UNIT ONE

BASIC CONCEPTS OF THERMODYNAMICS

INTRODUCTION

THERMODYNAMICS
 It is the science of the relations between heat, work and the properties of the systems.
 How to adopt these interactions to our benefit?
Thermodynamics enables us to answer this question.

The macroscopic approach to the study of thermodynamics that does not require knowledge of
the behaviour of individual particles is called classical thermodynamics. It provides a direct and
easy way to the solution of engineering problems. A more elaborate approach, based on the
average behaviour of large groups of individual particles, is called statistical thermodynamics.

Areas of Application of Engineering Thermodynamics

 Automobile engines
 Turbines
 Compressors, pumps
 Fossil- and nuclear-fueled power station
 Propulsion systems for aircraft and rockets
 Combustion engines
 Biomedical applications
 Heating, ventilating, and air-conditioning system

THERMODYNAMIC SYSTEMS

System, Boundary and Surroundings

 In our study of thermodynamics, we will choose a small part of the universe to which we
will apply the laws of thermodynamics. We call this subset a system.

 The system is a macroscopically identifiable collection of matter

on which we focus our attention. (e.g.: the water kettle or the aircraft
engine).
 The mass or region outside the system is called the
surroundings.
 The surface or envelop that enclose and separates the system
from the surroundings is called the boundary. (e.g.: walls of the kettle,
the housing of the engine).
 The boundaries may be real physical surfaces or they may be imaginary for the
convenience of analysis.
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 E.g.: If the air in this room is the system, the floor, ceiling and walls constitutes real
boundaries. The plane at the open doorway constitutes an imaginary boundary.
 The boundaries may be at rest or in motion.

TYPES OF SYSTEMS

 Two basic kinds of systems:

1. Closed systems (control mass)
2. Open system ( control volumes)

Thermodynamic
systems

closed/control open
mass system/control
volume

isolated
closed system
system

Closed system is a system in which there is no exchange of mass or matter between a system
and its surroundings but there is an exchange of energy between a system and its surroundings.

Mass is always considered to be constant. Examples: preservation of drinks in a refrigerator,

preservation of fruits and vegetable in a refrigerator, etc.

No mass entry or exit

2
Open system is a system in which there is the exchange of both mass and energy between a
system and its surroundings. Most of the engineering devices are open system. Example: boiling
of water, reheating of soup, a pump and a deflating balloon etc.

Isolated system is a system in which there is no exchange of both mass and energy between a
system and its surroundings. It is of fixed mass and energy. Example: warm water in a thermos
flask.

In summary
System Mass exchange Energy exchange
Closed No Yes
Open Yes Yes
Isolated No No

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PROPERTIES OF A SYSTEM

 To describe a system and predict its behavior requires knowledge of its properties and
how those properties are related.
 A property is a macroscopic characteristic of a system.
 A numerical value can be assigned at a given time without knowledge of the previous
behavior (history) of the system
 E.g. Gina weighs 73 kg and is 1.71 m tall. We are not interested in how she got to that
stage as well as what she ate. These bio data may be useful way of identification for
police purposes.
 If she is a student, one may say Gina is a student at the Koforidua Polytechnic.
 Gina comes from Takoradi. She has three sisters and a singer.
 All of the above are properties of Gina. Also, you can pick and choose a set of her traits
that best describe her for a given situation.
 It is a point function hence the differential is exact.
Since a property is not dependent on the path, any change depends only on the initial and
final states of the system. Using the symbol to represent a property,
Mathematically

= represents the change in the property as the system changes from state 1 to state 2.

Categories of Properties
Thermodynamic properties are divided into two general categories:
1. Extensive property
2. Intensive property

 Intensive property
is the one whose value is independent of the size or extent of the system. Temperature,
pressure and velocity as well as specific properties are examples since they are the same
for the entire system, or for parts of the system. If we bring two systems together,
intensive properties are not summed.
 Extensive property
is the one whose value depends on the size or extent of the system. Mass, volume,
momentum, and kinetic energy are examples. If two systems are brought together the
extensive property of the new system is the sum of the extensive properties of the original
two systems. If mass is increased, the value of extensive property also increases.

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Specific property
It is the value of an extensive property per unit mass of system. That is if we divide an extensive
property by the mass, a specific property results hence the conversion of extensive property to
intensive. For instance, if volume is divided by mass the result is a specific volume and the
reciprocal is density.

STATE, PHASE, EQUILIBRIUM, PATH, PROCESS AND CYCLE

State

It refers to the condition of a system as described by its properties. It gives a complete

description of the system.

State function: Some values of system properties have nothing to do with the history of
the system, they are decided by system state. The change values depend on the initial and
the final state, and have nothing to do with the change ways. This kind of
physical quantity is called state function.

Thermodynamic state function/variable = variable

independent of history. E.g. U, T, P, V, etc

State function characteristics

1. Different ways come to the same final, the value change is the same ;
2. Move one cycle, numerical value go back to the origin;
3. In mathematics, State function has the character of full differential

Any operation in which one or more properties of a system change is called a change of state.

Phase

It is a quantity of mass that is homogeneous throughout in chemical composition and physical

structure. E.g. solid, liquid, vapour, gas.

Phase consisting of more than one phase is known as heterogeneous system.

Path

The succession of states passed through during a change of state is called the path of the system.

Process

When any of the properties of a system changes, the state changes and the system is said to have
undergone a process. A process is a transformation from one state to another. However, if a
system exhibits the same values of its properties at two different times, it is in the same state at
these times. A system is said to be at steady state if none of its properties changes with time.
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Dead state is the state a system is said to be in when it is in thermodynamic equilibrium with its
environment.

Types of Processes

As a matter of rule we allow one of the properties to remain a constant during a process. We
have the following:

 Isothermal (T)
 Isobaric (p)
 Isochoric / isometric (v)
 Isentropic (s)
 Isenthalpic (h)
 Isosteric (concentration)
 Adiabatic (no heat addition or removal)

Isobaric

Isometric
cccc

Isothermal

Adiabatic

Process Paths

Quasi–Static / Quasi (almost)-Equilibrium Process

The processes can be restrained or unrestrained. We need restrained processes in practice.

No real process is quasistatic, but such process can be approximated by performing them
very slowly.
Any reversible process is necessarily a quasistatic one. However, some quasistatic
processes are irreversible.
A quasi-static process is one in which
 The deviation from thermodynamic equilibrium is infinitesimal.
 All states of the system passes through are equilibrium states.
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  If we remove the weights slowly one by one the pressure of the gas will displace the
piston gradually. It is quasistatic.
 On the other hand if we remove all the weights at once the piston will be kicked up by the
gas pressure.(This is unrestrained expansion) but we don’t consider that the work is done
- because it is not in a sustained manner
 In both cases the systems have undergone a change of state.
 Another e.g.: if a person climbs down a ladder from roof to ground, it is a quasistatic
process. On the other hand if he jumps then it is not a quasistatic process.

Why quasi-static process?

 Approximates many processes with acceptable accuracy.
 Instrumental in deducing relationships that exist among the properties of systems at
equilibrium.
Equilibrium

 When the properties are constant from point to point and when there is no tendency for
change with time, a condition of thermodynamic equilibrium exists.
 Equilibrium generally requires all properties to be uniform throughout the system.
 There are mechanical, thermal, phase and chemical equilibria.

Types of Equilibrium
Between the system and surroundings, if there is no differences in
 Pressure Mechanical equilibrium
 Potential Electrical equilibrium
 Concentration of species Species equilibrium
 Temperature Thermal equilibrium
If a system would undergo a large change in its properties when subjected to some small
disturbance, it is said to be in metastable equilibrium.
A mixture of gasoline and air, and a bowling ball on top of a pyramid are examples.

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Cycle
A thermodynamic cycle is a sequence of quasiequilibrium processes that begins and ends at the
same state. At the conclusion of a cycle all properties have the same values they had at the
beginning.

UNITS

The system of units called SI, takes mass, length, and time as primary dimensions and regards
force as secondary. SI is the abbreviation for Systeme International d’Unites (International
System of Units), which is the legally accepted system in most countries. The conventions of the
SI are published and controlled by an international treaty organization.
There are seven base units in the SI: m, kg, s, K, mol (mole), A (ampere), cd (candela).
The last two are rarely encountered in engineering thermodynamics.

Units and dimensions for Mass, Length and Time

Quantity Unit Dimension Symbol
mass kilogram M kg
length meter L m
time seconds t s

SI units for other physical quantities are also derived in terms of the SI base units. Some of the
derived units occur so frequently that they are given special names and symbols, such as the
newton. SI units for quantities pertinent to thermodynamics are given in the table below:

Quantity Dimension Units Symbol Name

Velocity m/s
Acceleration m/s2
Force Kg m/s2 N newton
Pressure Kg m/s2 (N/m2) Pa pascal
Energy Kg m2/s2 (N m) J joule
Power Kg m2/ (J/s) W watt

Since it is frequently necessary to work with extremely large or small values when using the SI
unit system, a set of standard prefixes is provided in the table below to simplify matters.
Units can be used to our advantage. They can be used to check formulas; they can even be used
to derive formulas.

