ME 100 BASICS OF MECHANICAL ENGINEERING

Module I
Thermodynamics
Definition

The world moves on energy. Energy in one form or another is used for all the activities of
human beings. Human development to its present state has been the result of harnessing the energy
resources of the universe. The subject of thermodynamics deals with energy in its various forms.

The word ‘thermodynamics’ is the combination of two words: thermo and dynamics. Thermo
means temperature or heat and dynamics means movement or change. Thus thermodynamics covers
movement of heat or energy conversion involving heat energy.

Thermodynamics is the branch of physical science dealing with the conversion of energy from
one form to another, especially involving heat. In other words, it is the science dealing with the
relationship between heat and work and the properties of substances.

Some of the present-day applications of thermodynamics are

 Automobiles

 Aircraft and rocket propulsion

 Heating and cooling devices

 Power plants

 Alternate energy systems

 Cryogenic engines

 Biomedical applications

Historic Perspective

The principles of thermodynamics were in existence since the creation of the universe.
Aristotle (384-322 BC) promoted the ideology of the four elements: water, air, earth and fire. Hero
of Alexandria (~20 BC) developed the primitive steam engine, aeolipile.

Thermodynamics emerged as a distinct science with the construction of the steam engines in
England in the 17th century. Thomas Sareery’s (1650-1715) steam engine was first used to pump
water out of mines. This engine was improved and made more efficient by James Watt (1736-1819).
Zeonard Sadi Carnot (1796-1832) developed the theoretical concepts of the two reservoir engine
giving maximum efficiency.

These inventions helped to bring in industrial revolution in Europe and the world has never
looked back. Richard Trevithier steam locomotive, Charles Parson’s reaction turbine and Gustaf de
Laval’s impulse turbine were important inventions which drove the industrial revolution forward.

The term thermodynamics was first used in a publication by Lord Kelven in 1849. The first
textbook on thermodynamics was written in 1859 by William Rankine. The four fundamental laws
of thermodynamics emerged through the theoretical and experimental works of many scientists,
notably Celsius, Boyle, Kelvin, Joule, Helmholtz, Carnot, Maxwell, Nernst etc.

Fundamental Concepts

Thermodynamic System

In any scientific or engineering analysis it is essential to clearly identify the material on which
we focus our attention.

A thermodynamic system (or simply system) is defined as a prescribed quantity of matter or

region in space upon which attention is concentrated for study.

This quantity of matter or region is separated from its surroundings by a boundary. The
boundary or wall may coincide with real surfaces (eg. piston head and cylinder walls) or may be
imaginary (eg. inlet section of a turbine).

Another classification of system boundaries is as movable or rigid depending on whether they

allow a change in volume of the system. A rigid wall does not allow a change in volume whereas a
movable one is non-restrictive with respect to volume. Examples are: a rigid casing inclosing a steam
turbine, a movable boundary enclosed by a moving piston in a cylinder.

Boundaries can also be classified into diathermia or adiabatic depending upon whether they
allow exchange of energy in the form of heat between the system and its surroundings. An adiabatic
wall is restrictive with respect to energy flow in the form of heat whereas a diathermia boundary
allows flow of heat energy across the boundary.
 The combination of matter and space outside the system boundary with which the system
directly interacts constitutes its surroundings. However, at a distance there will be no effect and hence
such distant space or matter is not considered as the environment or surroundings of the system.

Interactions are mass and energy flows or interchanges between a system and its surroundings.
Only the mass and energy which cross the system boundary constitute interactions and not those flow
within the system.

The totality of all systems and their surroundings form the universe.

Classification of Systems

Thermodynamic systems are classified into three types based on the kinds of interactions
between the system and its surroundings.

1. Closed Systems are those that exchange energy (heat and work) but not mass with their
environment. Since the mass of the system remains constant it is also known as control mass.

The nature of the boundary of a system usually decides the type of interactions that are
possible. An adiabatic system is a closed system with adiabatic walls. So that it does not allow
heat interactions with the surroundings.

2. Open Systems exchange energy (heat and work) and mass with their environment. Mass
exchange can be as bulk flow, or diffusion, or both. The boundary of the system is permeable.
Flow systems are........ open systems since they allow mass flow. An open system specified
with a fixed volume is called control volume.

When the terms control mass (closed system) and control volume (open system) are used, the
system boundary is often referred to as control surface.
3. Isolated Systems are completely isolated from their environment. They exchange neither
matter nor energy (heat and work) with their surroundings. So, an isolated system is one in which
both energy and mass are constant. A system enclosed by a rigid and adiabatic wall cannot exchange
energy or mass with its surroundings, and, therefore, is an isolated system.

Isolated System

Classify the following systems:

Steam turbine balloon

Car radiator storage battery

Space station LPG Cylinder

Electric motor human hand

Pressure Cooker jet engine

Submarine thermos flask

Screw jack mercury thermometer

Comparison of closed, open & isolated systems

CLOSED SYSTEM OPEN SYSTEM ISOLATED SYSTEM

1 Has fixed mass; hence, When it has fixed volume it Has both fixed mass and
also called control mass is also called control fixed volume
volume

2 Mass does not cross the Mass can enter and leave Mass does not cross the
system boundary across the system boundary system boundary

3 Energy, both in the form Both heat and work can No energy, neither heat nor
of heat and work can cross the system boundary work can cross the system
cross the system boundary
boundary

4 System boundary can System boundary is usually System boundary is fixed

usually move fixed
 5. Examples:- Greenhouse Ocean IC engine in suction Universe Insulated gas
IC engine in and exhaust strokes cylinder
compression and
expansion strokes

Working Substance

All thermodynamic devices employ some material, usually a fluid, as a medium of energy
transport between the system and its surroundings. This fluid is known as the working substance or
working fluid. In a steam power plant the working substance is water. In petrol and diesel engines it
is mostly air that is flowing. Therefore, in such systems air is considered to be the working substance.
In refrigerators and air-conditioners, the working substances are the refrigerants used.

Thermodynamic Properties

The working substance of a system can be a pure substance or a mixture of substances. A

property of a system is any of its identifiable or observable characteristic. A thermodynamic property
is a characteristic which is relevant to thermodynamics, ie., which is concerned with the interaction
of energy in the form of heat and work between a system and its surroundings. Examples are mass,
volume, energy, pressure and temperature.

Classification of Properties

Thermodynamic properties can be divided into two categories : extensive and intensive.

Extensive Properties are those whose values depend on the size or extent of the system. Mass m,
volume V, total energy, E are some examples of extensive properties.

A B C

D E

Subdivisions of a System

The value of the extensive property of a system is the sum of its values for the parts into which
the system is divided. For the system divided into parts A, B, C, D, E and F, the total mass of the
system is the sum of the individual masses of the divisions.

Intensive Properties are not additive. Their values are independent of the size or extent of the system
Pressure, temperature, density are some examples of intensive properties. In a system divided into
parts, each part has the same pressure, temperature and density as the whole system.

m extensive ½m ½m
 v properties ½v ½v
P P P
T intensive T T
P properties P P
To differentiate extensive & intensive properties

A simple method to determine whether a property is intensive or extensive is to divide the

system into two equal parts with a partition. The values of intensive properties of the two halves will
be the same as those of the undivided system, whereas the values of the extensive properties of the
halves will only be half of the values of the original system.

Extensive properties per unit mass are called specific properties. Some examples of specific
properties are

v
Specific volume, v  and
m

E
Specific total energy, e  Specific properties may be considered as intensive properties,
m
since their values are independent of the mass of the system. However, they are not true intensive
properties in the sense of their definition.

(temperature, pressure, viscosity, velocity, thermal conductivity, volume, mass, enthalpy,

entropy are all examples of properties)

Problem-solving Technique

Solving problems especially complicated problems, require a systematic approach. By using

a step-by-step approach, an engineer can reduce the solution of a complicated problem into the
solution of a series of simple problems.

Step 1: Problem statement: In your own words state the problem, the key information given and the
quantities to be found.

Step 2: Schematic : Draw a simple but realistic sketch of the physical system involved and list the
relevant information on the figure. This helps one to see the entire problem at once.

Step 3: Assumptions and appropriations : State any appropriate assumptions and approximations
made to simplify the problem to make it possible to obtain a solution. Assume reasonable values for
missing quantities.

Step 4. : Physical laws and formulae : Apply all the relevant basic physical laws and principles and
reduce them to the formulae applicable, incorporating the simplifying assumptions.
Step 5: Calculations : Substitute the known quantities in to the simplified relations (formulae) and
perform the calculations to determine the unknowns.

Pay particular attention to the units of the quantities. Also, don’t give a false implication of
high precision by copying all the digits from the screen of the calculator - round the results to an
appropriate number of significant digits.

Keep in mind that the solutions are forms of communication to others. Therefore, neatness,
organisation, completeness and visual appearance are of utmost importance for maximum
effectiveness. Carelessness and skipping steps to save time often end up costing more time and
unnecessary anxiety.

It may be observed that for some problems, some of the steps described may not be applicable
or necessary. However, the importance of a logical and orderly approach to problem-solving is
incontrovertible. Most difficulties encountered in problem solving are not due to a lack of knowledge,
rather, they are due to a lack of organisation.

University questions

THERMODYNAMIC SYSTEM

Explain about closed and open systems (Jan 2007)

Differentiate between closed system and open system, (May 2008)

Give examples

THERMODYNAMIC PROPERTY

What is meant by property of a system? What are its classifications? (June, 2006)

What are intensive and extensive properties? From the following properties, differentiate intensive
and extensive properties. (May, 2008)

(i) Volume (ii) Kinetic energy

(iii) specific enthalpy (iv) internal energy

(v) density (vi) temperature

(vii) flow work (viii) pressure

Describe question paper structure

Part A : 2 from each module – 2 × 5 = 10 questions; no choice; 4 marks each – total 40 marks

Part B : 2 from each module of which one only need be answered 1 × 5 = 5 questions; 12 marks each
– total 60 marks
THERMODYNAMIC SYSTEM

Define thermodynamic system

Explain closed and open systems with sketches and examples

(Give the comparison chart and examples with sketches)

What is thermodynamic system?

Distinguish between control mass and control volume.

THERMODYNAMIC PROPERTIES

Definition: The thermodynamic property is any of the identifiable or observable characteristic of a

system, which is relevant to thermodynamics, ie. concerning heat and work energy interactions.

Classification : Extensive properties are those whose values depend upon the size or extent of the
system. Examples: volume mass, total energy.

Intensive properties are those whose values are independent of the size or extent of the system.
Examples : pressure, temperature, density.

Extensive properties expressed per unit mass are called specific properties. Specific properties
behave like intensive properties, as their values are independent of the size of the system. Examples
 V
are specific volume     , specific energy
 m

(i) Volume value depends on size – extensive property

(ii) Kinetic energy = ½mc2 mass dependent – extensive property

(iii) Specific enthalpy = sH/m pecific property – intensive property

(iv) Internal energy value depends on size – extensive property

(v) Density value independent of size – intensive property

(vi) Temperature value independent of size – intensive property

(vii) Flow work – work is energy in transit, not a property process dependent, not a system
characteristic

(viii) Pressure value independent of size – intensive property.

