete combustion of the fuel to take place.
A weak mixture is the one which has excess air than the stiochiometric amount of air.
A rich mixture is the one which has insufficient amount of air for the combustion of the fuel.
The amount of air required for combustion is called theoretical or stoichiometric air. If more air
is provided than that required to completely burn the fuel, Oxygen will appear in the products.
Excess air usually expressed in percentage of that required for complete combustion. Therefore,
30% excess air means 130% theoretical air is provided.
− ℎ
% =
ℎ
Note
Normally air is supplied in excess in order to prevent the possibility of incomplete combustion of
some parts of the fuel, hence preventing formation of CO, a very poisonous gas.
Examples 7.1
1. Propane burns in air according to the equation;
79 79
3 +5 +5× →3 +4 +5× 2
21 21
1 kmole of propane has a mass of; (3 × 12) + (8 × 1) = 44
Mass of air required for complete combustion of 1 kmol of this fuel is;
79
5 × 2 × 16 + 21 × 5 × 2 × 14 = 686.7
686.7
Therefore, the stoichiometric air fuel ratio is; = = 15.6 kg air/kg fuel
44
2. Methane (Acetelyne) burns according to the following chemical equation.

79 79
+2 +2× → +2 +2× 2
21 21
1 kmol of CH4 has a mass of; 1 × 12 + 4 × 1 = 16
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79
Mass of stoichiometric required air for 1 kmol of CH4 = 2 × 2 × 16 + 2 × 21 × 2 × 14 =
274.7
274.7
∴ ℎ , = 16 = 17.2 kg air/ kg fuel
If air was supplied as 20% excess air, them the actual air fuel ratio is; 1.2 × 17.2 = 20.64
kg air/ kg fuel
For gaseous fuels, the ratio is usually given by volume but for solid and liquid fuels the ratios are
expressed by mass. The result for percentage of excess air is positive for a weak mixture and
negative for a rich mixture.
Note
For boiler plants, the mixture is usually greater than 20% weak. For gas turbines, it can be as
much as 300% weak. Petrol and diesel engines have to meet various conditions of load and speed
and operate over a wide range of mixture strength.
7.4 Mixture strength

/
This is defined as; ℎ= /
Where fuels contain some Oxygen, this oxygen will be available for the combustion process and
therefore, the fuel requires a smaller supply of air.
If less air is supplied than that required for complete combustion, the products will contain CO
hydrogen and perhaps even unburnt fuel and Carbon.
7.5 Avogadro’s Hypothesis

It states that the volume of one mole of any gas is the same as the volume of one mole of any
other gas for the same conditions of temperature and pressure or equal moles of gases for the
same conditions of temperature and pressure have equal volumes.
A mole is the amount of substance of a system which contains as many elementary entities as
there are atoms in 12 g of carbon, 12C. The unit symbol for a mole is mol but in SI units it is
convenient to use kilomole with unit symbol kmol.
The mass per kmol of any substance is known as the molar mass, M and the mass, m in
kilograms of n kilomoles is given by = .
Relative masses of the various molecules are commonly used and the relative molecular mass is
numerically equal to the molar mass, M but is dimensionless.
7.6 Wet and dry analysis

When analyzing the products of combustion, the sample is usually cooled down to a temperature
below the saturation temperature of steam present. In this case, the steam content is not included
in the analysis and this is called the dry analysis of the products. Since the products of
combustion are usually gases at the flue gas temperature, it is common to quote the analysis by
volume.
An analysis which includes steam in the analysis is called the wet analysis.
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Examples 7.2
1. A gas fired boiler uses fuel of the following percentage volumetric analysis: 48% Hydrogen,
22.5% methane, 19% Carbon monoxide, 6% Nitrogen and 4.5% carbon dioxide. The air is
supplied in 25% excess of the stoichiometric air supply and with this air – fuel ratio
combustion is complete. Calculate the percentage analysis of the flue gases based;
a) on a volumetric analysis of the dry flue gases. (CO2 10.4%, N2 85.1%, O2 4.5%)
b) on a mass analysis of for the total wet flue gases (CO2 13.7%, N2 70.8%, O2 4.2%, H2O
11.3%).
2. A gaseous fuel consists of 45% methane, 25% hydrogen, 17% carbon monoxide, 3 %
oxygen, 6% carbon dioxide and 4% nitrogen by volume.
a) Calculate the stoichiometric air – fuel ratio by volume.
b) Calculate the wet volumetric analysis and mass analysis of the products of combustion.
3. A fuel for the petrol engine consists of 86% carbon and 14% hydrogen by mass.
a) Calculate the stoichiometric A/F ratio by mass
b) If the fuel is burnt with 10% excess air, calculate the dry volumetric analysis of the
products of combustion.
4. Ethyl alcohol is used in a spark ignition engine. Calculate:

a) the stoichiometric A/F ratio. (8.957/1)
b) the A/F ratio and wet and dry analysis by volume of the exhaust gases for a mixture
strength of 90%. (9.952; CO2 11.19%, H2O 16.79%, O2 1.88%, N2 70.16%; CO2 13.45%,
O2 2.24%, N2 84.31%)
c) the A/F ratio and wet analysis by volume of the exhaust gases for a mixture strength of
120%. (7.47; CO2 6.94%, CO 6.94%, H2O 20.83%, N2 65.29%)
7.7 First law of thermodynamics as applied to combustion processes

In the study of chemical reactions especially combustion we are interested in determining the
amount of heat liberated during this reaction. The first law of thermodynamics states that in the
steady flow process, with no work, and no change in potential and kinetic energies, then;
= −
In order to use the above equation, with reactants and products consisting of different substances,
it is necessary to adopt a common baseline to evaluate the enthalpies for different substances. As
a baseline for enthalpy, we use H = 0 for an element in its natural state at 250C, 1 atmosphere.
The enthalpy of compounds at the reference state can be determined experimentally.
= −
For example, for the case of carbon dioxide;
ℎ + ℎ → ℎ
Where h denotes enthalpy per molecule and n is the number of moles of the constituents
involved in the reaction.
51 SM
At 250C and 1 atmosphere, enthalpy of carbon is zero and that of O2 is also zero. The enthalpy of
a compound is taken as the enthalpy of formation of that compound.
7.7.1 Enthalpy of formation

The enthalpy of formation ∆ is the increase of enthalpy when a compound is formed from its
constituent elements in their natural and standard states.
Enthalpy of a substance at 250C and 1 atmosphere is called the enthalpy of formation of that
substance since it is numerically equal to the heat liberated when that substance is formed.
The enthalpy of formation is usually used to calculate the heat of reaction of combustion for a
number of hydrocarbons. Table7.4 below shows the enthalpy of formation of common
compounds in combustion of fuels:
Table 7.4 Enthalpies of formation of common compounds in combustion of fuels
Compound Chemical formula Enthalpy of formation( kJ/kmol)
Carbon monoxide CO -110530
Carbon dioxide CO2 -393510
Water - Liquid H2O -285830
Vapor H2O -241810
Methane CH4 -74850
Ethane C2H6 -84670
Propane C3H8 -103850
Benzene C6H6 +82930
Octane gas C8H18 -208450
Octane liquid C8H18 -249900
Examples 7.3
1. Propane burns in air according to the following chemical equation:
79 79
3 +5 + 5 × 21 →3 +4 + 5 × 21 2
If 1500 m3/s of propane, measured at room temperature is burnt in a combustor, determine

the power output of the combustor.
2. 80 kg/s of liquid octane is run through a combustion chamber. If the combustion chamber is
used boil water at 40 bar for a steam power plant, the water entering the combustion chamber
as a saturated liquid at a rate 20 kg/s, determine the enthalpy of the outgoing steam. Take the
combustor efficiency as 90%.
The heat given off when a fuel is completed oxidized with reactants and products both at 250C is
called the heat of combustion.
7.7.2 Higher heating values and lower heating values