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SI Unit Prefixes

Factor Prefix Symbol

tetra T
giga G
mega M
kilo k
hecto h
centi c
milli m
micro
nano n
pico p

Example
Express the energy unit J (joule) in terms of base units.
Solution
Recalling that energy is force times distance:

DENSITY, SPECIFIC VOLUME, AND SPECIFIC WEIGHT

Density is mass per unit volume; specific volume is volume per unit mass. By comparing the two
definitions, we can see that the two properties are related by

Associated with (mass) density is weight density, or specific weight :

Specific weight is related to density through and

For water, nominal values of and are, respectively, 1000 kg/ and 9810 N/
For air, at standard conditions, the nominal values are 1.21 kg/ and 11.86 N/
Example
The mass of air in a room 3 m × 5 m × 20 m is known to be 350 kg. Determine the density,
specific volume, and specific weight of the air.

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Solution

TEMPERATURE AND THE ZEROTH LAW OF THERMODYNAMICS

The temperature is a thermal state of a body which distinguishes a hot body from a cold one.
The temperature of a body is proportional to the stored molecular energy ie the average
molecular kinetic energy of the molecules in a system.

Instruments for measuring ordinary temperatures are known as thermometers and those for high
temperatures are called pyrometers.

It has been found that a gas will not occupy any volume at a certain temperature. This
temperature is called absolute zero temperature. The temperatures measured with absolute zero
as basis are called absolute temperatures. Absolute temperature is stated in degrees centigrade.
The point of absolute temperature is found to occur at 273.15oC below the freezing point of
water.

TEMPERATURE SCALE
The Kelvin scale is related to the Celsius scale by

The Rankine scale is related to the Fahrenheit scale by

The temperature scales in the two unit systems are related by

When we are dealing with temperature differences , the temperature interval on both scales is
the same. Raising the temperature of a substance by 10°C is the same as raising it by 10 K. That
is,

Expressing Temperature Rise in Different Units

During a heating process, the temperature of a system rises by 10°C. Express this rise in
temperature in K, °F, and R.
Analysis: This problem deals with temperature changes, which are identical in Kelvin and
Celsius scales.
Then,

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The temperature changes in Fahrenheit and Rankine scales are also identical and are related to
the changes in Celsius and Kelvin scales through,

And

THE ZEROTH LOW OF THERMODYNAMICS

 When two bodies are in thermal equilibrium with a third body, they are in thermal
equilibrium with one another.
 If two systems (say A and B) are in thermal equilibrium with a third system (say C)
separately (that is A and C are in thermal equilibrium; B and C are in thermal
equilibrium) then they are in thermal equilibrium themselves (that is A and B will be in
thermal equilibrium)
 This statement is called the zeroth law of thermodynamics. Example of application of the
zeroth law of thermodynamics is using clinical thermometer to measure the temperature
of a patient.

PRESSURE

Pressure is defined as a force per unit area. Pressures are exerted by gases, vapours and liquids.
Thus it is the difference between the pressure exerted by a fluid of interest and the ambient
atmospheric pressure. Such devices indicate the pressure either above or below that of the
atmosphere. When it is above the atmospheric pressure, it is termed gauge pressure and is
positive. When it is below atmospheric, it is negative and is known as vacuum. Vacuum readings
are given in millimeters of mercury or millimeters of water below the atmosphere.

The pressure relative to the atmospheric pressure is called the gauge pressure, and the pressure
relative to an absolute vacuum is called absolute pressure.

The fundamental SI unit of pressure is N/m2 sometimes called pascal, Pa.

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However, in this text it is convenient to work with multiples of the Pascal: the kPa, the bar, and
the MPa.

1 bar  105 N / m2  105 Pa

1 kPa  103 N / m 2
1 MPa  106 N / m2

Recalling that,

Also,

Although atmospheric pressure varies with location on the earth, a standard reference value can
be defined and used to express other pressures.

1 sta n dard atmosphere (atm)  1.01325 x 105 N / m2

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UNIT 2
THE FIRST LAW OF THERMODYNAMICS
P – V WORK

One form of mechanical work frequently encountered in practice is associated with the
expansion or compression of a gas in a piston–cylinder device. During this process, part of the
boundary (the inner face of the piston) moves back and forth. Therefore, the expansion and
compression work is often called moving boundary work, or simply boundary work

Consider the gas enclosed in the piston–cylinder device shown in Figure below. The initial
pressure of the gas is P, the total volume is V, and the cross-sectional area of the piston is A. If
the piston is allowed to move distance ds in a quasi-equilibrium manner, the differential work
done during this process is

But

Recalling that,

Note that in the above equation, P is the absolute pressure, which is

always positive. However, the volume change dV is positive during an
expansion process (volume increasing) and negative during a
compression process (volume decreasing). Thus, the boundary work is
positive during an expansion process and negative during a
compression process.

The total boundary work done during the entire process as the piston
moves is obtained by adding all the differential works from the initial
state to the final state:

In terms of specific volume v,

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The differential area dA of the quasiequilibrium expansion process on the P-V diagram is equal
to P dV, which is the differential work.
The total area A under the process curve 1–2 is obtained by adding these differential areas:
Area

On the P-v diagram, the area represents the boundary work done per unit mass.

SIGN CONVECTIONS

Engineering thermodynamics is frequently concerned with devices such as internal combustion

engines and turbines whose purpose is to do work. Hence, in contrast to the approach generally
taken in mechanics, it is often convenient to consider such work as positive. That is,

 Work done BY the system is POSITIVE

 Obviously work done ON the system is NEGATIVE
 Heat given TO the system is POSITIVE
 Obviously Heat rejected BY the system is NEGATIVE

WORK AND HEAT

 All our efforts are oriented towards how to convert heat to work or vice versa:
 Heat to work Thermal power plant
 Work to heat Refrigeration

Point function

When two properties locate a point on the graph then those properties are called point function
(dependent only on the end points). Examples are pressure, temperature, volume etc. The
differential of a point function is an exact differential. An exact differential will be denoted with
the operator d

The integral of an exact differential, for example dT and dV, would be

and respectively.
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Path function

There are certain quantities which cannot be located on a graph by a point but are given by the
area on the graph. In such cases, the area on the graph of a particular process is a path of the
process. Such quantities are called path functions. Examples are heat, work etc. The differential
of a path function is called an inexact differential (dependent on the path).

An inexact differential will be denoted with the operator , hence differential form of both work
and heat are respectively denoted with

Heat and work are inexact differential hence their change cannot be written as difference
between their end states. Thus

, and is shown as

Similarly,

, and is shown as

Comparison of Work and Heat

Similarities:

1. Both are path functions and inexact differentials.

2. Both are boundary phenomenon i.e., both are recognized at the boundaries of the system
as they cross them.
3. Both are associated with a process, not a state. Unlike properties, work or heat has no
meaning at a state.
4. Systems possess energy, but not work or heat.
Dissimilarities:
1. In heat transfer temperature difference is required.
2. In a stable system there cannot be work transfer, however, there is no restriction for the
transfer of heat.
3. The sole effect external to the system could be reduced to rise of a weight but in the case
of a heat transfer other effects are also observed.

THE FIRST LAW OF THERMODYNAMICS

The first law applied to a cycle

 When a closed system executes a complete cycle the sum of heat

interactions is equal to the sum of work interactions.
Mathematically


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Alternate statement

When a closed system undergoes a cycle, the cyclic integral of heat is equal to the cyclic integral
of work.

Mathematically

The first law applied to a process

 Increase in internal energy = Heat added  Work done

From sign convection, Heat added to the system will be considered as positive and the work
done, on the system, as negative.
Mathematically
U  Q  W
The energy balance in differential form is

E consist of

U – internal energy

KE – the kinetic energy

PE – the potential energy

Introducing an alternative form of the balance

Time rate form of the energy balance

 An isolated system which does not interact with the

surroundings and Therefore, E remains
constant for such a system.
 Let us reconsider the cycle 1 – 2 along path A and 2 –
1 along path B as shown in the fig at the RHS.
 Work done during the path A = Area under 1-A-2-3-4
 Work done during the path B = Area under 1-B-2-3-4

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  Since these two areas are not equal, the net work interaction is that shown by the shaded
area.
 The net area is 1A2B1.
 Therefore some work is derived by the cycle
 First law compels that this is possible only when there is also heat interaction between the
system and the surroundings.
 In other words, if you have to get work out, you must give heat in.
 The first law can be construed to be a statement of conservation of energy.
 For a process we can have Q = 0 or W = 0
 We can extract work without supplying heat (during a process) but sacrificing the
energy of the system
 We can add heat to the system without doing work (in process) which will go to
increasing the energy of the system.
 Energy of a system is an extensive property.

Engineering Implications

 When we need to derive some work, we must expend thermal or internal energy.
 Whenever we expend heat energy, we expect to derive work interaction (or else the heat
supplied is wasted or goes to change the energy of the system).
 If you spend money, either you must have earned it or you must take it out of your bank
balance!!