When engineering calculations are performed it is necessary to measure the physical quantities
involved in terms of specified units. A unit is any specified amount of a quantity by comparison with
which any other quantity of the same kind is measured. For example, meters, kilometers, feet and
miles are all units of length. Similarly, seconds and hours are units of time.
 Because physical quantities are related by definitions and laws, a relatively small number of
them are sufficient to measure all others. These are called primary dimensions. The others are
measured in terms of primary dimensions and are called secondary. For example, if length and time
are primary dimensions, area and velocity became secondary dimensions.

Once a set of primary dimensions is adopted, a base unit of each primary dimension is
specified. Units for all other (secondary) quantities are then derived in terms of the base units and are
called derived units.

SI is the abbreviation for Le Systems International d’Unites (International System of Units).

It was adopted in 1960 and is the legally accepted system i most countries. The primary dimensions
and their base units are given in Table 1. Table 2 gives the non-SI units recognized for use along with
SI units.

Amount of Substance

The basic SI unit for mass is the kilogram (kg). Since all materials are known to consist of
atoms, molecules, etc., the amount of substance can also be expressed in terms of the number of such
particles present in the matter. This unit is called the mole (abbreviated to ‘mol’) and is defined as
the amount of substance that contains the same number of elementary particles as the number of
atoms in 0.012 kg of carbon-12. This number of atoms is called Avogadro’s number, NA , and is equal
to 6.022×1023. If the mass of an atom of a substance is ‘m’, the mass of one mol of that substance is
= m × NA . This quantity, molar mass, denoted by ‘M’ , is also called molecular weight. i.e., M = m
× NA. Hence the number of moles in a given mass of the substance is given by

total mass
n = n=
M

Derived units

The secondary quantities are expressed in terms of the derived units. Some of the derived nits
occur so frequently that they are given special names and symbols. Thus, the units of pressure, energy
and power in SI are pascal (Pa), joule (J) and watt (W) respectively. The SI unit of pressure, Ps, is
very small in magnitude. Hence, for convenience pressure is commonly expressed in kilopascal and
megapascal. To facilitate working with extremely large of small values when using SI units, a set of
standard prefixes are used, as given in Table 3, to express these quantities in terms of appropriate
multiples of SI units.

Pressure

Pressure is an important quantity in thermodynamic analysis. Though its SI unit is the pascal
(Pa), sometimes pressure is expressed in terms of an independent unit, the standard atmosphere (atm).
One standard atmosphere is defined as equal to the pressure exerted by a column of 760 mm of
mercury at specified conditions. The pressure exerted by 1 mm column of mercury at these conditions
is called 1 torr.

1 atm = 760 torr = 101325 Pa = 101.325 k Pa

1 torr = 1 mm Hg = 0.1333 kPa

A pressure which is less than atmospheric is referred to as vacuum. A pressure which is less
than atmospheric pressure by 600 mm Hg is called a vacuum of 600 mm Hg.

Most of the pressure measuring devices like the Bourden pressure gauge, measure the
difference in pressure between the fluid and the atmosphere. This pressure difference or the pressure
indicated by the gauge is called gauge pressure. The absolute pressure, P , of the fluid is then given
by

P = Patm + Pguage, for pressure above atmospheric pr.

P = Patm - Pguage, for vacuum

The relationships are illustrated in the figure.

Temperature

In its primitive concept, temperature is a measure of the hotness of a system as felt by the
human body. Under molecular theory, it is a measure of the motion of the molecules due their energy.

Relationship among absolute, atmospheric, gauge and vacuum pressures

The basic SI unit for temperature is kelvin (K). One kelvin is defined as the fraction 1/273.16 of
the thermodynamic temperature of the triple point of water. Quite often, the Celsius temperature (oC)
is used to express temperature of a substance. The Celsius temperature is defined as C = K – 273.15.
 The Celsius temperature scale was defined by using the ice point and boiling point of water at
atmospheric pressure. In Celsius temperature scale, the interval between the ice point and the boiling
point was divided into 100 equal parts. The ice point was given the arbitrary value of zero, so that the
boiling point became 100oC.

Experiments were conducted using various gases keeping them at constant pressure.

Rankine and Fahrenheit temperature scales

These scales have a unit interval of temperature equal to five-ninth the size of a unit interval
of temperature on the Kelvin and Celsius scales. By definition, the Rankine scale is an absolute scale
based solely on the temperature of the triple point of water.

T (R) = 9/5 T(K)

The Fahrenheit scale is related to the Rankine scale by the equation

o
F) = T (R) - 459.67

Thus, at ice point where the kelvin temperature is 273.15, the Rankine temperature is
9
/5(273.15) = 491.67 R

and the Fahrenheit temperature is

o
F) = 491.67 - 459.67

= 32oF
o o
Therefore, C) + 32

Comparison of Temperature Scales

FIXED POINT CELSIUS KELVIN FAHRENHEIT RANKINE

1. Steam point 100 373.15 212 671.67

2. Triple point of H2O 0.01 273.16 32.02 491.69
3. Ice point 0 273.15 32 491.67
4. Absolute zero -273.15 0 -459.67 0
and the values of volume were plotted as a function of temperature. These gave a family of straight
lines that interest at zero volume when extrapolated.
Absolute temperature Scale

This unique temperature of the intersection point is known as the absolute zero temperature,
which corresponds to -273.15oC. The absolute temperature scale begins at absolute zero temperature
and is always positive. Based on the concept of temperature as a measure of molecular motion of
matter, at absolute zero temperature, there is no molecular motion.

In the SI system the absolute temperature is given in kelvin (K). Thus we define

K = oC + 273.15

For most engineering calculations, the formula k = oC + 273 may be used

STP and NTP

The reference conditions, standard temperature and pressure are 15 oC and 760 mm by Hg
respectively. The normal temperature and pressure are taken as 0oC and 760 mm Hg respectively.

Temperature and the zeroth law of thermodynamics

Although we will familiar with temperature as a measure of hotness or coldness, it is not easy
to define it directly. It is common experience that when a hot body is brought into contact with a cold
body heat flows from the hot body to cold body. When the heat transfer stops the bodies are said to
have reached thermal equilibrium.

System A System B System A System C System B System C

Consider the arrangement at fig (a) above where two systems A and B separated by an
adiabatic wall are both in contact with a third system C through a diathermic wall. When the heat -
flows between A and C, and B and C stops, we can say that systems A and B are in thermal
equilibrium with system C. Now if the walls are interchanged to the arrangement at fig (b), it is
observed that there is no heat transfer between the systems A and B or they are in thermal equilibrium.
This experience leads to the formulation of the zeroth law of thermodynamics.

The zeroth law of thermodynamics says that if two bodies are in thermal equilibrium with a
third body, they are in thermal equilibrium with each other.

The zeroth law was first formulated and named by R H Fowler in 1931. Therefore its value as
a fundamental physical principle was recognized more than half f century after the formulation f the
first and second laws of thermodynamics. It was named the zeroth law since it should have preceded
the first and second laws of thermodynamics.

On the bases of the zeroth law of thermodynamics we can say that there must be some property
of the systems (bodies) which attains equal value when the systems attain thermal equilibrium with
each other. Thus property is called temperature.

The zeroth law also gives us a method to measure the temperature of a system. If the third
body is replaced with a thermometer, the zeroth law can be restated as, two bodies are in thermal
equilibrium if both have the same temperature reading even if they are not in contact.

The temperature of a body is measured by bringing a thermometer in contact with the body
till the thermometer and the body reaches thermal equilibrium. At that state both have the same value
of temperature. Therefore, the temperature of the thermometer indicated on it gives the temperature
of the body.

Several properties of materials change with temperature in repeatable and predictable way,
and this forms the basis for temperature measurement. Examples are mercury in glass thermometer
based on expansion of mercury, resistance thermometer, etc.

State

The thermodynamic state of a system is the inside condition fo the system at any given instant
of time. The state of a system at any given instant is determined by the values of its properties at that
instant.

At a given state each property of the system has a definite value. The system can change its
condition due to work and heat interactions with its surroundings. When the system changes from
one state to a second state its properties will have a different set of definite values. In other words,
when any of the properties of a system changes, a change of state occurs.
Thermodynamic equilibrium

If a system has no tendency for a change of state, spontaneously or under outside influences,
it is in thermodynamic equilibrium. In such a case the values of its properties do not change and there
are no interactions between the system and its surroundings.

An intensive property of a system is defined to have a value at a point in the system. For
example, the intensive property temperature, T has a value at each point in the system and may vary
from point to point. Similar is the case with the intensive property pressure, P. If the system has no
interactions with the surroundings, these intensive properties tend to equalise in course of time and
attain the same value at all points in the system. Then it is possible to quote one value of the property
for the system as it is uniform throughout that system.

Thus, if the system is in an equilibrium state it must have the same intensive properties at all
points in the system. In other words, a state of a system can be defined only when it is in equilibrium.

Thermodynamic process

Whenever one or more of the thermodynamic properties of a system change there is a change
of state of the system. This change of state of a system is known as a thermodynamic process. Also,
since the state of a system can be defined only when it is in equilibrium, a process is any
transformation of a system form one equilibrium state to another.

A process between states 1 and 2, and the process path

The series of states through which a system passes during is called the path of the process. To
describe the process completely one must specify the initial and final states of the process as well as
the path it follows and the interactions with its surroundings.

Thermal equilibrium exists when there is no spontaneous change in the coordinates of a system
in mechanical and chemical equilibrium when it is separated from its surroundings by diathermic
walls. In other words, there is no exchange of heat between the system and its surroundings. In thermal
equilibrium all parts of the system are at the same temperature and this temperature is the same as
that of the surroundings, i.e, TS = TE

In other words, PS = PE means that there is no energy flow as work. TS = TE means that there
iS iE means that no mass flow exists. They also imply that PS, TS
iS remain uniform and constant. The former set of conditions ensures
external equilibrium and the latter internal equilibrium. In other words, in a stat of thermodynamic
equilibrium, the system is in both external and internal equilibrium.

When the conditions for any one of the mechanical, chemical and thermal equilibria is not
satisfied, the system is considered to be in a state of non-equilibrium.

Thermodynamic equilibrium

When the properties of a system change in any way, either spontaneously or due to external
influences, the system is said to undergo a change of state. If the system has no tendency for a change
of state, spontaneously or under outside influences it is in complete thermodynamic equilibrium. In
that case, the values of its properties do not change and there are no interactions between the system
and its surroundings.

A complete thermodynamic equilibrium implies

1. mechanical equilibrium

2. chemical equilibrium

3. thermal equilibrium

When there is no unbalanced force or toque in the interior of a system and also none between
a system and its surroundings, the system is said to be in a state of mechanical equilibrium. When
there is mechanical equilibrium, the pressure of the system must be the same as that of its
environment, i.e., PS = PE .