Higher heating value (HHV) of a fuel is the heat of combustion with liquid water in the products
and Lower heating value (LHV) of a fuel is the heat of combustion with water vapor in the
products. More heat is given off with liquid water in the products compared to when we have
water vapor and the difference is due to the latent heat of water i.e. with water vapor in the
products, some of the energy which would have been released goes into vaporizing the water or
is retained in the water vapor.
52 SM
The amount of liquid water in the products is determined by the relationship between the partial
pressure of the water and the saturation pressure.
The heat given off with reactants and products both at 250C and 1 atmosphere is independent of
the amount of excess pressure since the enthalpies of oxygen and nitrogen are both zero at 25 0C.
Therefore, the results for heat liberated for theoretical air and any percentage of excess air will
be the same.
For rich mixtures, we have a deficiency of air resulting into incomplete combustion and therefore
less heat will be liberated.
If the combustion process is caused to proceed adiabatically i.e. if the reaction chamber or steady
flow reactor is well insulated, then all the energy released in the chemical reaction goes into
heating up the products. In this case the, the maximum temperature reached by the products is
called the adiabatic temperature and it represents the maximum temperature achievable for
given reactants.
7.7.3 Dissociation
Because combustion temperatures are often high enough, dissociation of product molecules must
be accounted for; Dissociation is the breakup of molecules into constituents e.g. at high
temperatures, water molecules at some extent break up into hydrogen and oxygen, carbon oxide
to carbon monoxide and oxygen and hydrogen molecules into hydrogen molecules. Dissociation
affects the composition of combustion products and also since energy is required for
dissociation, the temperature achieved for an actual combustion reaction with dissociation will
be less than that calculated on the basis of no dissociation.
7.8 Energy economy and alternative energy sources

Fossil fuels supply a very high percentage of the world’s energy needs, but there are two main
reasons why alternative energy sources are required for the future generations:
 The production of green house gases like CO2 from fossil fuel based energy systems is
causing a worsening of the green house effect and there is also a risk to the ecosystem from
other associated gases like SOx and NOx
 Secondly, the earth’s fossil fuels supply is finite (under depletion)
Assignment
Read and makes notes on the various alternative energy sources that can used to handle the
negative issues associated with fossil fuels. Clearly indicate the advantages and drawbacks
associated with each energy source.
53 SM

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CHE 1201 – THERMODYNAMICS – LECTURE NOTES

2.4 Specific heat capacities ......................................................................................................6

6.1 The Carnot cycles ............................................................................................................ 25

7.6 Wet and dry analysis ....................................................................................................... 50

1.2.1 Closed system

1.2.2 Open system

1.3.1 Intensive properties

1.3.2 Extensive properties

1.4 Homogeneous substance

1.5.1 Sensible heat

1.7.1 A cyclic process

1.7.2 Quasi – static process

1.8 Thermal equilibrium

1.9 Chemical equilibrium

1.10 Mechanical equilibrium

1.10.1 Steady flow

1.10.2 Zeroth law

1.11 Temperature and its measurement

2.1 Criteria of reversibility

2.2 Equations of state

2.3 Determination of work during a volume change

Figure2.1 Work due to volumetric expansion

2.3.1 Constant Volume process (Iso - volumetric)

Figure 2.1 Iso - volumetric process

From =∫ , but = 0 hence =0

2.3.2 Constant pressure process

Figure5.3 Isobaric process

2.3.3 A process with a hyperbolic equation

2.3.4 Polytropic processes

2.4 Specific heat capacities

2.5 Internal energy

From the definition of specific heat capacity Cv, then; =

2.7 Relationship between Cp and Cv

3. FIRST LAW OF THERMODYNAMICS

3.1 Applied to cyclic processes

3.2 As applied to change of state processes for closed systems

From − = ∆ and with = ∴ =0

2. Constant temperature process

3. Constant pressure process

3.3 First law of thermodynamics as applied to open systems

3.3.1 The working fluid

Figure3.1 Change of state of the working fluid as a result of heating

Figure3.2 Temperature - volume relations for 3 different pressures

3.3.2 Steady - flow systems

3.3.3 Steady – flow process

3.3.4 Mass balance for a steady flow process

3.3.5 Energy balance for steady – flow systems

3.3.6 Some examples of steady – flow Engineering devices

b) Turbines and compressors

Figure3.4 U - tube and Shell and Tube heat exchangers

Figure3.6 Throttling valve

4. SECOND LAW OF THERMODYNAMICS

4.1 Heat engines

4.2 Steam plant

Figure 4.1 Schematic diagram of a steam plant

4.3 Open gas turbine plant

Figure 4.2 Schematic diagram of an open gas turbine plant

4.4 Closed gas turbine system

4.5 Heat engine performance