TRY QUESTIONS

1. Determine the work done by the air which enters into an evacuated vessel from
atmosphere when the valve is opened. The atmospheric pressure is 1.013 bar and 1.5
of air at atmospheric condition enters into the vessel. [-151.95 kJ]
2. In an internal combustion engine, during the compression stroke the heat rejected to the
cooling water is 50 kJ/kg and the work input is 100 kJ/kg. Calculate the change in
internal energy of the working fluid stating whether it is a gain or loss. [50kJ/kg]
3. A 2.5-kW electric resistance heater submerged in water is turned on and kept on for
3minutes. During the process, 300 kJ of heat is lost from the water. Calculate the internal
energy of the water. [150 kJ]
4. A cylinder containing air comprises a system. Cycle is completed as follows:
(i) 82000 N-m of work is done by the piston on the air during compression stroke
and 45kJ of heat are rejected to the surroundings
(ii) During expansion stroke 10000 N-m of work is done by the air on the piston.
Calculate the quantity of heat added to the system.
[63kJ]

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5. A system undergoes a cycle consisting of the three processes listed in the table. Compute
the missing values (a, b, c, d).
All quantities are in kJ.
Process Q W
1 a 100 100
b c
3 100 d

[200, 50, 100, 300]

6. The specific heat capacity of the system during a certain process is given
If the mass of the gas is 6kg and its temperature changes from
25 find:
(i) Heat transferred;
(ii) Mean specific heat of the gas.
[420 kJ, 0.7 kJ/kg ]
7. 150 kJ of work is supplied to a closed system. If the initial volume is 0.6 and pressure
of the system changes as p = 8 - 4V.
Where p is in bar and Vis in , determine the final volume and pressure of the system.
[0.707 5.172 bar]
8. Each line in the following table gives information about a process of a closed system.
Every entry has the same energy units. Fill in the blank spaces in the table.

Process Q W
A +50 -20 +50
B +50 +20 +20
C -40 +60 +20
D -90 +50 0
E +50 +20 -100

9. A closed system of mass 5 kg undergoes a process in which there is work of magnitude 9

kJ to the system from the surroundings. The elevation of the system increases by 700 m
during the process. The specific internal energy of the system decreases by 6 kJ/kg and
there is no change in kinetic energy of the system. The acceleration of gravity is constant
at g = 9.6 m/s2. Determine the heat transfer, in kJ. [-5.4 kJ]

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INTERNAL ENERGY, ENTHALPY, AND SPECIFIC HEATS OF IDEAL
GASES

The Ideal Gas

Ideally, the behavior of air is characterized by its mass, the volume it occupies, its temperature
and the pressure condition in which it is kept. An ideal gas is governed by the perfect gas
equation of state which relates the state pressure, volume and temperature of a fixed mass (m is
constant) of a given gas (R is constant) as

Where

P – Pressure (Pa)

V – Volume (m3)

T – Absolute Temperature (K)

T (K) = 273 + t( )

m – mass (kg)

R – gas constant (J/kg.K)

The ideal gas equation (1) can be expressed as

Where , (m3/kg)

The equation of state can be written in the following forms, depending on what is needed to be
calculated

i. In terms of the pressure

ii. In terms of the volume

iii. In terms of the mass

iv. In terms of the temperature

v. In terms of the gas constant

vi. In terms of the density

The specific gas constant R, is a property related to the molar mass (M) in kg/kmol,
of the gas and the Universal gas constant RO as
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Where

For AIR, molar mass is 29 kg/mol

For OXYGEN, molar mass is 32 kg/mol

Alternative Gas Equation During A Change Of State

The equation of state can be used to determine the behavior of the gas during a process, i.e. what
happens to its temperature, volume ad pressure if any one property is changed. This is defined by
a simple expression relating the initial and final states such as:

This can be rewritten in terms of the final condition; hence the following equations are
generated:

Final Pressure

Final Temperature

Final Volume

Specific Heats

The specific internal energy can be expressed as a function of temperature and specific volume;
that is,

Using the chain rule from calculus, the differential can be stated as

For a gas obeying the ideal gas model, specific internal energy depends only on temperature.
Hence, the specific heat capacity at constant volume , is also a function of temperature alone.
That is

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This is expressed as an ordinary derivative because u depends only on T.

By separating variables,

This can be integrated to give

This implies,

Recalling that

Likewise, the specific enthalpy can be expressed as a function of temperature and pressure; that
is,

Similarly,

Similarly, for a gas obeying the ideal gas model, the specific enthalpy depends only on
temperature, so the specific heat , is also a function of temperature alone. That is

By separating variables,

This can be integrated to give

This implies,

Recalling that

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Enthalpy

Using the definition of enthalpy,

From ideal gas,

It implies,

For ideal gases, u, h, and varywith temperature only. That is

Differentiating with respect to temperature T,

We have,

 Making substitution,
 The specific heat ratio is also a property of particular interest; it is defined as

 R is a positive quantity. Therefore, for any perfect gas

 is the amount of heat to be added to raise the temperature of unit mass of a substance
when the pressure is kept constant.
 is the amount of heat to be added to raise the temperature of unit mass of a substance
when the volume is kept constant.
 Physical interpretation of why
 When heat is added at constant pressure, part of it goes to raising the piston (and weights)
thus doing some work. Therefore, heat to be added to raise the system’s temperature by 1
K must account for this. Consequently, more heat must be added than in volume is
constant scenario (where the piston does not move).
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  When heat is added at constant volume, the whole amount subscribes to increase in the
internal energy.
 and increase with increasing temperature.

Substituting k into the above equation

 and
 For air, ,

 The change in internal energy or enthalpy for an ideal gas during a process from state 1 to
state 2 is given by

And

THERMODYNAMIC PROCESSES

Thermodynamic Processes for gases

There are four distinct processes which may be undertaken by a gas

a) Constant volume process, known as isochoric process; given by:

b) Constant pressure process, known as isobaric process; given by:

c) Constant temperature process, known as isothermal process; given by:

d) Polytropic process is given by:

Note: when , the process is known as adiabatic process.

The following processes are going to be discussed. The first law of thermodynamics as applied to
process will be employed to discuss the various processes.

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The following the processes to be considered

1. Adiabatic process
2. Isothermal process
3. Isochoric process
4. Isobaric process
5. Polytropic process

Reversible Adiabatic Process

This is a type of processes for which there is no, or negligibly small, heat transfer.
Apply the first to process,

For an adiabatic process,

Implying that

kJ/kg

The differential form of the first law for the adiabatic process is

But
or, for a quasiequilibrium process,

From ideal gas,

Implying that,

Assuming 1 kg mass, m

But

Implying,

Rearrange and integrate between states 1 and 2, assuming constant Cv:

24
Apply the law of log and laws of indices,

Let

For an adiabatic process, . Let

, ,
Making substitution and simplifying,

From,

Dividing both sides by T, we get

Integrating

Substituting

Dividing throughout both sides by

But or
Hence substituting

Applying rules of log and simplifying

25
Expression for Adiabatic work, W

A reversible adiabatic process for a perfect gas is shown on a p-v diagram below:

The work done is given by the shaded area, and

this area can be evaluated by integration.

Since then

But

Example
1. Air is contained in an insulated, rigid volume at 20°C and 200 kPa. A paddle wheel,
inserted in the volume, does 720 kJ of work on the air. If the volume is2m3, calculate the
final temperature assuming constant specific heats.

Solution

To determine the final state of the process we use the energy equation, assuming zero heat
transfer. We have . The mass is found from the ideal-gas equation to be

The first law, taking the paddle-wheel work as negative, is then

2. Ten kilograms of air are expanded adiabatically from 500°C and 6 MPa to400 kPa.
Determine the work accomplished.
Solution
26
 Isothermal Process

An isothermal process is a constant-temperature

process. The energy equation is

For a gas that approximates an ideal gas, the

internal energy depends only on the temperature
and thus for an isothermal process; for
such a process

Using the ideal-gas equation PV = mRT, the work

for a quasiequilibrium isothermal process can be
found to be

Where .

Isochoric (isometric) Process

This is a constant-volume process.

Here,

The energy equation be written as,

Because,

For a gas, approximated by an ideal gas with

constant Cv, we would have

27
But

Implying

Isobaric Process

The first law, for a constant-pressure

quasiequilibrium process is,

For a gas that behaves as an ideal gas, we have

For a process involving an ideal gas for which is

constant there results

But

Work done is W  p  V2  V1 
For a nonequilibrium process the work must be accounted for directly in the first law and it
cannot be expressed as . For such a process the above three equations would not be
valid.

Polytropic Process

During actual expansion and compression processes of gases, pressure and volume are often
related by where n and C are constants. A process of this kind is called a polytropic
process.