When a system does not tend to undergo a spontaneous change of internal structure, such as a
chemical reaction, or a transfer of matter from one part of the system to another, such as diffusion or
solution, or between the system and its surroundings, then it is said to be in a state of chemical
equilibrium. A state of chemical equilibrium signifies that the chemical potentials of the system and
iS iE

tendency for the change in chemical composition.

 If the external force is changed by removing the weight, there will be an unbalanced force
between the system and the surroundings and under the gas pressure the piston will jump up till it hits
the stops.

Thus, the finite unbalanced force causes the system to pass through non-equilibrium states and
finally come to an equilibrium sate as described by the properties P2, V2, T2. But the intermediate
states passed through by the system are non-equilibrium states and hence cannot be described by
system-wide thermodynamic coordinates. The initial and final equilibrium states of the system are
represented by points 1 and 2 in the P-V diagram, but the process path is non-existent. Any broken
line can be drawn between points 1 and 2 as a representation of this non-equilibrium process, though
it has no meaning.

If the weight on the piston is made up of many infinitesimally small pieces of weights and
these weights are removed one by one very slowly from the top of the piston, at any instant of the
upward travel of the piston, the departure of the state of the system from the thermodynamic
equilibrium state will be infinitesimally small. So every state passed through by the system will be
equilibrium and all the states through which the system passes can be described by means of
thermodynamic coordinates referring to the system as a whole.

Processes occur due to the interaction between a system and its environment. These are the
basic units of behaviour of a thermodynamic system. Process executed by open systems are flow
processes and those executed by closed systems are non-flow processes.

Quasi-state process

A system can change its stat only by interacting with its environment. However, a system in
thermodynamic equilibrium ceases to be in equilibrium when the change occurs. Thus,
thermodynamic equilibrium specifies only static states. “Consequently they do not have any practical
use. However, their advantage is that they can be specified by very few variables and simple
relationships. In order to retain this advantage of the condition of thermodynamic equilibrium, the
concept of quasi-state process is developed.

As the name implies, a quasi-static process is almost static. A quasi-static process (or quasi-
equilibrium process) is defined as one during which the system will always be in thermodynamic
equilibrium. Or, a quasi-static process is succession of equilibrium states.
 Consider a system of gas contained in a cylinder. The system initially is in an equilibrium
state, represented by the properties P1, V1, T1. The weight on the piston balances the upward force
exerted by the gas. Once a system is in thermodynamic equilibrium and the surroundings are kept
unchanged, no interaction will take place.

A process performed in this ideal way is called a quasi-static process. The path of a quasi-
static process is the locus of a series of equilibrium states through which the system passes during the
process, as shown in the P-V diagram.

A quasi-static process is an idealised process and is not a true representation of an actual

process. Engineers are interested in quasi-static process for reasons.

1. they are easy to analyse, and

2. they serve as standards with which actual process can be compared.
The most common process, all assumed to be quasi-static, are :
Isochoric or isometric (constant volume)
Isobaric or isopiestic (constant pressure)
Isothermal (constant temperature)
Adiabatic (no heat exchange)

Point function vs. Path function

At a given state each property has a definite value that can be assigned without the knowledge
of how the system arrived at that state. The temperature of air in the room has a certain value at the
moment that does not depend on whether the room heated up to that temperature or cooled down to
it.

Consider the change of state of a system from initial state 1 to final state 2, as shown in figure.
It can be seen that state 2 may be reached from state 1 by following many different paths like A and
B. The state 2 whether reached by path A or B will have the same values of properties P2, V2.
Therefore, the change in value of a property as the system is changed from one state to another is
determined solely by the two end states and is independent of the path followed to reach that state.
Because of this characteristic the state is a point function so also the parameters that define the state,
viz, its properties.

Many different paths for the change of state of a system

Accordingly, the change in value of a property between any two given states is the same
irrespective of the path or process between the states. Thus, the change in the properties of the system

as it moves from state 1 to state 2 will be  dP  P2  P1 and  dV  V2  V1 irrespective of whether

the path followed for the change is 1-A-2 or 1-B-2, or any other.
The converse of the above is also true. Any quantity whose change is independent of the path
of change is a point function and hence is a property.
In contrast to a state a process is a path. The quantity, the value of which depends on the path
followed during a change of state is a path function. For example, the areas under curves 1-A-2 and
2
1-B-2 are different and we cannot write  da  a 2  a1 . In fact, the initial value of a1, and the final
1

2
value a2 have no meaning. Hence we can only denote  da 1 a 2 , signifying that the value of ‘a’ can
1

only be determined if the path followed from 1 to 2 is specified.

Summarising, properties are point functions, signifying that the change in their values is
independent of the path of the process. Conversely, if the value of a quantity is point function, i.e.,
independent of the process path, then that quantity is the change in a property.
Similarly, if the value of a particular quantity depends on the details of the path followed by
the process, and not solely on the end states, it is a path function and that quantity cannot be a property.
Thus, energy interactions which depend on the path of the process are path functions.
Reversible and irreversible processes

A process is a reversible process if it can be completely reversed. It implies that when carried
out in the opposite direction the system follows the same path as it followed in the forward direction.
Thus the system is resorted to its initial conditions. In addition, the interactions between the system
and the surroundings are also equal and opposite in direction. Hence the surroundings are also restored
to the initial conditions.

A quasi-static process implies an infinitely slow process and in the absence of friction, may
be thought of as a succession of equilibrium states. Such a process can be reversed restoring the
system and its surroundings to the initial states. Thus, a quasi-static process without friction is a
reversible process. A non-equilibrium process can not be completely reversed and the system can not
be brought back to the initial state without leaving a net change in the surroundings. Such a process
is an irreversible. All real process are irreversible process.

Thermodynamic cycle

A thermodynamic cycle is a sequence of processes that begins and ends at the same state. At
the conclusion of a cycle all properties of the system have the same values they had at the beginning.
Consequently, over the cycle the system experiences no net change of state. Cycles that are repeated
periodically play prominent roles in many applications. For example, steam circulating through a

power plant executes a cycle. Thus, for a cycle  dP1  0 and  dP2  0 .

Thermodynamic Cycle

Previous University Questions

1. What is zeroth law of thermodynamics?

The zeroth law of thermodynamics states that if two systems are in thermal equilibrium with
a third system, they are in thermal equilibrium with each other.
Significance : 1. It forms the basis for definition of temperature.

2. It provides the method for measurement of temperature.

2. Define quasi-static process and state its salient characteristics

Definition: A quasi-static process is defined as one during which the system will always be in
thermodynamic equilibrium. Hence a quasi-static process is a succession of equilibrium states.

Salient characteristics :

i) A quasi-static process is in idealised process and is not a true representation of an actual process.

ii) Quasi-static processes are easy to analyse and serve as standards with which actual process can be
compared.

iii) A quasi-static process is a succession of equilibrium states, the system being always in
thermodynamic equilibrium during the process.

iv) Since the changes in the state of a system in a quasi-static process are infinitesimally small so as
to remain in thermodynamic equilibrium always, such a process is extremely slow.

Equation of State

It is possible to deduce general relations between thermodynamic properties which hold for a
limited class of systems. Since relations between thermodynamic properties are independent of
whether the substance is in motion or not, we need to refer to only closed systems. The distinguishing
characteristics of these systems with a pure working substance in a single phase (usually gaseous) are
that, when in equilibrium.

a) they only change when heat and mechanical work cross their boundary.

b) only two independent properties are necessary to determine their thermodynamic state.

For such a system the only measurable thermodynamic properties are the pressure, P, volume,
V, and temperature, T. If we fix the volume and temperature at some arbitrary values, the value of P
at equilibrium is determined by nature. Similarly, if P and T are chosen arbitrarily, then the value of
V at equilibrium is fixed. That is, of the three thermodynamic coordinates P, V and T, only two are
independent variables. This implies that there is an equation of equilibrium which connects these
thermodynamic coordinates. Such an equation, expressing the relation between P, V and T is called
an equation of state or characteristic equation.

An equation of state expresses the individual peculiarities of one system as compared to anther
system and must, therefore, be determined either by experiment or by molecular theory. An equator
of state is thus only as accurate as the experiments that led to its formulation and holds only within
the range of values measured. As soon as this range is exceeded, a different form of equation of state
may valid.

An equation of state is a mathematical function relating the thermodynamic coordinates of a

closed system in equilibrium, in the form,

f(P,V,T) = 0

Gas laws

A gas is a substance in gaseous phase, for which the evaporation from its liquid phase is
complete. Examples are air, oxygen, carbon dioxide within the pressure and temperature ranges
normally encountered. A vapour is a substance whose evaporation from its liquid phase is only partial.
Hence a vapour contains liquid particles in suspension. When the evaporation is complete the vapour
is said to be dry. When a dry vapour is further heated it becomes a super heated vapour. Steam is a
common example of a vapour. Thus dry and superheated vapours are gases.

The terms “ideal gas” and “perfect gas” are identical terms having the same meaning and
defined as gases obeying the ideal gas equation of state.

Under the kinetic (molecular) theory of gases an ideal gas conforms to the following
assumptions.

1. The gas molecules are perfectly elastic, i.e., there is no loss of momentum when they collide.

2. The molecules are point masses, i.e., they possess mass but have no (negligible) volume
compared to the dimensions of the system containing them.

3. The intermolecular forces are absent (negligible)

Real gases do not satisfy these assumptions. But, surprisingly, it has been found that the ideal
equation can be used to represent the behaviour of a large class of real gases with an accuracy usually
sufficient for engineering applications. In any case, this equation can be used to predict qualitatively
the behaviour of most gases, and the results so obtained can be employed as a guide for design or
performance purposes.

Real gases tend to behave ideally at low pressures and at high temperatures (which causes
expansion and low pressures). Hence, this condition is also used to define ideal gases with the
expression “all gases behave ideally at zero pressure.”

Comparison of Ideal and Real gases

IDEAL GAS REAL GAS

 Obeys the ideal gas equation of Equations of state are more complicated.
state.
  Molecules are assumed to be Molecules have finite sizes.
point masses.
 Intermolecular forces are Intermolecular forces are significant.
assumed to be negligible.
 Molecules are considered to be Molecules change momentum on
perfectly elastic. collision.

Boyle’s law
The first law concerning the equation of state of a gas were made by Robert Boyle (1629-
1691), an English chemist, in the year 1662. His experimental observation, known as Boyle’s law,
states that
The volume of a given quantity of gas whose temperature remains constant varies inversely
as its pressure.

We can write Boyle’s law as

1
V when T is constant
P

or PV = C where C represents constant

For different states, this equation can be written as

P1V1 = P2V2 = P3V3 = C, for constant T

Charles’ law

In 1787, the French physicist, Jacques Charles (1747 - 1832) showed from his experiments the
relation between volume and temperature, known as Charles’ law.

The volume of a given quantity of gas varies directly as its absolute temperature if the pressure
is held constant.

Charles’ experiment also showed that the pressure of a given quantity of gas varies directly as
its absolute temperature if the volume is held constant.
 Mathematically, Charles’ law can be written as

V
= constant, when pressure is constant
T

P
= constant, when volume is constant
T

This law is also known as Gay-Lussac’s law.

Ideal gas equation of state

By combining Boyle’s law and Charles’ law into a single equation we can obtain a general gas
law known as the ideal gas equation of state or characteristic equation of gas.

Consider a closed system of an ideal gas at state 1 with the coordinates of P1 V1 and T1 which
is taken to state 2 with coordinates of P2, V2 and T2. To go from state 1 to state 2 the system follows
the path 1-a-2. 1-a is a constant volume process and a-2 is a constant pressure process.

For the constant volume path 1-a

Pa P1

Ta T1
 Pa
or Ta  T1 (1)
P1

For the constant pressure path a-2

V2 Va

T2 Ta

But Va = V1, and Pa = P2. Thus we can write

V2 V1 P1

T2 T1 P2

P2 V2 P1V1
Or 
T2 T1

PV
Or = a constant.
T

If the constant for a gas per unit mass is R, and the mass of the gas is m, the above equation
becomes

PV
 mR
T

or PV = mRT-------(a)

This is called the ideal gas equation of state or characteristic equation of state and the constant
R is called the characteristic gas constant whose values are different for different gases R is usually
expressed in the unit kJ/kgK

V V
The characteristic gas equation may also be written as P  RT . But   , the specific
m m
volume. Therefore the equation becomes

P = RT ..... (b)

The characteristic gas equation is

PV = mRT, which can be written as

M
PV  m RT where M is the molar mass of the gas.
M

m
Or PV  MRT
M

m
i.e., PV = nMRT, because  n , no. of moles.
M
 It has been observed that for most gases the product of molecular weight (M) and the
characteristic gas constant (R) is nearly the same value. This product (MR) is called the Universal
Gas Constant (R) and is considered to be the same for all gases. Therefore, the above equation can be
written as

PV  nRT ..... (c)

V
Or P  RT
n

Or P  RT ..... (d) where  is the molar volume

The four equations (a), (b), (c) and (d) are all different forms of the ideal gas equation of state.

The Avogadro’s law states that equal volumes of gases at the same temperature and pressure
contain the same number of molecules (elementary particles). It, therefore, follows that the value of
 will be the same for all gases at the same temperature and pressure.

At normal temperature (0oC = 273K) and pressure (1 atm = 101.235 kPa), the molar volume
of all gases is found to be 22.4 m3/kmol. Substituting these values in equation (d), we get

101.325 × 22.4 = R × 273

101.235  22.4 kJ
Or R  8.314
273 kmolK

The ideal gas equation of state or the perfect gas law can be written as

PV = mRT

P = RT

PV  nRT

P  RT

where P = pressure

m = mass
V = volume

V
 = specific volume =
m

n = amount of gas in moles

V
 = molar volume =
n
 R = specific (characteristic) gas constant

R = universal gas constant.

Previous University Examination Questions:

 Explain the following: Boyle’s Law, Charles’ Law

 Write notes on universal gas constant.

 What is an ideal gas? Discuss the derivation of gas laws for an ideal gas.

 State perfect gas law and explain universal gas constant in thermodynamics. List the
limitations of perfect gas law.

 Calculate the characteristic gas constant for oxygen.

R 8.314
R O2    0.2598 kJ
M O2 32 kgK

Energy, Heat and Work

Energy

Thermodynamics is defined as the science of energy. Everyone has an intuitive understanding

of the concept of energy. But it is difficult to define energy precisely. Energy can be considered as
the ability to cause changes, the capacity to do work, the capability for action interaction.

Energy can exist in many forms such as thermal, mechanical, kinetic, potential, electric,
magnetic, chemical and nuclear. The sum of all these forms of energy is the total energy, E of a
system. It is an extensive property, being dependent on the size of the system.

Mechanical energy can be defined as the form of energy that can be converted to mechanical
work completely and directly by an ideal machine such as an ideal turbine. Kinetic and potential
energy are two forms of mechanical energy. Thermal energy is not mechanical energy since it can
not be completely converted to mechanical work. Fluid flow produces mechanical work and flowing
fluid is the result of pressure. The unit for pressure, Pa = N/m2, or Nm/m3 or J/m3, in other words,
energy per unit volume. Thus the energy associated with fluid flow is given by PV ( pressure
multiplied by volume). It is convenient to call this flow energy and is another form of mechanical
energy. Thus,

Emech = flow energy + kinetic energy + potential energy

= PV + ½mC2 + mgZ
 Internal energy is the sum of all microscopic forms of energy of a system. It is related to the
molecular structure and the degree of molecular activity. Thus it is the sum of the kinetic and potential
energies of the molecules. The internal energy, U, is thus a part of the total energy of a system.

The kinetic energy of molecules consists of translational, rotational and vibrational velocities.
The average velocity and the degree of activity of the molecules are proportional to the temperature
of the gas. Hence this is called thermal energy.

The internal energy associated with the atomic bonds in a molecule is called chemical energy.
During a chemical reaction such as a combustion process, some chemical bonds are destroyed while
others are formed. As a result the internal energy changes.

An atom consists of neutrons and protons bound together by very strong nuclear forces in the
molecules and electrons orbiting it. The tremendous amount f energy associated with the strong bonds
within the nucleus of the atom itself is called nuclear energy.

Thus, internal energy consists of the following components of microscopic energy.

1. thermal energy

2. chemical energy

3. nuclear energy

The chemical energy changes when the structure of the electrons of atoms changes due to a
chemical reaction. A nuclear reaction involves changes in the nucleus. An atom preserves its identity
during a chemical reaction but loses it during a nuclear reaction.

It is not practically possible to measure the absolute internal energy of a system in a given
state. This is not essential in thermodynamic analysis as it is concerned with only changes in internal
energy and not their absolute values.

Static and dynamic forms of energy

These forms of energy so far discussed which constitute the total energy of a system, can be
contained or stored in a system, and thus are static forms of energy. The forms of energy not stored
in a system are the dynamic forms of energy, or energy interactions. This represent the energy gained
or lost by a system during a process and are recognized at the system boundary. For a closed system
the tow forms of energy interactions are heat transfer and work. An energy interaction is heat transfer
if it occurs due to a temperature difference. Otherwise, it is work. An open system can exchange
energy also through mass transfer since whenever there is mass transfer the energy content of the
mass is, also transferred with it.
Heat

Heat is defined as the dynamic energy that is transferred across the boundary of a system due
to a temperature difference between the system and its surroundings. Therefore, an energy interaction
is heat, only if it occurs because of a temperature difference, and the heat transfer stops when the
system and its surroundings reach the same temperature. The transferred heat becomes part of the
internal energy of the recipient system.

Heat is energy in transition and is recognized only as it crosses the boundary of a system. The
amount of heat transfer depends on the process under which the transfer occurs and hence is a path
function and not a property of the system. The process of heat transfer if assumed to occur quasi-
statically allows calculation of the quantity of heat transferred.

Being a form of energy the unit of heat in SI system is the kilojule (kJ). We shall use the sign
convention that heat into a system from its surroundings is positive and the heat out of a system is
negative.

Specific heat

Experience is that different amounts of energy are required to raise the temperature of identical
masses of different substances b the same degree. These different rates of energy volume process.
The energy required to do the same with a constant pressure process is the specific heat at constant
pressure.

The specific heat at constant pressure, Cp is always greater than the specific heat at constant
volume, Cv because at constant pressure the system is allowed to expand and the energy for this
expansion work must also be supplied to the system.

Work

Work, like heat, is an energy interaction between a system and its surroundings. Heat is the
energy interaction driven by a temperature difference between the system and its surroundings.
Energy interactions not caused by a temperature difference between the system and its surroundings
are all work.
 More specifically, work is the energy transfer-associated with a force acting through a
distance. Such work interactions are involved in a moving piston, a rotating shaft and an electric wire
crossing the system boundary.

Work is also a form of energy transfer and, therefore, has the SI unit kJ. The work done per
unit time is called power. The unit of power is kJ/s or kilowatt (kW)

Heat and work are directional quantities, and thus the complete specification of a heat or work
interaction requires the specification of both the magnitude and the direction. The generally accepted
formal sign convention for heat and work interactions is:

Storage is indicated by a property called specific heat

1kg 1kg
IRON WATER
20→30oC 20→30oC

4.5 kJ 41.8 kJ

Comparison of Energy Storage Capabilities

The specific heat is defined as the energy required to raise the unit mass of a substance by one
unit of temperature.

Since this is energy interaction its amount depends on the type of process executed. In
thermodynamics, specific heats under two processes are considered, specific heat at constant volume,
Cv and specific heat at constant pressure, Cp.

The specific heat at constant volume is the amount of energy required to raise the temperature
by one unit of mass of a substance through a constant
 When a gas is heated at constant pressure, it expands thus doing work in addition to increasing
its temperature. The heat supplied to it is used partly in raising its temperature and partly in doing
work against external pressure.

When a gas is heated at constant volume no work is done and the heat supplied to it is used
only for raising the temperature. Hence the amount of heat required to be supplied to 1kg of gas to
raise its temperature by 1oC at constant pressure will be greater than that at constant volume.

Therefore, the specific heat at constant pressure, Cp is greater than the specific heat at constant
volume, Cv or Cp > Cv

CP
Therefore, the ratio  1 . Cpair = 1.005 kJ/kg, Cvar = 0.718 kJ/kg
CV

CP
The ratio is denoted by γ, called the adiabatic index. Its volume for air, γair = 1.4.
CV

In case of solids and liquids, the values of Cp and Cv are almost equal, since they are
considered incompressible. Hence, usually, only one value of specific heat is specified for solids and
liquids.

The word ‘incompressible’ is used to mean that the change in volume due to heat transfer is
small in comparison with the volume of the system and the energy transfer required for such small
change in volume is negligible and the whole (almost) of the energy transferred goes towards the
change in temperature.

To make a fluid flow in a system work has to be done. To evaluate the net amount of work to
push the fluid into and out of the system given in the figure, consider the inlet (1) and (2) sections.
Since a steady flow is assumed, the mass flow rats at (1) and (2) m kg/s are the same. The inlet and
outlet pressures are P1 and P2 respectively. An element of the fluid of mass m, length l1 and area of
cross section A1 is entering the system at the inlet. The work done to push this element into the
system,

W1 = P1A1l1 = P1V1 (V1= m v1) (negative)

At the outlet, this element is pushed out with the work

W2 = P2 A2 l2 = P2V2. (V2 = mv2) (positive)

Therefore, the net flow work = W2 - W1

= P2V2 - P1V1 = P2 V2 - P1 V1 (per unit mass)

This represents the amount of work done on a system minus the work done on its surroundings to
cause the flow of the fluid through the system. It should be kept in mind that the product Pv represents
flow work only in steady flow systems. Flow work exists only to cause the fluid to cross the
boundaries of a flow system.

Heat transfer to a system and work done a system are positive; heat transfer from a system and
work done on a system are negative.