The pressure for a polytropic process can be expressed as

Substituting this relation into

We obtain

28
Since . For an ideal gas , this equation can

also be written as

It follows also that for any polytropic process, we can write

Since polytropic process behaves like reversible adiabatic process,

Implying,

Rearrange and integrate between states 1 and 2, assuming constant Cv:

Apply the law of log and laws of indices,

Let

Heat transfer during polytropic process

Using non-flow energy equation, the heat flow/transfer during the process can be found,

29
Also

Making substitution,

In a polytropic process, the index n depends only on the heat and work quantities during the
process.

Each quasiequilibrium process of an ideal gas is associated with a particular value for n as
follows:

Isothermal:

Constant-volume (isochoric):

Constant-pressure (isobaric):

Adiabatic:

If the constant n is none of the values , k, 1, or 0, then the process can be referred to as a
polytropic process.
30
TRY QUESTIONS

1. Energy is added to a piston-cylinder arrangement, and the piston is withdrawn in such a

way that the temperature (i.e., the quantity PV) remains constant.

The initial pressure and volume are 200 kPa and 2 m3, respectively. If the final pressure is
100 kPa, calculate the work done by the ideal gas on the piston. [277 kJ]

2. Air is compressed in a cylinder such that the volume changes from 0.2 to 0.02 m3. The
initial pressure is 200 kPa. If the pressure is constant, the work is nearest. [-36 kJ]

3. Estimate the work necessary to compress the air in a cylinder from a pressure of 100 kPa
to that of 2000 kPa. The initial volume is 1000 cm3. An isothermal process is to be
assumed. [-0.3 kJ]
31
4. Estimate the work done by a gas during an unknown equilibrium process. The pressure
and volume are measured as follows:

P 200 250 300 350 400 450 500 kPa

V 800 650 550 475 415 365 360 cm3

[132 J]

5. The force needed to compress a nonlinear spring is given by F = 10x2 N, where x is the
distance the spring is compressed, measured in meters. Calculate the work needed to
compress the spring from 0.2 to 0.8 m. [1.68 J]

6. Air is compressed in a cylinder such that the volume changes from 0.2 to 0.02 m3. The
pressure at the beginning of the process is 200 kPa. If the temperature is constant at 50°C,
the work is nearest [-92 kJ]

7. Ten kilograms of air at 800 kPa are heated at constant pressure from 170 to 400°C. The
work required is nearest [660 kJ]

8. A 200-mm-diameter piston is lowered by increasing the pressure from 100 to 800 kPa
such that the P-V relationship is PV2 = const. If V1 = 0.1 m3, the work done on the system
is nearest [-18.3 kJ]

9. Air is expanded in a piston-cylinder arrangement at a constant pressure of 200 kPa from a

volume of 0.1 m3 to a volume of 0.3 m3. Then the temperature is held constant during an
expansion of 0.5 m3. Determine the total work done by the air. [70.6 kJ]

10. 0.2 kg of air is compressed slowly from 150 kPa and 40°C to 600 kPa, in an adiabatic
process. Determine the final volume.

[Take k=1.4, R=0.287] [0.0445 m3]

11. Find the work needed to adiabatically compress 2 kg of air in a cylinder at 400 kPa and

400°C to 2 MPa [563 kJ]

12. Four kilograms of air expand in an insulated cylinder from 500 kPa and 227°C to 20 kPa.
What is the work output? [863 kJ]

32
UNIT 3

PROPERTIES OF PURE SUBSTANCES

INTRODUCTION

 Pure substance is one with uniform and invariant chemical composition.

 Examples: elements and chemical compounds are pure substances. (water, stainless steel)
 Mixtures are not pure substances. (E.g. humid air).
 Air is treated as a pure substance though it is a mixture of gases.
 In a majority of cases a minimum of two properties are required to define the state of a
system. The best choice is an extensive property and an intensive property.

Properties Of Substance

 Gibbs Phase Rule determines what is expected to define the state of a system.
 Given by the relation:
 Where F = Number of degrees of freedom (i.e. no. Of properties required), C = Number
of components and P = Number of phases.
 Example: Nitrogen gas, C = 1; P = 1. Therefore, F = 2
 It implies, to determine the state of the ntrogen gas in a cylinder, two properties are
adequate.
 A closed vessel containing water and steam in equilibrium. How many degree of freedom
has this system? P = 2, C = 1.
 Therefore, F = 1. If any one property is specified it is sufficient.
 If the degree of freedom is zero it implies the triple point is uniquely defined.

Properties of Liquids

The most common liquid is water. It has peculiar properties compared to other liquids.
 Solid phase is less dense than the liquid phase (ice floats on water)
 Water expands on cooling (a fully closed vessel filled with water will burst if it is cooled
below the freezing point).
 The largest density of water near atmospheric pressure is at 4 oC

P–V–T RELATION

We begin our study of the properties of pure, simple compressible substances and the relations
among these properties with pressure, specific volume, and temperature. From experiment it is
known that temperature and specific volume can be regarded as independent and pressure
determined as a function of these two: p = p (T, v). The graph of such a function is a surface, the
p–v–T surface.

33
P–v–T Surface
Figure 3.1 is the p–v–T surface of a substance such as water that expands on freezing. Figure 3.2
is for a substance that contracts on freezing and most substances exhibit this characteristic.

The coordinates of a point on the p–v–T surfaces represent the values that pressure, specific
volume, and temperature would assume when the substance is at equilibrium.

p–v–T surface and projections for a substance that expands on freezing.

There are regions on the p–v–T surfaces of figures above labelled solid, liquid, and vapour. In
these single-phase regions, the state is fixed by any two of the properties: pressure, specific
volume, and temperature, since all of these are independent when there is a single phase present.
Located between the single-phase regions are two-phase regions where two phases exist in
equilibrium: liquid–vapour, solid–liquid, and solid–vapour. Two phases can coexist during
changes in phase such as vaporization, melting, and sublimation. Within the two phase regions
pressure and temperature are not independent; one cannot be changed without changing the
other. In these regions the state cannot be fixed by temperature and pressure alone; however, the
state can be fixed by specific volume and either pressure or temperature.

Three phases can exist in equilibrium along the line labelled triple line.

A state at which a phase change begins or ends is called a saturation state. The dome shaped
region composed of the two-phase liquid–vapour states is called the vapour dome. The lines
bordering the vapour dome are called saturated liquid and saturated vapour lines. At the top of
the dome, where the saturated liquid and saturated vapour lines meet, is the critical point. The
critical temperature Tc of a pure substance is the maximum temperature at which liquid and

34
vapour phases can coexist in equilibrium. The pressure at the critical point is called the critical
pressure, pc. The specific volume at this state is the critical specific volume.

Characteristics of the critical point

1. It is the highest temperature at which the liquid and vapour phases can coexist.
2. At the critical point hfg , ufg and vfg are zero.
3. Liquid vapour meniscus will disappear.
4. Specific heat at constant pressure is infinity
5. A majority of engineering applications (e.g. steam based power generation; Refrigeration,
gas liquefaction) involve thermodynamic processes close to saturation.

The P-T Diagram

The diagram below shows the P-T diagram of a pure substance. This diagram is often called the
phase diagram since all three phases are separated from each other by three lines. The
sublimation line separates the solid and vapor, the vaporization line separates the liquid and
vapor regions, and the melting (or fusion) line separates the solid and liquid regions. These three
lines meet at the triple point, where all three phases coexist in equilibrium. The vaporization
line ends at the critical point because no distinction can be made between liquid and vapor
phases above the critical point. Substances that expand and contract on freezing differ only in the
melting line on the P-T diagram.
The slope of sublimation and the
vapourisation curves for all
substances are positive.

The slope of the fusion curve

however may be positive or
negative. The fusion curves of
most substances have a positive
slope. Water is one of the
important exceptions.

A P-T diagram

35
Phase Change Terminologies and Definitions

Suffices: Solid i

Liquid f

Vapour g

Phase change Name Process Process suffix

1. Solid-liquid fusion freezing, melting if

2. Solid-vapour sublimation frosting, defrosting ig
3. Liquid-vapour evaporation evaporating, condensation fg

STEAM FORMATION

Formation of steam

Consider a cylinder fitted with a piston which can move freely upwards and downwards in it.
Let, for the sake of simplicity, there is 1kg of water at 0C with volume v f m3 under the piston.
Further the piston is loaded with load W to ensure heating at constant pressure. Now if the heat is
imparted to water, a rise in temperature will be noticed and this rise will continue till boiling
point is reached. The temperature at which water starts boiling depends upon the pressure and as
such for each pressure (under which water is heated) there is a different boiling point. This
boiling point is known as the temperature of formation of steam of saturation temperature.

It may be noted during heating up to the boiling point that there will be slight increase in volume
of water due to which piston moves up and hence work is obtained as shown in the figure above.
This work, however, is so small that is can be neglected.

Now, if supply of heat to water is continued it will be noticed that rise of temperature after the
boiling point is reached nil but piston starts moving upwards which indicates that there is
increase in volume which is only possible if steam formation occurs. The heat being supplied
does not show any rise of temperature but changes water into vapor state (steam) and is known
as latent heat or hidden heat. So long as the steam is in contact with the water, it is called wet
steam (Fig above) and if heating of steam is further progressed such that all the water particles
36
associated with steam are evaporated; the steam so obtained is called dry and saturated steam. If
v f m3 is the volume of 1kg of dry and saturated steam then work done on the piston will be

p  vg  v f 
Where p is the constant pressure due to weight ‘W’) on the piston.