Heat and work are energy transfer mechanisms between a system and its surroundings. Their
similarities are

1. Both heat and work are boundary phenomena.

2. Systems process energy, but not heat or work.

3. Both are associated with processes, not states of a system.

4. Both are path functions, and not properties.

Flow Work

Consider a steady-flow system where in both mass, and energy can cross the system
boundaries. The term ‘steady’ denotes a process or system that negative during a compression
process.

The total inflow work done during the entire process from state 1 to 2 is obtained by adding
all the differential works from the initial state to the final state.

1 W2   PdV
1

This integral can be evaluated only if we know the functional relationship between P and V during
the process, i.e., the equation for the process path on the PV diagram.

It can be seen from the PV diagram that the differential area da below the process path is equal
to PdV , which is the differential work. The total area under the process curve 1-2 is obtained by
adding these differential areas.

2 2
i.e., Area =  da   PdV
1 1

Thus, the area under the process curve on the PV diagram is equal in magnitude to the work done
during a quasi-static expansion for compression process of a closed system.
First Law of Thermodynamics

The first law of thermodynamics is essentially the statement of the principle of the
conservation of energy for thermodynamic systems. It states that energy can be neither created nor
destroyed but only converted from one form to another.

This conservation of energy principle can be rephrased as follows. The net change (increase
or decrease) in the total energy of the system during a process is equal to the difference between

Non-flow work

In a closed system work is transferred across the system boundary due to compression or
expansion of the gas inside the system. During such a process part of the system boundary (e.g. the
inner face of the piston in a cylinder) moves back and forth. Therefore, the expansion and compression
work is also called moving boundary work.

Non-Flow work given by area under the process curve

Consider the gas enclosed in the piston-cylinder device, where the piston has a cross sectional
area, A. Let the gas be at a state when the pressure is P and the volume V. If the piston is allowed to
move a distance ds in a quasi-static manner, the differential work done during this process is

Hence this work is sometimes called the PdV work.

The volume change dV is positive during an expansion process (volume increasing) and
negative during a compression process (volume decreasing). Thus the work done is positive during
at expansion process and the total energy entering and total energy leaving the system during the
process.
Total energy entering the system – Total energy leaving the system =
Change in total energy of system

i.e., Ein – Eout

This is often referred to as the energy balance equation

In the case of a stationary system with no electric, magnetic or surface tension effects the
above energy balance can be written as

(Qin - Qout) + (Win - Wout) + (Emass in – Emass out

For a closed system undergoing a cycle the initial and final states are identical, or the properties
have the same values. Hence there will be no change in the value of the total energy of the system. In

reduces to

(Qin - Qout) + (Win - Wout) = 0

i.e. Qnet in – Wnet out = 0

Or Qnet in = Wnet out

i.e.  Qin   Wout Q  W

This is the first law for a closed system undergoing a cycle, which can be stated as :

When a closed system undergoes a thermodynamic cycle, the net heat supplied to the system
from the surroundings is equal to the net work done by the system on the surroundings.

For a closed system which is stationary and has no electric, magnetic, or surface tension
effects, all the stored energy is in the form of i
undergoing a process the energy balance can be written as

(Qin - Qout) + (Win - Wout 2 –U1

Qnet in – Wnet out = U2 – U1

or Qnet in = (U2 – U1) + Wnet out

This is the first law equation for a closed system undergoing a process, which can be stated
as:

When a closed system executes a thermodynamic process, the net heat supplied to the system
equal s the sum of the net work done by the system and the increase in its internal energy.

It follows from the first law that the energy of an isolated system is constant. This is so because
for an isolated system there cannot be any interaction, i.e.,
 A perpetual motion machine of the first kind (PMM1) is a machine which would supply
mechanical work continuously without some form of energy disappearing simultaneously. Since this
contravenes the first law of thermodynamics, PMM 1 is impossible.

Enthalpy

For a constant pressure non-flow process the energy balance equation is

1Q2 = (U2 – U1) + 1W2

1 Q2   PdV  P(V)12  P(V2  V1 )  P2V2  P1V1 , since P = P1 = P2

1

Substituting, the energy balance equation becomes

1Q2 = (U2 – U1) + P2V2 – P1V1)

= (U2 + P2V2) – (U1 + P1V1)

i.e. 1Q2 = H2 – H1 , where H = U + PV

The composite term (U+PV) has been found to occur frequently in the thermodynamic expressions.
Hence it is defined as enthalpy, H. It has great utility when flow processes are considered, since it is
the sum of internal energy (U) and flow energy (PV).

Since both u and PV are state functions or properties of a system, their sum, enthalpy, H, is
also a property. Since enthalpy is stored energy of a system it is an extensive property and has the
unit kilojoule (kJ) Enthalpy per unit mass, or specific enthalpy, h=H/m kJ/kg.

As seen above, the heat transfer in a constant pressure quasi-equilibrium process is equal to
the change in enthalpy, which includes both the change in internal energy and the change in flow
energy for this particular process.

Specific heats and the characteristic gas constant

The energy balance equation is

1q2  (U2  U1 ) 1 W2

1 W2   Pd  0 since d  0 for a constant volume process

1

 1q 2   U2  U1  for a constant volume process.

or Cv   T2  T1    U2  U1 
Thus, in a constant volume heat transfer process the whole of the heat transfer shows up as the
change in internal energy of the system.

Or (U2 – U1) = Cv(T2 – T1) for unit mass.

In differential form, dU = CvdT

dU
Or Cv 
dT

Consider one kg of a gas which is heated at constant pressure from initial temperature T1 to
final temperature T2. The energy balance equation is (as derived earlier),

1q2 = (h2 – h1), where h is the specific enthalpy

i.e. Cp(T2 – T1) = (h2 – h1)

Thus the change in enthalpy of a system is given by the heat transferred during a constant pressure
process, i.e., (h2 – h1) = Cp(T2 – T1) for unit mass.

In differential form, dh = CpdT

dh
Or Cp 
dT

These formulae for dU and dh apply irrespective of the type of process undergone by a system.

Consider a closed system of an ideal gas. For unit mass of the gas the ideal gas equation is P
= RT. The specific enthalpy of the gas is given by, h = U + P.

Substituting for P, h = U + RT

 1. Constant Volume Process

Constant Volume Process

The relationship for an ideal gas is

P1V1 P2 V2

T1 T2

But V1 = V2 = V for a constant volume process.

P1 P2 P
  or = constant
T1 T2 T

Work done by gas, W  PdV

2
W2   PdV = 0, since dV = 0
1

The energy balance equation is

  dU  W

ie, 1 2   U2  U1   0 = mCv(T2 – T1) and  = U.

 2. Constant pressure process

Differentiating both sides of the equation, we get

dh = du + Rdt
But dh = Cp dT and du = Cv dT. Substituting,
Cp  C v  R

or Cp  Cv  R for an ideal gas

 Cp 
R  Cp  C v  C v   1
 Cv 
CP
But   , the adiabatic index
CV

 R  Cv    1

 1 
or Cv  R  
  1 
Cp

Cv

 1 
Cp  Cv  R  
  1 

  
ie, Cp  R  
  1 

These three relationship for Cv and Cv apply for ideal gases only.

Heat and work transfers in thermodynamic process.

A change in state of a gaseous system occurs due to a process. There are five such non-flow
processes which are of interest.
Constant volume (isochoric)

Constant pressure (isobaric)

Constant temperature (isothermal)

Polythopic.

adiabatic (constant entropy – no heat transfer)

In the derivations, the gas is assumed to be an ideal gas.

Work done by gas, W  PdV

2 2
dV C
1W2   PdV   since P 
1 1
V V

2
dV V
 C  C  l n V 4  C l n 2
2

1
V V1

V  V 
 P1V1 l n  2   P2 V2 l n  2   P1V1  P2 V2  C 
 V1   V1 

The energy balance equation is

1 2   U2  U1   1W2 mCv  T2  T1   1W2

or 1 2  1W2 , since T2 – T1 = 0

V 
 P1V1l n  2 
 V1 

 V2 
= mRT l n    P1V1  P2 V2  mRT for an ideal gas
 V1 

P  V P
 mRT l n  1   P1V1  P2 V2 and so 2  1
 P2  V1 P2

This means that all the heat added during an isothermal process is converted into work. The
equation PV = C represents the isothermal process. This, when plotted on the PV diagram will be a
rectangular hyperbola. Therefore, the process is also called a hyperbolic process.
 3. Polytropic process

An equation of the form PVn = constant, where ‘n’ is a constant can be used to describe many
processes which occur in practice. Such a process is called a polytropic process. The value of x
depends on the type of process. It is possible to find the value of x by curve-felting the experimental
results of a process. The different processes discussed so far are particular cases of this general
process called polytropic process.

The ideal gas relationship is

P1V1 P2 V2

T1 T2

But P1  P2  P for a constant pressure process.

V1 V2 V
  or = constant
T1 T2 T

Work done by gas, W  PdV

2 2

1 W2   PdV  P  dV = P  V2  V1  = P2V2 – P1V1

1 1

= mRT2 – mRT1 (  for an ideal gas PV = mRT)

= mR (T2 – T1)

The energy balance equation is:

1 2   U2  U1   1W2  mCv  T2  T1   mR  T2  T1   m  T2  T1   Cv  R 

 mCp  T2  T1  ( Cp – Cv = R for an ideal gas)

 4. Constant temperature process

For a constant temperature process T1 = T2 = T. Hence the ideal gas relationship

P1V1 P2 V2
 reduces to
T1 T2

C
P1V1  P2 V2  C or PV  C (constant) ie, P 
V

The index ‘n’ is called the polytropic index.

PVn  C

p1/ n V  C1/ n

p1/ n V  C1 For n = .

p1/  V  C1

po v  C1 po V  C1

V = const.

C
For a polytropic process, PVn  P1V1n  P2 V2n  C or P  ........ (1)
Vn

The ideal gas relationship can be written as

P1V1 P2 V2
 . Substituting for P1 and P2 from above,
T1 T2

C V1 C V2

V1n T1 V2n T2

1 1
ie, n 1

T1V1 T2 V2n 1
  T1V1n 1  T2 V2n 1 .......... (2)

P1V1n  P2 V2n can be written as

n
 V1  P2
   Taking logarithms of both sides.
 V2  P1

v  p 
n l n 1   l n  2 
 v2   p1 

l n  p1 / p 2 
or n
l n  v1 / v 2 

n 1
 V1  T2
From (2) above    Taking logarithms of both sides.
 V2  T1

 V1   T2 
 n  1 l n    l n 
 V2   T1 

l n  T2 / T1 
or n  1 
l n  V1 / V2 

n 1
T p  n
Similarly, 2   2 
T1  p1 

n  1 l n  T2 / T1 
Therefore, 
n ln  p 2 /p1 

n

 p 2  v1 
n  T 1/ n 1   T2 
n / n 1

       2   
 T 
 1  2  1   T1 
 p v


Work done by the gas during the process is:

W  PdV

2 2
C
ie, 1W2   PdV   n
dV (from equations)
1 1V

2
2
 V  n 1 
n
 C V dV  C   
C
V21n  V11n  
1  n  1 1 1 n

P2 V2n V21n  P1V1n V11n P2 V2  P1V1

 
1 n 1 n
 P1V1  P2 V2
or, 1W2 
n 1

mR  T1  T2 
Also, 1W2  from ideal gas equation.
n 1

The energy balance equation is:

1 2   U2  U1   1W2

mR
 mCv  T2  T1    T2  T1 
n 1

mR
 mCv  T1  T2    T1  T2 
n 1

 R 
 m  T1  T2    Cv 
 n  1 

 R R   1 
 m  T1  T2      Cv  R  
 n 1  1    1 

 R 1   n 
 mR  T1  T2      mR  T1  T2   
 n 1  1    n  1   1 

  n mR n
  T1  T2   1W2
 1 n 1  1

5. Adiabatic Process

An adiabatic process is one where there is no interaction of energy in the form of heat transfer
between the system and its surroundings during the process. In an adiabatic expansion of a gas in a
piston cylinder arrangement, no heat transfer takes place through the piston and the cylinder walls.
Work is done by the gas during the expansion at the expense of its internal energy.
 The functional relationship between the properties pressure and volume during an adiabatic
process can be developed as follows.

Enthalpy is given by

H = U + PV

Differentiating, dH = dU + PdV + VdP

dU = dH – PdV – VdP

The energy balance equation is (in differential form)

  dU  W  dU  PdV

 dH  PdV  VdP  PdV , substituting dU

ie,   dH  VdP

But for an adiabatic process,   0

Therefore, dU + PdV = 0

Cv dT = – PdV ................ (1)

Also dH – VdP = 0

Cp dT = VdP .............. (2)

Cp VdP
Dividing (2) by (1) 
Cv PdV

dV dp  Cp 
ie,     
v p  Cv 

dp dv
or  0
p v

Integrating, ln P + g ln V = ln C (where C is a constant)

Or PV  C (taking antilogarithms)

C
PV  P1V1  P2 V2  C or P  .............. (1)
V

Work done during the adiabatic process is:

W  PdV
 2 2
C
or 1 W2   PdV   dV from (1) above
1 1 V

2
2
 V 1 
 C V 
dV  C   
C

V21  V11 
1    1 1 1 

P2 V2 V21  P1V1 V11

 , from (1) above
1 

P2 V2  P1V1

1 

P1V1  P2 V2
or 1 W2 
 1

mR  T1  T2 
Also, 1 W2  for an ideal gas.
 1

The energy balance equation is:

1 2   U2  U1   1W2

But 1 3  0 for an adiabatic process. Hence U2  U1  1W2

Process P.V.T. Relationship 1 W2 1 2

Constant Volume P1 P2
 0 mCv  T2  T1 
V=C T1 T2

Constant Pressure V1 V2
 P  V2  V1  mCp  T2  T1 
P=C T1 T2

Constant V  V 
P1V1  P2 V2 P1V1 l n  2  P1V1 l n  2 
Temperature T = C  V1   V1 

P1V1n  P2 V2n
Polytropic P1V1  P2 V2 n
 1W2
PVn = C n 1  1
T1Vn 1  T2 V2n 1

P1V1  P2 V2
Adiabatic P1V1  P2 V2
0
PV   C  1
T1V11  T2 V21
University Questions

1. Explain the following:

First law of thermodynamics

Enthalpy

Internal energy

2. What is the first law of thermodynamics as referred to a closed system undergoing cyclic
change?

3. What is internal energy? Explain

4. Define specific heat. Why gases have two specific heats?

5. What is meant by Cp and Cv? Why is Cp greater than Cv?

6. Define a relationship between the specific heats and the gas constant

7. Obtain an expression for flow work in thermodynamics.

8. Explain adiabatic, isothermal and polytropic process

9. Derive an expression of PdV work done during a reversible polytropic process.

10. Derive an expression for heat transfer in a polytropic process.

11. Derive an expression for work done in an adiabatic process.

12. Define adiabatic process. Show that for a reversible adiabatic process of a given mass of
perfect gas, PV -- = Constant.

13. Derive the expression for work done in an isothermal process.

14. Derive an expression for the work done and heat transfer during a polytropic process.

15. Work done and heat transferred are not thermodynamic properties. Give reasons.

Second law of thermodynamics

The first law of thermodynamics is a statement of the principle of conservation of energy and
all processes satisfy the energy balance. But spontaneous processes in nature occur only in one
direction - heat transfer from higher temperature to lower temperature, water flow downwards, etc.
The first law does not specify this direction of process.

It is also observed that work can be completely converted into heat (joule’s experiments), but
the complete conversion of heat into work in a cycle is not possible. This degradation of energy (work
being a higher form of energy than heat) is not brought out by the first law. Moreover, it is seen that
more of high-temperature heat energy can be converted to work than lower-temperature heat. Thus,
high-temperature energy has a higher quality than the same amount of energy at a lower temperature.

This direction of process and the quality of energy are identified based on the second law of
thermodynamics, whereas the first law only deals with the quantity of energy.

A thermal energy reservoir is a body of large thermal energy capacity, that can supply or
absorb any amount of heat without undergoing any change in its thermodynamic properties. Some
practical examples of such reservoirs are: ocean, atmosphere. Thermal energy reservoirs are often
referred to as heat reservoirs since they supply or absorb energy in the form of heat. A reservoir that
supplies energy is called a source, and one hat absorbs energy is called a sink.

A heat engine is a thermodynamic system which operates in a cycle during which heat is
absorbed and a part of the heat is converted ot work. The thermal efficiency of a heat engine is the
ratio of the net work output to the total heat input during a cycle.

Wnet
Thermal efficiency,  
Q total

A refrigerator or heat pump is a device that, operating in a cycle, transfers heat from a low-
temperature body to a high-temperature body. Refrigerators and heat pumps operate on the same
cycle but differ in their objectives. The objective of a refrigerator is to maintain the refrigerated space
at a lower temperature b removing heat form it, whereas the objective of a heat pump is to maintain
a heated space at a high temperature.

Co-efficient of performance, COP, is the measure of the efficiency of a refrigerator and a heat
pump.

Desired ouput Heat removed

COPRe f  
Required input Wnet in

Desired output Heat added

COPHP  
Required input Wnet in

The Kelvin-Plach statement of the second law pertains to heat engines and can be expressed
as follows:

It is impossible to construct a device that operates in a cycle and produces on effect other than
exchange of heat with a single reservoir and the production of work.
 This means that a heat engine must exchange h eat with a low-temperature sink as well as a
high-temperature source to produce work.

The Clausius statement of the second law is related to refrigerators or heat pumps. It is
expressed as follows:

It is impossible to construct a device that operates in a cycle and produces no effect other than
the transfer of heat from a lower temperature body to a higher-temperature body.

This implies that a refrigerator or heat pump can operate only with a net supply of work from
the surroundings.

A perpetual motion machine of the second hind (PMM 2) is a machine that produces work
utilizing the internal energy of only one heat reservoir. This violates the second law of
thermodynamics (Kelvin - Planck statement). Hence, PMM 2 is impossible. Otherwise, is would be
possible to run a power-plant by extracting heat from the surrounding air.

The Kelvin-Planck and Clausius statements of the second law appears quite unconnected But
it can be proved that they are equivalent in all respects.

Two statements are considered equivalent, when one implies the other and vice versa, or when
the violation of one implies the violation of the other and vice versa. That is, K  C if, K  C and
C  K or K  C and C  K , where K denotes the Kelvin-Planck Statement and C denotes the
Clausuis statement, where k denotes the Kelvin Planck statement and C denotes the Clausius
statement.
 Consider a refrigerator that requires no work to transfer QL units of heat from a low
temperature reservoir to a high temperature reservoir, thus violating the clausius statement (-C).
Suppose that a heat engine also operates between the same two reservoirs in such a way that the same
heat QL is delivered to the low temperature reservoir. The engine violates no law, but the refrigerator
and the engine together constitute a self - contained machine that takes ( QH - QL) from the high
temperature reservoir and converts all this heat into work without producing any change in the low
temperature reservoir, thus constituting a violation of the Kelvin-Planck Statement) (-K). Therefore,
– C  – K.

Now consider an engine that rejects no heat to the low temperature reservoir and therefore,
violates the Kelvin-Planck statement (-K). Suppose that a refrigerator also operates between the same
two reservoirs and uses up all the work performed by the engine. The refrigerator does not violate
any law but the engine and the refrigerator together constitute a self-contained machine that transfers
QL heat from the low temperature reservoir to the high temperature reservoir without producing any
change elsewhere. Therefore, the engine and the refrigerator together violates the clausius statement
(-C)

Therefore –K  C

Therefore, both statements of the second law are equivalent. That is , K≡ C

Entropy

The second law of thermodynamics when applied to a cycle can be expressed as Wout = Qin-Q
or W = QH – QL for a heat engine cycle and heat removed,

QL = QH – W for a refrigeration cycle.

When the second law is applied to a process, it is seen that there exists a function, R whose
change in value from one state to another of a system is independent of the process undergone by the
system. Therefore, it is a point (state) function or a property of the system. This property is called
entropy. Thus, entropy can be defined s the thermodynamic property whose change in value during a
process is given by

2
R
S2  S1   , where S is entropy, R the infinitesimal quantity of heat transfer at
1
T

temperature T during the reversible process. The unit for entropy is kJ/K. It is an extensive property
S
and therefore, specific entropy, s  kJ / kg K .
m

The infinitesimal change in entropy dS due to reversible heat transfer --- at temperature T is

R
dS 
T

In the case of a reversible adiabatic process

δQR= 0

Therefore dS = 0

or S = constant

A reversible adiabatic process is an isentropic process.

QR  TdS  dA  area 

2 2
QR   TdS   dA = Area under the curve 1-2.
1 1

Therefore, the area under the reversible process curve on the T-S diagram represents the heat
transferred during the process.
Third law of thermodynamics

Work involves orderly motion of molecules as in the expansion and compression of a gas.
Heat or thermal energy is due to the random motion of molecules signifying disorder. Orderly energy
can be readily converted into disorderly energy- eg. mechanical energy into internal energy. But there
are limitations on the conversion of disorderly energy into orderly energy as given in the second law
of thermodynamics.

When heat is added to a system the disorderly motion of molecules increases and so also the
entropy of the system. The reverse occurs when heat is removed from the system. So entropy and
disorder are interrelated. It may be observed that the entropy of a system is a measure of the degree
of molecular disorder existing in the system.

The greatest order is achieved when entropy is zero. The entropy value with reference tothe
entropy at absolute zero of temperature is known as absolute entropy. This is dealt with in the third
law of thermodynamics formulated primarily by WH Nernst(1864 - 1941).

The third law states that the entropy of a perfect crystal is zero at absolute zero of temperature
and it represents the maximum degree of order.

Air standard cycles

The devices or systems used to produce a net power output are called engines. Heat engines
produce power by converting energy absorbed in the form of heat. These devices operate on a
thermodynamic cycle. Such cycles are called power cycles. Such cycles can be categorised into
vapour power cycles and gas power cycles. In vapour cycles, the working substance exists in liquid
phase during some part and in vapour phase during the other part of the cycle. In gas power cycles
the working fluid remains in the gaseous phase throughout the entire cycle.