Again, if supply of heat to the dry and saturated steam is continued at constant pressure there will
be increase in temperature and volume of steam. The steam so obtained is called superheated
steam and it behaves likes a perfect gas. This phase of steam formation is illustrated in Fig
above.

Terms

1. Sensible heat of water( h f ): It is defined as the quantity of heat absorbed by 1kg of

water when it is heated from 0C (freezing point) to boiling point. It is also called total
heat (or enthalpy) of water or liquid invariably.
2. Latent heat or hidden heat ( h fg ): It is the amount of heat required to convert water at a
given temperature and pressure into steam at the same temperature and pressure. It is
expressed by the symbol h fg and its value is available from steam tables. The value of
latent heat is not constant and varies according to pressure variation.

Graphical representation of steam formation

37
PROPERTY TABLES

For most substances, the relationships among thermodynamic properties are too complex to be
expressed by simple equations. Therefore, properties are frequently presented in the form of
tables. Some thermodynamic properties can be measured easily, but others cannot and are
calculated by using the relations between them and measurable properties.
The results of these measurements and calculations are presented in tables in a convenient
format. In the following discussion, the steam tables are used to demonstrate the use of
thermodynamic property tables. Property tables of other substances are used in the same manner.

For each substance, the thermodynamic properties are listed in more than one table, tables C 1 to
C3. In fact, a separate table is prepared for each region of interest such as the superheated vapour,
compressed liquid, and saturated (mixture) regions. Before we get into the discussion of property
tables, we define a new property called enthalpy.

Enthalpy- A Combination Property

Observing the tables, one will notice two new properties: enthalpy h and entropy s. Entropy is a
property associated with the second law of thermodynamics, and we will discuss it later in the
second law of thermodynamics.
However, it is appropriate to introduce enthalpy at this point. In the analysis of certain types of
processes, particularly in power generation and
refrigeration (Fig. below) we frequently encounter
the combination of properties .
For the sake of simplicity and convenience, this
combination is defined as a new property,
enthalpy, and given the symbol h:

Or

Both the total enthalpy H and specific enthalpy h are simply

referred to as enthalpy since the context clarifies which one
is meant.
.
The analysis of control volume

Saturated Liquid and Saturated Vapour States

The properties of saturated liquid and saturated vapour for
water are listed in Tables C–1 and C–3. Both tables give the
same information. The only difference is that in Table C–3
properties are listed under temperature and in Table C–3

38
under pressure. Therefore, it is more convenient to use Table C–3 when temperature is given and
Table C–3 when pressure is given. The use of Table C–3 is illustrated in Fig. below.

The subscript f is used to denote properties of a saturated liquid, and the subscript g to denote the
properties of saturated vapour.

These symbols are commonly used in thermodynamics and originated from German. Another
subscript commonly used is fg, which denotes the difference between the saturated vapour and
saturated liquid values of the same property.
For example,
specific volume of saturated liquid

specific volume of saturated vapour

difference between and ( that is, )

The quantity is called the enthalpy of vaporization (or latent heat of vaporization). It
represents the amount of energy needed to vapourize a unit mass of saturated liquid at a given
temperature or pressure. It decreases as the temperature or pressure increases and becomes zero
at the critical point.

Saturated Liquid–Vapour Mixture

During a vaporization process, a substance exists as part liquid and part vapour. That is, it is a
mixture of saturated liquid and saturated vapour. To analyze this mixture properly, we need to
know the proportions of the liquid and vapour phases in the mixture. This is done by defining a
new property called the quality or dryness fraction x as the ratio of the mass of vapour to the
total mass of the mixture:

Where

Implying

Quality has significance for saturated mixtures only. It has no meaning in the compressed liquid
or superheated vapour regions. Its value is between 0 and 1. The quality of a system that consists
of saturated liquid is 0 (or 0 percent), and the quality of a system consisting of saturated vapour
is 1 (or 100 percent). In saturated mixtures, quality can serve as one of the two independent
intensive properties needed to describe a state. Note that the properties of the saturated liquid
are the same whether it exists alone or in a mixture with saturated vapour. During the
vaporization process, only the amount of saturated liquid changes, not its properties.

39
The same can be said about a saturated vapour. A saturated mixture can be treated as a
combination of two subsystems: the saturated liquid and the saturated vapor. However, the
amount of mass for each phase is usually not known. Therefore, it is often more convenient to
imagine that the two phases are mixed well, forming a homogeneous mixture (Fig. below).
Then the properties of this “mixture” will simply be the average properties of the saturated
liquid–vapor mixture under consideration. Here is how it is done.

Consider a tank that contains a saturated liquid–vapor mixture. The volume occupied by
saturated liquid is and the volume occupied by saturated vapour is .The total volume V is
the sum of the two:

But

But

Dividing by yields

Since
Simplifying further,

But

Solving for quality, we obtain

The relative amounts of liquids and vapour

phases in a saturated mixture are specified by
The analysis given above can be repeated for internal the quality x

energy and enthalpy with the following results:

(kJ/kg)
(kJ/kg)
All the results are of the same format, and they can be summarized in a single equation as

where y is v, u, or h. The subscript “avg” (for “average”) is usually dropped for simplicity. The
values of the average properties of the mixtures are always between the values of the saturated
liquid and the saturated vapour properties (Fig. below). That is,

In conclusion, since all the saturated-mixture states are located under the saturation curve, to
analyze saturated mixtures, one needs saturated liquid and saturated vapour data.

40
The v value of a saturated liquid-vapour mixture lies between the vf and vg
values at the specified Tor P. Quality is related to the horizontal distances on
P-v and T-v diagrams.
Examples

1. A rigid tank contains 50 kg of saturated liquid water at 90°C. Determine the pressure in
the tank and the volume of the tank.

Solution
Reading from the saturation liquid table,
P=
At 90 oC, specific volume of saturated liquid is

Then the total volume of the tank becomes

2. A rigid tank contains 10 kg of water at 90°C. If 8 kg of the water is in the liquid form and
the rest is in the vapor form, determine the
(a) pressure in the tank and
(b) volume of the tank.
Solution
Reading from the saturation liquid table,
P=
(b) At 90 oC

Volume of the tank can be found using,

41
Alternatively, first determine the quality x, then the average specific volume v, and finally the
total volume:

And

3. A vessel having a capacity of 0.05 m3 contains a mixture of saturated water and saturated
steam at a temperature of 245 oC. The mass of the liquid present is 10 kg. Find the
following:
i. The total mass present
ii. The specific volume

36.5 1061.4 1740.2 0.0546

Solution

The mass, m=?

Volume of liquid =

Volume of vapour,

Mass of vapour,

The total mass of mixture,

iii. The specific volume,

42
 Quality of the mixture,

Superheated Vapour

In the region to the right of the saturated vapour line and at temperatures above the critical point
temperature, a substance exists as superheated vapour. Since the superheated region is a single-
phase region (vapour phase only), temperature and pressure are no longer dependent properties
and they can conveniently be used as the two independent properties in the tables. The format of
the superheated vapour tables is illustrated in Fig. below.

In these tables, the properties are listed against

temperature for selected
pressures starting with the saturated vapor data. The
saturation temperature is given in parentheses following
the pressure value.

Compared to saturated vapour, superheated vapour is

characterized by
Lower pressure (P at a given T)
Higher temperature ( T at a given P)
Higher specific volumes ( at a given P or T)
Higher internal energy (u at a given P or T)
Higher enthalpies (h at a given P or T)

Linear Interpolation
The states encountered when solving problems often do
not fall exactly on the grid of values provided by property
tables. Interpolation between adjacent table entries then
becomes necessary. Care always must be exercised when A partial listing of a superheat table.
interpolating table values. Linear interpolation is assumed to
remain valid when using the abridged tables of the text for the solved examples and end-of-
chapter problems.