Thermodynamic cycles can also be classified into closed and open cycles. In closed cycle the
working fluid is returned to the initial state at the end of the cycle and is recirculated- eg. steam power
plant. In open cycles, the working fluid is renewed at the end of each cycle instead of being
recirculated - eg. automobile engine.

Heat engines are classified as internal combustion and external combustion engines,
depending on how the heat is supplied to the working fluid. In external combustion engines, like
steam power plants, heat is supplied to the working fluid from an external source such as a furnace,
a nuclear reactor, or the sun. In internal combustion engines like automobile engines this is done y
burning the fuel within the system boundaries.

The thermodynamic cycles of actual heat engines are difficult to analyse because of the
presence of complicating effects such as friction, turbulence, irreversibility, loss of heat and the
chemical reaction of combustion. Hence, to make the mathematical analysis feasible the cycles are
simplified by neglecting these effects. Thus, the idealizing assumptions are:

1) The working substance at all times is air which behaves like an ideal gas with constant specific
heats.

2) All processes are quasi-static.

3) There is no friction or turbulence.

4) There is no loss of heat through engine walls.

5) The processes are reversible, with heat addition and rejection occuring with external heat
reservoirs.

Such a cycle is called an airstandard cycle or ideal cycle and the thermal efficiency of heat
engines operating on such cycles is called the air standard efficiency or ideal efficiency.

An air standard cycle resembles the actual cycle closely but consists of idealised processes.
Hence the air standard efficiency is considerably higher than the thermal efficiency of an actual cycle.
4 4
QL   TdS  TL  dS  TL S4  S3 
3 3

 TL S3  S4  if sign convention is ignored. Substituting for QH and QL in the efficiency

equation,

TH  S2  S1   TL S3  S4 
th 
TH  S2  S1 

TH  S2  S1   TL S2  S1 
 , since S3 = S2, S4 = S1
TH  S2  S1 

TH  TL TL
 or th  1 
TH TH

Reversible isothermal heat transfer is very difficult to achieve in reality because it would
require very large heat exchangers and a very long time. Therefore, it is not practical to build an
engine that would operate on a cycle that approximates the Carnot cycle.

The importance of the Carnot cycle is that being the most efficient power cycle, it is the
standard against which the actual or the ideal cycles can be compared. From the expression of the
thermal efficiency of the carnot cycle, it can be seen that the thermal efficiency increases with an
increase in the temperature at which heat is supplied to the system or with a decrease in the
temperature at which heat is rejected from the system. This is equally applicable to both ideal and
actual cycles.

The Carnot Cycle

The Carnot cycle is composed of four reversible processes :

1-2 : isothermal heat addition at temperature TH

2-3 : adiabatic ( isentropic) expansion

3-4 : isothermal heat rejection at temperature TL

4-1 : adiabatic (isentropic) compression

The Carnot cycle can be executed in a piston - cylinder device with air as the working fluid.
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 .

The thermal efficiency of the Carnot cycle is given by

Net work done

ηth =
Total heat supplied

Heat supplied –Heat rejected

= ( By first law. Qnet = Wnet for a eye)
Heat supplied

QH  QL

QH

2 2
QH   T dS  TH  dS  TH S2  S1 
1 1
The Otto Cycle

The Otto cycle is invented by the German engineer Nikolaus Otto in 176 developing the idea
of a four-stoke engine put forth by the Frenchman Alphonse Beau de Rochas in 1862. The cycle has
the following processes.

1-2 : Adiabatic (isentropic) compression

2-3 : Constant volume heat addition

3-4 : Adiabatic (isentropic) expansion

4-1 : Constant volume heat rejection

The air standard thermal efficiency of the Otto cycle is given by

Heat supplied -Heat rejected

otto 
Heat supplied

mCv  T3  T2   mCv  T4  T1 

mCv  T3  T2 

where m is the mass of air in the piston-cylender device, Cv the specific heat at constant volume, and
T1,T2,.......... are the absolute temperatures at respective states.

Thus, otto 
 T3  T2    T4  T1  T  T 
1 4 1
 T3  T2   T3  T2 

T1  T4 / T1  1
1 .......... (1)
T2  T3 / T2  1

For adiabatic process 1-2

T1V11  T2 V21
 1
T V 
or 2   1  ............. (2)
T1  V2 

Similarly, for adiabatic process 3 – 4

T3V31  T4 V41

1
T V 
or 3   4 
T4  V3 

But V2 = V3 and V1 = V4, 2-3 and 4-1 being constant volume processes. Therefore,

T2 T3 T4 T3
 or 
T1 T4 T1 T2

 T4  T 
Hence   1   3  1 . Therefore, equation (1) above becomes
 T1   T2 

T1 1 1
otto  1  1 1
T2 T2 / T1  V1 / V2 1

1
otto  1  1


where  is the compression ratio and   Cp / Cv

1
T4 T4 T3 T2  
 .  C  .  C .  1 (from equations 2, 3 & 4)
T1 T3 T2 T1   

  C ............ (5)

Equation (1) can, therefore, be written as

1 1  1
Diesel  1  . 1 . C (from equations 2, 3 & 5)
  C  1

Or Diesel  1 
1 
  1 
 C
 
 1     C  1 
 

 Cp 
where  = compression ratio, and  C = cut off ratio, and  = adiabatic index  .
 Cv 

1.1 Diesel cycle

Diesel cycle is the cycle on which the diesel engine works. Air standard diesel cycle consists
of four reversible processes. Heat is supplied at constant pressure and rejected at constant volume.
Expansion and compression of air takes place adiabatically. Fig. 1.38 shows these processes on p-V
diagram.

Consider a cylinder containing ‘m’ kg of air. Let p1, V1 and T1 be the pressure, volume and
temperature of air inside the cylinder at state 1. This air is compressed adiabatically to state 2, doing
work on the air. Curve 1-2 in the p-V diagram represents this process. Now heat is supplied to the air
at constant pressure from an external hot body till state 3 is reached. This process is represented by a
horizontal line 2-3 in the p-V diagram.

At state 3, the hot body is removed and the air is allowed to expand adiabatically to state 4, doing
external work. This process is represented by curve 3-4 in the p-V diagram. Heat is rejected at
constant volume to an external cold body till state 1 is reached. This process is represented by a
vertical line 4-1 in the p-V diagram. Thus the air finally returns to its original state after completing
a cycle.

Heat supplied during constant volume process 2-3 = mCp (T3 – T2)

Heat rejected during constant volume process 4-1 = mCv (T4 – T1)

Air Standard efficiency,

Heat rejected
η  1
Heat supplied

mC v (T4  T1 )
 1
mC p (T3  T2 )

C v (T4  T1 )
 1
C p (T3  T2 )

1 (T  T1 )
 1  4 (i)
γ (T3  T2 )
 V3 V V
Let be the cutoff ratio ρ, 4 be the expansion ratio r1 and 1 be the compression ratio r.
V2 V3 V2
The relation between these three ratios is obtained as follows.

V4 V4 V2
 
V3 V2 V3

V1 V2
 
V2 V3

1 r
r1  r  
ρ ρ

r
r1 
ρ

For the adiabatic process 1-2,

γ 1
T2  V1 
 
T1  V2 

γ 1
V 
T2  T1  1 
 V2 

T2 = T1r - 1 (ii)

For the constant pressure process 2-3,

T3 V3
 ρ
T2 V2

T3 = T2  

T3 = T1 r - 1   (iii)

For the adiabatic process 3-4,

γ 1
T3  V4  γ 1
   r1
T4  V3 

γ 1
r r γ 1
  
ρ  ρ γ 1

ρ γ 1
T4  T3 
r γ 1

Substituting for T3 from equation (iii)

 ρ γ 1
T4  T1 r γ 1ρ 
r γ 1

T4 = T1 (iv)

Substituting the expressions for T2, T3 and T4 in equation (i),

1 T1ρ γ  T1
η  1

γ T1 r γ 1ρ  T1 r γ 1 
1 1  ρ γ  1
η  1   
r γ 1 γ  ρ  1 

The above expression shows that the air standard efficiency of Diesel cycle is a function of
compression ratio, cutoff ratio and the ratio of specific heats.

Thus, under ideal air standard conditions the efficiency of the Diesel cycle differs from that of
the Otto cycle by the quantity in the brackets. Since the cut-off ratio,  C is always greater than 1.
Therefore, the efficiency of the Diesel cycle is always less than that of the Otto cycle for the same
compression ratio i.e., otto  Diesel

However, diesel engines can employ much higher compression ratios than petrol engines since
the fuel is introduced into the cylinder at the end of the compression stroke thus avoiding chances of
engine knock. They are, therefore, more efficient than petrol engines.

OTTO CYCLE DIESEL CYCLE

1. Consists of two reversible adiabatic Consists of two reversible adiabatic

(isentropic) processes and two reversible (isentropic) processes, one constant
constant volume processes with heat pressure heat addition process and one
addition and rejection during the constant constant volume heat rejection process.
volume processes.

2. Air standard efficiency is given by Air Standard efficiency is given by

1
 1
 1
  1  1

 
1  c  1   
where  =
     c  1 
 
where r = compression ratio,  =
compression ratio.  C = cut-off ratio.
adiabatic exponent.
 = adiabatic exponent.
 3. For the same compression ratio, the Diesel engine work on cycles
efficiency of the Otto cycle is higher than approximating the Diesel cycle.
that of the Diesel cycle, i.e., otto  Diesel Much higher compression ratios can be
4. Petrol engines work on cycles adopted in diesel engines due to absence
approximating the Otto cycle. of engine knock. Hence, practical diesel
engines work at higher efficiencies than
5. Compression ratios of practical petrol
petrol engines.
engines are limited by engine knock thus
limiting the efficiencies achievable.

net work done

Diesel 
total heat supplied

heat supplied – heat rejected QH  QL mCp  T3  T2   mCv  T4  T1 

= = 
heat supplied QH mCp  T3  T2 

mCv  T4  T1  Cv  T4  T1 
1  1e 
mCp  T3  T2  Cp  T3  T2 

1  T4  T1 
Diesel  1  ........... (1)
  T3  T2 

Adiabatic process 1-2 T1V11  T2 V21

1
V  1 V1
T1   2  T2  r 1
T2  (2) compression ratio, r 
 V1   V2

V2 V3
Constant pressure process 2-3 
T2 T3

V3 V
T3  T2  rC T2 - (3) cut – off ratio rc  3
T2 V2

Adiabatic process 3-4 T4 V41  T3V31

1 1
V  V 
T4   3  T3   3  re T2 [from (3)
 V4   V1 

1
V V   er 1 .  e
 3 . 2   c T2  T2
 V2 V1   r 1

e
 T2 (4)
 1
Substituting in (1) for T1, T3 and T4 from (2), (3) & (4) respectively

  c 1    1
 1 T2  1 T2  T2  c 
1   1    1 
Diesel 1 1
  
 C T2   T2  T2   C  1

1   C  1 1     1 
1  1  1  C 
    C  1
1
     C  1 

Worked-out Problems

Molar mass, gas constant and ideal gas specific heats of some common gases

SUBSTANCE SYMBOL M (kg/kmol) R (kJ/kg K) SPECIFIC HEAT (kJ/kg K)