Examples
1. The temperature of steam at 1600 kPa and u=3000kJ/kg is nearest?
Solution
At 1600 kPa=1.6 MPa, the internal energy of steam (saturated vapour) is
. Since , we read from superheated vapour tables.
43
 Since u=3000 kJ/kg does not fall exactly on the grid values provided by the property
table, we employ linear interpolation.
T oC u, kJ/kg
400 2950
T 3000
500 3119

Interpolating,

Simplifying further, T= 424.3 oC

2. Determine the enthalpy of steam at 400 kPa and v=0.7 m 3/kg

Solution
At 400 kPa=0.4 MPa, v=0.7 m 3/kg lies between 0.6548 and 0.7726 m 3/kg.
Therefore we need to do linear interpolation

h, kJ/kg v, m 3/kg
3067 0.6548
h 0.7000
3273 0.7726

Further simplification yields, h=3146 kJ/kg

Central Differences
Sometimes, a property which grid value is known on the property table is given and we are
required to find change in some of the properties such as change in enthalpy, change in
temperature, change in internal energy, etc. If we encounter such problems, central differences
approach must be employed.
Example
Estimate Cp for steam at 4 MPa and 350 oC.
Using
At P= 4 MPa and T=350 oC, h=3092 kJ/kg
Finding the central differences for h=3092 kJ/kg

T oC h, kJ/kg
300 2961
350 3092 central differences
400 3214

44
Extrapolation
Sometimes, the states encountered when solving problems often do not fall exactly on the grid
of values provided by property tables. Extrapolation outside adjacent table entries then becomes
necessary.
Example,
1. Determine the temperature of water at a state of P = 0.5 MPa and h = 2800 kJ/kg.
Solution
At 0.5 MPa, h= 2800 kJ/kg falls outside the grid property values hence extrapolation is
required.
T oC h, kJ/kg
T 2800
200 2855
250 2961

Extrapolating,

T=174 oC

The Use of Steam Tables to Determine Properties

The criteria for determining whether we have compressed liquid, saturated mixture, or
superheated vapour is same for enthalpy h, specific volume v, entropy s and internal energy u,
for a given pressure instead of temperature.

Defining the criteria using internal energy,

If
If
If
Temperature can also be used to determine if liquid is compressed or saturated mixture or
superheated vapor. The following is the criteria.
If
If
If

45
 1. Determine the missing properties and the phase descriptions in the following table for
water:

T, P, kPa u, kJ/kg x Phase description

200 0.6
125 1600
1000 2950
80 500
800 0.0

Solution
Row 1
The quality is given to be x = 0.6, which implies that 60 percent of the mass is in the vapor phase
and the remaining 40 percent is in the liquid phase. Therefore, we have saturated liquid–vapor
mixture at a pressure of 200 kPa. Then the temperature must be the saturation temperature at the
given pressure:
(Table C-2)
At 200 kPa, we also read from Table C-2 that uf = 504.50 kJ/kg and ufg = 2025 kJ/kg. Then the
average internal energy of the mixture is

Row 2
At 125 , interpolate from table C-1 for uf = 524.83 kJ/kg and ug = 2534.3 kJ/kg
Next we compare the given u value to these uf and ug values, keeping in mind that
If
If
If
In our case the given u value is 1600, which falls between the uf and ug values at 125°C.
Therefore, we have saturated liquid–vapor mixture. Then the pressure must be the saturation
pressure at the given temperature:

(Table C-1)

The quality is determined from

Row 3
This is similar to case (row 2), except pressure is given instead of temperature. Following the
argument given above, we read the uf and ug values at the specified pressure. At 1 MPa, we have
uf = 761.7 kJ/kg and ug = 2583.6 kJ/kg. The specified u value is 2950 kJ/kg, which is greater than
the ug value at 1 MPa. Therefore, we have superheated vapour, and the temperature at this state
is determined from the superheated vapor table by interpolation to be

46
 (Table C-3)
We would leave the quality column blank in this case since quality has no meaning for a
superheated vapor.
Row 4
At 500 kPa, interpolate for Tsat =151.83°C. We then compare the given T value to this Tsat value,
keeping in mind that
If
If
If
In our case, the given T value is 75°C, which is less than the Tsat value at the specified pressure.
Therefore, we have compressed liquid.
Normally we would determine the internal energy value from the compressed liquid table. But in
this case the given pressure is much lower than the lowest pressure value in the compressed
liquid table (which is 5 MPa), and therefore we are justified to treat the compressed liquid as
saturated liquid at the given temperature (not pressure):
(Table C-1)
We would leave the quality column blank in this case since quality has no meaning in the
compressed liquid region.
Row 5
The quality is given to be x = 0, and thus we have saturated liquid at the specified pressure of
800 kPa. Then the temperature must be the saturation temperature at the given pressure, and the
internal energy must have the saturated liquid value:
At 800 kPa, T = 170.4 °C, u = uf = 720.2 kJ/kg (Table C-2)
TRY QUESTIONS
1. Find the dryness fraction, specific volume and internal energy of steam at 7 bar and
enthalpy 2550kJ/kg. [0.897, 0.2449 m3/kg, 2379.67 kJ/kg]
2. A 20-m3 tank contains nitrogen at 23 °C and 600 kPa. Some nitrogen is allowed to
escape until the pressure in the tank drops to 400 kPa. If the temperature at this point
is 20 °C, determine the amount of nitrogen that has escaped. [44.6 kg]
3
3. A 3-m rigid vessel contains steam at 10 MPa and 500°C. The mass of the steam is?

[91 kg]

47
UNIT 4
THERMODYNAMICS PROPERTIES OF FLOW
PROCESSES AND APPLICATIONS TO FLUID
TRANSPORTING EQUIPMENT
CONSERVATION OF MASS

In developing the mass rate balance for control volumes, let mass flowing in have subscript i and
mass flowing out have subscript e. when apply to such a control volume, the conservation of
mass principle states

Denoting the mass contained within the control volume at time t by , this statement of the
conservation of mass principle can be expressed in symbols as

Mass and Volume Flow Rates

For one-dimensional flow, mass flow rate becomes

(kg/s)

or in terms of specific volume

(kg/s)

Where A is area in m2, V is velocity in m/s, is average fluid density in kg/m3 and v is specific
volume in m3/kg.

Volumetric flow rate is the product of area and velocity. i.e.

(m3/s)

Mass Balance for Steady-Flow Processes

Many engineering systems can be idealized as being at steady state, meaning the all properties
contained within a control volume does not change with time ( constant). Then the
conservation of mass principle requires that the total amount of mass entering a control volume
equal the total amount of mass leaving it.

48
For a garden hose nozzle in steady operation, for example, the amount of water entering the
nozzle per unit time is equal to the amount of water leaving it per unit time.

When dealing with steady-flow processes, we are not interested in the amount of mass that flows
in or out of a device over time; instead, we are interested in the amount of mass flowing per unit
time, that is, the mass flow rate . The conservation of mass principle for a general steady-flow
system with multiple inlets and outlets can be expressed in rate form as steady flow:

(kg/s)

It states that the total rate of mass entering a control volume is equal to the total rate of mass
leaving it.

Many engineering devices such as nozzles, diffusers, turbines, compressors, and pumps involve a
single stream (only one inlet and one outlet). For these cases, we denote the inlet state by the
subscript 1 and the outlet state by the subscript 2, and drop the summation signs. Then the above
equation reduces, for single-stream steady-flow systems, to

Steady flow (single stream):

For incompressible (constant density) fluids such as liquids, the conservation of mass relation is
given by.

Steady incompressible flow:

(m3/s)

For single-stream steady-flow systems it becomes

Steady, incompressible flow (single stream):

Note: for incompressible liquids, density is constant hence density cancels out from both sides
of the general steady-flow equation.

FLOW WORK AND THE ENERGY OF A FLOWING FLUID

Unlike closed systems, control volumes involve mass flow across their boundaries, and some
work is required to push the mass into or out of the control volume. This work is known as the
flow work, or flow energy, and is necessary for maintaining a continuous flow through a control
volume.

The flow work per unit mass of fluid is:

(kJ/kg)
49
Flow work is expressed in terms of properties. It is the product of two properties of the fluid
hence it is viewed as a combination property (like enthalpy) and refers to it as flow energy,
convected energy, or transport energy instead of flow work.

TOTAL ENERGY OF A FLOWING FLUID

The total energy of a simple compressible system consists of three parts: internal, kinetic, and
potential energies. On a unit-mass basis, it is expressed as

(kJ/kg)

Where v is the velocity and z is the elevation of the system relative to some external reference
point.

NB: The total energy consists of three parts for a nonflowing fluid and four parts for a flowing
fluid.

Nonflowing fluid

Flowing fluid

The fluid entering or leaving a control volume possesses an additional form of energy called flow
energy Pv. The total energy of a flowing fluid on a unit-mass basis is denoted by as in above
equation).

But the combination Pv+u=h, called enthalpy.

Hence the above flowing fluid equation reduces to

(kJ/kg)

ENERGY TRANSPORT BY MASS

Recalling that is total energy per unit mass, the total energy of a flowing fluid of mass m is
simply m , provided that the properties of the mass m are uniform. For a fluid stream with
uniform properties flowing with a mass flow rate of , the rate of energy flow with that stream
is m .

That is,

Amount of energy transport:

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 (kJ)

Rate of energy transport:

(kW)

APPLICATION OF FIRST LAW TO STEADY FLOW PROCESS

Steady Flow Energy Equation (S.F.E.E.)

In many practical problems, the rate at which the fluid flows through a machine or piece of
apparatus is constant. This type of flow is called steady flow.

Assumptions

The following assumptions are made in the system analysis:

i. The mass flow through the system remains constant

ii. Fluid is uniform in composition
iii. The only interaction between the system and surroundings are work and heat.
iv. The state of fluid at any point remains constant with time
v. In the analysis only potential, kinetic and flow energies are considered.
Energy rate balance

For steady state system,

The above equation reduces to become what is known as the energy balance

(kW)

System Integration
In engineering practice, several types of individual components are creatively combined to
achieve some overall objective, subjected to constraints such as minimum total cost. This
important engineering activity is called system integration.
The simple power plant is example system integration. This system consists of four components
in series, a turbine-generator, condenser, pump, and boiler. We are going to write steady flow
energy equation for each of the individual component of the system integration below.

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 Simple vapour power plant
Writing the steady state energy equation for each of the components of the simple vapour power
plant above.
Pump
Let the entry of the pump be at state 1 and the exit is at state 2.
Apply the energy balance,

Boiler
Entry at state 2 and exit at state 3.
Apply the energy balance,

Turbine
Entry at state 3 and exit at state 4.
Apply the energy balance,

Condenser
Entry at state 4 and exit at state 1.
Apply the energy balance,

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Neglecting ke and pe.
The equation reduces to become

Solving heat lost from the condenser,

But

Example 1

Air at a temperature of 15 passes through a heat exchanger at a velocity of 30 m/s where its
temperature is raised to 800 . It then enters a turbine with the same velocity of 30 m/s and
expands until the temperature falls to 650 . On leaving the turbine, the air is taken to a velocity
of 60 m/s to a nozzle where it expands until the temperature has fallen to 500 . If air flow rate
is 2 kg/s, calculate the power output from the turbine assuming no heat loss. [Take specific heat
of air,

Solution

Turbine

State 2

From

exchanger

To Nozzle

State 3

Writing the steady flow energy equation for turbine,

Neglecting heat(Q) from exchanger and potential energy and simplifying,

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But

Nozzle
A nozzle is a flow passage of varying cross-sectional area in which the velocity of a gas or liquid
increases in the direction of flow. Inlet pressure is less than outlet pressure.

For this system,

Applying the energy equation to the system,

Or
Simplifying further,

If , then

Diffuser
In a diffuser, the gas or liquid decelerates in the direction of flow. Inlet pressure is greater than
exit pressure.
Similarly,

Applying the energy equation to the system,

54
But

Throttling Valves
Throttling valves are any kind of flow-restricting devices that cause a significant pressure drop in
the fluid. This process is adiabatic as no heat flows from and to the system, but it is not
reversible.

As mentioned earlier on, in this system,

Applying the energy equation to the system

This shows that enthalpy remains constant (isenthalpic process) during adiabatic throttling
process.
The throttling process is commonly used for the following purposes:
i. For determining the condition of steam (dryness fraction)
ii. For controlling the speed of the turbine
iii. Used in refrigeration plant for reducing the pressure of the refrigerant before entry
into the evaporator.

The temperature and internal energy change in a throttling process depend on whether the fluid
behaves as an ideal gas or not. Since the enthalpy of an ideal gas is a function of temperature
alone, it follows that

And, therefore,

Implying
For an ideal gas, therefore, the throttling process takes place at
i. Constant enthalpy
ii. Constant temperature, and
iii. Constant internal energy

Example 2
A stream of gases at 7.5 bar, 750°C and 140 m/s is passed through a turbine of a jet engine. The
stream comes out of the turbine at 2.0 bar, 550°C and 280 m/s.

55
The process may be assumed adiabatic. The enthalpies of gas at the entry and exit of the turbine
are 950 kJ/kg and 650 kJ/kg of gas respectively. Determine the capacity of the turbine if the gas
flow is 5 kg/s.

Solution
Conditions at 1
Pressure,
Velocity,
Enthalpy,
Condition at 2
Pressure,
Velocity,
Enthalpy,
Gas flow,
Writing the steady flow energy equation for turbine

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UNIT 5
GAS POWER CYCLE
INTRODUCTION

Two important areas of application for thermodynamics are power generation and refrigeration.
Both are usually accomplished by systems that operate on a thermodynamic cycle.
Thermodynamic cycles can be divided into two general categories: power cycles and
refrigeration cycles.

The devices or systems used to produce a net power output are often called engines, and the
thermodynamic cycles they operate on are called power cycles. The devices or systems used to
produce a refrigeration effect are called refrigerators, air conditioners, or heat pumps, and the
cycles they operate on are called refrigeration cycles.

Thermodynamic cycles can also be categorized as gas cycles and vapor cycles, depending on the
phase of the working fluid. In gas cycles, the working fluid remains in the gaseous phase
throughout the entire cycle, whereas in vapour cycles the working fluid exists in the vapor phase
during one part of the cycle and in the liquid phase during another part.

Thermodynamic cycles can be categorized yet another way: closed and open cycles. In closed
cycles, the working fluid is returned to the initial state at the end of the cycle and is recirculated.
In open cycles, the working fluid is renewed at the end of each cycle instead of being
recirculated. In automobile engines, the combustion gases are exhausted and replaced by fresh
air–fuel mixture at the end of each cycle. The engine operates on a mechanical cycle, but the
working fluid does not go through a complete thermodynamic cycle.

Heat engines are categorized as internal combustion and external combustion engines, depending
on how the heat is supplied to the working fluid. In external combustion engines (such as steam
power plants), heat is supplied to the working fluid from an external source such as a furnace, a
geothermal well, a nuclear reactor, or even the sun. In internal combustion engines (such as
automobile engines), this is done by burning the fuel within the system boundaries. In this unit,
various gas power cycles are analyzed under some simplifying assumptions.

BASIC CONSIDERATION IN THE ANALYSIS OF POWER CYCLES

Most power-producing devices operate on cycles. The cycles encountered in actual devices are
difficult to analyze because of the presence of sufficient time for establishment of the
equilibrium conditions during the cycle. When the actual cycle is stripped of all the internal
irreversibilities and complexities, we end up with a cycle that resembles the actual cycle closely
but is made up totally of internally reversible processes. Such a cycle is called an ideal cycle.

57
 A simple idealized model enables engineers to
study the effects of the major parameters that
dominate the cycle without getting bogged down in
the details. The conclusions reached from the
analysis of ideal cycles are also applicable to actual
cycles. The thermal efficiency of the Otto cycle, the
ideal cycle for spark-ignition automobile engines,
for example, increases with the compression ratio.
This is also the case for actual automobile engines.

Heat engines are designed for the purpose of

converting other forms of energy(usually, in the
form of heat) to work, and their performance is
Reduction of complex processes to
expressed in terms of the thermal efficiency
manageable level by utilizing some ,which is the ratio of the most work produced by the
idealizations. engine to the total heat input:

The ideal cycles are internally reversible, but, unlike Carnot cycle, they are not necessarily
externally reversible. Therefore, the thermal efficiency of an ideal cycle operating between the
same temperatures limits. However, it is still considerably higher than the thermal efficiency on
an actual cycle because of the idealizations utilized.

The idealizations and simplifications commonly employed in the analysis of the power cycles
can be summarized as follows:

1. The cycle does not involve any friction. Therefore, the working fluid does not experience
any pressure drop as it flows in pipes or devices such as heat exchangers.
2. All expansion and compression processes take place in a quasiequilibrium manner.
3. The pipes connecting the various components of a system are well insulated, and heat
transfer through them is negligible.

Neglecting the changes in kinetic and potential energies of the working fluid is another
commonly utilized simplification in the analysis of power cycles. This is a reasonable
assumption since in devices that involve shaft work, such as turbines, compressors, and pumps,
the kinetic and potential energy terms are usually very small relative to the other terms in the
energy equation. Fluid velocities encountered in devices such as condensers, boilers, and mixing
chambers are typically low, and the fluid streams experience little change in their velocities,
again making kinetic energy changes negligible. The only devices where the changes in kinetic
energy are significant are the nozzles and diffusers, which are specifically designed to create
large changes in velocity.

58
Property diagrams such as P-v and T-s diagrams serve as valuable aids in the analysis of
thermodynamic processes. On both the P-v and T-s diagrams, the area enclosed by the process
curves of a cycle represents the network produced during a cycle. The T-s diagram is
particularly useful as a visual aid in the analysis of ideal power cycles. An ideal power cycle
does not involve any internal irreversibilities, and so the only effect that can change the entropy
of the working fluid during a process is heat transfer.

On a T-s diagram, a heat-addition process proceeds in the direction of increasing entropy, a

heat-rejection process proceeds in the direction of decreasing entropy, and an isentropic
(internally reversible, adiabatic) process proceeds at constant entropy. The area under the
process curve on a T-s diagram represents the heat transfer for that process. The area under the
heat addition process on a T-s diagram is a geometric measure of the total heat supplied during
the cycle , and the area under the heat rejectionprocess is a measure of the total heat rejected
. The difference between these two (the area enclosed by the cyclic curve) is the net heat
transfer, which is also the net work produced during the cycle. Therefore, on a T-s diagram, the
ratio of the area enclosed by the cyclic curve to the area under the heat-addition process curve
represents the thermal efficiency of the cycle. Any modification that increases the ratio of these
two areas will also increase the thermal efficiency of the cycle.

THE CARNOT CYCLE AND ITS VALUE IN ENGINEERING

The Carnot cycle is composed of four totally reversible

processes:

1. Isothermal heat addition,

2. Isentropic expansion,
3. Isothermal heat rejection,
4. Isentropic compression.
The Carnot cycle can be executed in a closed system (a
piston–cylinder device) or a steady-flow system
(utilizing two turbines and two compressors). Either a
gas or vapour can be utilized as the working fluid.

From the T-S diagram,

Heat supplied to the fluid is (1)

Heat rejected is (2)

Net work output is

Since process 2 – 3 and 4 – 1 are isentropic,

The Carnot cycle is the most efficient cycle that can be executed between a heat source at
temperature TH and a sink at temperature TL, and its thermal efficiency is expressed as

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Substituting equation 1 and 2 into 3 and simplifying,

RANKINE CYCLE

The electric power generating industry uses power cycles that operate in such a way that the
working fluid changes phase from a liquid to a vapour. The simplest vapour power cycle is
called the Rankine cycle, shown schematically below:
A major feature of such a cycle is that the pump requires very little work to deliver high pressure
water to the boiler. A possible disadvantage is that the expansion process in the turbine usually
enters the quality region, resulting in the formation of liquid droplets that may damage the
turbine blades.
The Rankine cycle is composed of the four ideal processes shown on the T-s diagram below:
1 2: Isentropic (reversible adiabatic) compression in a pump
2 3: Constant-pressure heat addition in a boiler
3 4: Isentropic (reversible adiabatic) expansion in a turbine
4 1: Constant-pressure heat rejection in a condenser

The major components

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 T – s diagram

Considering m kg of fluid:

Applying steady flow energy equation (S.F.E.E.) to pump, boiler, turbine and
condenser:

i. For the feed pump (as control volume), we get

Note: both state 1 and 2 are saturated liquid. and

ii. For boiler (as control volume), we get

iii. For turbine (as control volume), we get

iv. For condenser (as control volume), we get

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Now, efficiency of Rankine cycle is given by

The pump work is usually quite small compared to the turbine work and can most often be
neglected. With this approximation there results

Some other considerations

i.

ii. (kg/kWh)
Example
A steam power plant (Rankine cycle) is proposed to operate between the pressures of 10 kPa and
2 MPa with a maximum temperature of 400°C, as shown. Determine the maximum efficiency
possible from the power cycle, the work ratio and the specific consumption. [Take density of
water to be 1000 kg/m3]

Solution
At 10 kPa, state 1 is saturated
liquid.
State 3 is superheated vapour
At 2 MPa and 400°C

Let us include the pump work in

the calculation and show that it is
negligible.

The pump work is

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Using

The heat input is found to be

Since state 3 to state 4 is an isentropic process, to locate state 4, we recognize that

Hence

At 10 kPa,

This allows us to determine to be

The turbine work is

The efficiency is

Try
1. A simple Rankine cycle works between pressures 25 bar and 0.06 bar, the initial
condition of steam being dry saturated. Calculate the cycle efficiency, work ratio and
specific steam consumption.
2. A steam power plant is designed to operate on a Rankine cycle with a condenser pressure
of 100 kPa and boiler outlet temperature of 500°C. If the pump outlet pressure is 2 MPa,
calculate the ideal turbine work output, the boiler requirement and the maximum possible
thermal efficiency. [765 kJ/kg, 3048.7 kJ/kg, 25 %]

AIR-STANDARD ASSUMPTIONS

The actual gas power cycles are complex. To analyze it, it is needed to be reduced to a
manageable level; we utilize the following approximations, commonly known as the air-
standard assumptions for that reduction.

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 1. The working fluid is air, which continuously circulates in a closed loop and always
behaves as an ideal gas.
2. All the processes that make up the cycle are internally reversible.
3. The combustion process is replaced 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 its initial state.

INTERNAL COMBUSTION / RECOPROCATING ENGINE

Two principal types of reciprocating internal combustion engines are the spark-ignition (SI)
engine and the compression-ignition (CI) engine. In a spark-ignition engine, a mixture of fuel
and air is ignited by a spark plug. In a compression-ignition engine, air is compressed to a high
enough pressure and temperature that combustion occurs spontaneously when fuel is injected.

RECIPROCATING ENGINE

A reciprocating internal combustion engine consisting of a piston that moves within a cylinder
fitted with two valves.

The piston reciprocates in the cylinder between two fixed positions called the top dead center
(TDC)-the position of the piston when it forms the smallest volume in the cylinder-and the
bottom dead center (BDC)-the position of the piston when it forms the largest volume in the
cylinder. The distance between the TDC and the BDC is the largest distance that the piston can
travel in one direction, and it is called the stroke of the engine. The diameter of the piston is
called the bore.

The air or air–fuel mixture is drawn into the cylinder through the intake valve, and the
combustion products are expelled from the cylinder through the exhaust valve.

The minimum volume formed in the cylinder when the piston is at TDC is called the clearance
volume. The volume displaced or swept out by the piston as it moves between TDC and BDC is
called the displacement/swept volume. The ratio of the maximum volume (swept plus
clearance) formed in the cylinder to the minimum (clearance) volume is called the compression
ratio r of the engine:

64
Nomenclature for reciprocating engine

A parameter used to describe the performance of reciprocating piston engines is the mean
effective pressure (MEP). The mean effective pressure is the theoretical constant pressure that,
if acted on the piston during the power stroke, would produce the same net work as actually
developed in one cycle

net work for one cycle

MEP
displacement volume
Wnet
(kPa)
max min

The engine with a larger value of MEP delivers more net work per cycle and thus performs
better.

OTTO CYCLE: THE IDEAL CYCLE FOR SPARK-IGNITION ENGINES

The thermodynamic analysis of the actual four-stroke cycle is not a simple task. However, the
analysis can be simplified significantly if the air-standard assumptions are utilized. The resulting
cycle, which closely resembles the actual operating conditions, is the ideal Otto cycle.

65
A schematic of each stroke as well as a P-v diagram for an actual four-stroke spark-ignition
engine is given below,

P-v and T-s diagrams for an ideal Otto cycle

The Otto cycle is the ideal cycle for the spark-ignition reciprocating engines, and it consists of
four internally reversible processes:

Process 1 to 2: isentropic compression

Process 2 to 3: reversible constant volume heating (isochoric heat addition)

Process 3 to 4: isentropic expansion

Process 4 to 1: reversible constant volume cooling (isochoric heat rejection)

The thermal efficiency of the ideal Otto cycle under the cold air standard assumptions is given
by:

Where

is the compression ratio and is the specific heat ratio

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DIESEL CYCLE: THE IDEAL CYCLE FOR COMPRESSION-IGNITION
ENGINES

The Diesel cycle is the ideal cycle for CI reciprocating engines. In CI engines (also known as
diesel engines), the air is compressed to a temperature that is above the auto ignition temperature
of the fuel, and combustion starts on contact as the fuel is injected into this hot air. Therefore, the
spark plug and carburetor are replaced by a fuel injector in diesel engines.

T-s and P-v diagrams for the ideal Diesel cycle.

The diesel cycle also consists of four internally reversible processes:

Process 1 to 2: isentropic compression

Process 2 to 3: reversible constant pressure heating (isobaric heat addition)

Process 3 to 4: isentropic expansion

Process 4 to 1: reversible constant volume cooling (isochoric heat rejection)

The thermal efficiency of the Diesel cycle under the cold-air standard assumptions is given by:

67
Where r is the compression ratio defined above and is a new quantity called the cutoff ratio,
defined as the ratio of the cylinder volumes after and before the combustion process. This given
by

Comparing the thermal efficiency for the Diesel cycle to that of Otto cycle, one would notice that
under the cold-air-standard assumptions, the efficiency of a Diesel cycle differs from the
efficiency of an Otto cycle by the quantity in the brackets. This quantity is always greater than 1.
Therefore,

Try questions

1. Why is the Carnot cycle not suitable as an ideal cycle for all power-producing cyclic
devices?
2. What does the area enclosed by the cycle represent on a P-v diagram? How about on a T-
s diagram?
3. What is the difference between spark-ignition and compression-ignition engines?
4. Are the processes that make up the Otto cycle analyzed as closed-system or steady-flow
processes? Why?
5. What is the difference between fuel-injected gasoline engines and diesel engines?
6. For a specified compression ratio, is a diesel or gasoline engine more efficient?
7. Calculate the ideal air standard cycle efficiency based on the Otto cycle for a petrol
engine with a cylinder bore of 50mm, a stroke of 75mm, and a clearance of 21.3cm3.
[56.3%]

REFERENCES
1. Fundamentals of Engineering Thermodynamics, fifth edition by Michael J Moran,
Howard N. Shapiro.
2. Thermodynamics for Engineers by Merle C. Potter, Craig W. Somerton.
3. Thermodynamics an Engineer Approach, Fifth edition by Yunus A Cengel, Michael A
Boles.
4. Engineering thermodynamics, third edition by R. K. Rajput
5. Thermodynamics Demystified by Merle C. Potter

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