CP CV

Air 28.97 (29) 0.2870 1.005 0.718

Carbon dioxide CO2 44.01 (44) 0.1889 0.846 0.657

Helium He 4.003 (4) 2.0769 5.1926 3.1156

Hydrogen H2 2.016 (2) 4.1240 14.307 10.183

Methane CH4 16.043 (16) 0.5182 2.2537 1.7354

Nitrogen N2 28.013 (28) 0.2968 1.039 0.743

Oxygen O2 31.999 (32) 0.2598 0.918 0.658

Water (Steam) H2 O 18.015 (18) 0.4615 1.8723 1.4108

(Source: Cengel and Boles)

1. Ideal gas equation of state

1.1 Determine the mass of the air in a room whose dimensions are 4 m X 5 m X 6 m at 100 kPa and
25oC.

Given: Volume of room, V = 4x5x6 =120 m3

Pressure, P = 100 kPa

Temperature, T = 25 + 273 = 298 K

To find: Mass of air in the room, m

Assumption: Air is an ideal gas and Mair = 29 kg/kmol

Pormula: Ideal gas equation of state: P V = m R T Or m = P V / R T,

and R = RUniversal/M = 8.314/29 = 0.287 kJ/kg K

Calculation and result:

m = P V / R T = 100x 120 / 0.287x298 = 140.3 kg

1.2 A 100 litre container is filled with 1 kg of air at a temperature of 27oC. What is the pressure in the
container?

Given: Volume of container, V = 100 litre = 100 x 10-3 m3

Mass of air, m = 1 kg

Temperature, T = 27 + 273 = 300 K

To find: pressure, P of air.

Assumptions : Air is an ideal gas and R for air = 0.287 kJ/kg K

Formula: Ideal gas equation of state is P V = m R T. Or P = m R T / V

Calculation and result:

P = m R T / V = 1 x 0.287 x 300/ 100 x 10-3 = 861 kPa

1.3 A spherical balloon with a diameter of 6 m is filled with helium at 20oC and 200 kPa. Determine
the mol number and mass of helium in the balloon. The molecular weight of helium may be taken as
4kg/kmol.

Given: diameter of spherical balloon, d = 6 m

Temperature of He, T = 20 + 273 = 293 K

Pressure of He, P = 200 kPa

Molar mass of He, M = 4 kg/kmol

To find: mass of He in the balloon and its amount in number of moles

Assumptions: He is an ideal gas

Formula: Ideal gas equation of state is P V = m R T Therefore m = P V / R T

 number of moles, n = m/M and R = RUniversal / M

Calculations and result:

V = 4/3 πr3 = 4/3 π 33 = 113.14 m3

R = 8.314/4 = 2.079 kJ/kg K

M = P V / R T = 200x113.14/2.079x293 = 37.15 kg

N = m/M 37.15/4 = 9.28 kmol

1.4 The pressure in an automobile tyre depends on the temperature of the air in the tyre. When the air
temperature is 25oC, the pressure gauge reads 210 kPa. If the volume of the tyre is 0.025 m3, determine
the pressure rise in the tyre when the air temperature in the tyre rises to 50oC. Also determine the
amount of air that must be bled off to restore the pressure to the original value at this temperature.
Assume the atmospheric pressure is 100 kPa.

Given: V = 0.025 m3 constant

P1 = 210 kPa gauge = 210 + 100 = 310 kPa absolute

T1 = 25 + 273 = 298 K

T2 = 50 + 273 = 323 K

Patm = 100 kPa

To find : Pressure rise = P2 – P1 and

Amount of air to be bled = m2 – m at 50oC

Assumptions: Air is an ideal gas and Rair = 0.287 kJ/kg K

Formula: Ideal gas equation of state is P V = m R T. Or m = P V / R T

Also, P1 V1/ T1 = P2 V2/ T2 But V1 = V2. Therefore P1/T1 = P2/T2 Or P2 = P1 T2 / T1

Calculations and results:

P2 = P1 T2 / T1 = 310 x 323 / 298 = 336 kPa

Pressure rise in tyre = P2 – P1 = 336 – 310 = 26 kPa

m2 = P2 V2 / R T2 = 336 x 0.025 / 0.287 x 323 = 0.091 kg

 m at 310 kPa and 323 K = P V / R T = 310 x 0.025 / 0.287 x 323 = 0.084 kg

Amount of air to be bled = m2 – m = 0.091 – 0.084 = 0.007 kg = 7 grams

1.5 A 1 m3 tank containing air at 25oC and 500 kPa is connected through a valve to another tank
containing 5 kg of air at 35oC and 200 kPa. Now the valve is opened and the entire system is allowed
to reach thermal equilibrium with the surroundings which are at 20oC. Determine the volume of the
second tank and the final equilibrium pressure of air.

Given: TANK 1 TANK 2

Volume V1 = 1 m3 V2 = ?

Temperature T1 = 25 + 273 = 298 K T2 = 35 + 273 = 308 K

Pressure P1 = 500 kPa P2 = 200 kPa

Surrounding temperature T3 = 20 + 273 = 293 K

To find: Volume of tank 2 = V2 and final pressure = P3

Assumptions: Air is an ideal gas and its R = 0.287 kJ/kg K

Formula: Ideal gas equation of state is P V = m R T. ie., m + P V / R T and V = m R T / P

Calculation and results:

STEP 1: Find mass of air in tank 1

m1 = P1 V1 / R T1 = 500x1/0.287x298 = 5.85 kg

STE 2: Find volume of tank 2

V2 = m2 R T2 / P2 = 5x0.287x308/200 = 2.21 m3

STEP 3: Find the final pressure, P3 of the two tanks combined

P3 = m3 R T3 / V3 = (m1 + m2) R T3 / (V1 + V2) = (5.85+5) x0.287 x 293 / (1 + 2.21) = 284.23

kPa

2. First law of thermodynamics and specific heats of gases

2.1 During one cycle the working fluid in an engine engages in two work interactions: 15 kJ to the
fluid and 40 kJ from the fluid, and three heat interactions, two of which are known: 75 kJ to the fluid
and 40 kJ from the fluid. Evaluate the magnitude and direction of the third heat transfer.
Given: W1 = - 15 kJ Q1 = 75 kJ

W2 = 44 kJ Q2 = - 40 kJ

To find: Q3 = ?

Formula: According to the first law for a cycle, the energy balance equation is Qnet = Wnet

Calculation and result: Qnet = Wnet

Q1 + Q2 + Q3 = W1 + W2

75 + (-40) + Q3 = -15 + 44

Q3 = - 6 kJ (from the fluid)

2.2 Complete each line of the table below by filling up the shaded boxes, based on the first law for a
closed system:

Energy balance equation for a process is:

Qin = (E2 – E1) + Wout

Specific total energy, e = E/m

Q (kJ) W (kJ) E1 (kJ) E2 (kJ) m (kg) e2 –e1 (kJ/kg)

280 440 1020 860 3 - 53.33

-350 130 550 70 5 - 96

- 40 260 300 0 2 -150

300 550 750 500 1 - 250

- 400 -200 500 300 2 -100

2.3 An ideal gas requires 1150 kJ of heat to raise its temperature from 20oC to 100oC when heated
at constant pressure. When heat is supplied to the same gas at constant volume heat required is 825
kJ for the same temperature range. Determine CP, CV, characteristic gas constant and molecular
mass of the gas.

Given: T1 = 20 + 273 + 293 K T2 = 100 + 273 = 373 K

Q1-2 at constant pressure = 1150 kJ Q1-2 at constant volume = 825 kJ

To find: CP, CV, R, and M

Formula: Q1-2 for constant volume process = CV (T2 – T1) kJ/kg

Q1-2 for constant pressure process = CP (T2 – T1) kJ/kg

CP – CV = R R = RUniversal /M Or M = RUniversal/R

Calculation and results:

CP (T2 – T1) = Q1-2 at P const.

CP (373 – 293) = 1150 kJ/kg

CP = 1150 / 80 = 14.375 kJ/kg K

CV (T2 – T1) = Q1-2 at V const.

CV (373 – 293) = 825 kJ/kg

CV = 825 / 80 = 10.3125 kJ/kg K

R = CP – CV = 14.375 – 10.3125 = 4.063 kJ / kg K

M = RUniversal / R = 8.314 / 4.063 = 2.046 kg / kmol

2.4 Specific volume of a gas is 11.7 m3/kg at STP and the ratio of specific heats γ = 1.4. Determine
the values of the characteristic gas constant and the two specific heats.

Given: v = 11.7 m3/kg

P = 101.325 kPa (standard pressure)

T = 15 + 273 = 288 K (standard temperature)

γ = 1.4

To find: R, CP, CV

Assumption: the gas is an ideal gas

Formula: Ideal gas equation of state is Pv = RT, CP – CV = R, CV = R ( 1/γ – 1 )

Calculation and results:

Pv=RT
 R = P v /T = 101.325 x 11.7 / 288 = 4.116 kJ/kg

CV = R(1/γ-1) = 4.116/(1.4-1) = 10.29 kJ/kg K

CP = γ CV = 1.4 x 10.29 = 14.41 kJ/kg K

2.5 A certain mass of gas expanding at constant pressure does 10 kJ of work. Calculate the quantity
of heat which must be transferred to the gas and how much of this heat is used to raise the internal
energy of the gas? The ratio of the specific heats is 1.6.

Given: W1-2 = 10 kJ at constant pressure

γ = 1.6

To find: Q1-2 and (U2 – U1)

Formula: Energy balance equation for a process is Q1-2 = (U2 – U1) + W1-2

Q1-2 = m CP (T2 – T1) for a constant pressure process

(U2 – U1) = m CV (T2 – T1) for all processes

Calculation and results:

The energy balance equation is Q1-2 = (U2 – U1) + W1-2

ie., CP m (T2 – T1) = CV m (T2 – T1) + W1-2

m(T2 – T1) (CP – CV) = W1-2 = 10

m(T2 – T1) (γ CV –CV) = 10, since CP / CV = γ

CV m (T2 – T1) (γ – 1) = 10

(U2 – U1) = 10 / (1.6 – 1) = 16.67 kJ

Substituting in the energy balance equation,

Q1-2 = 16.67 + 10 = 26.67 kJ

2.6 A well-sealed room contains 60 kg of air at 200 kPa and 25o C. Now solar energy enters the
room at an average rate of 0.8 kJ/s while a 120W fan is turned on to circulate the air in the room. If
heat transfer through the walls is negligible, what will be the air temperature in the room in 30
minutes?

Given: m = 60 kg

P1 = 200 kPa

T1 = 25o C = 298 K

Solar power = 0.8 kJ/s (kW)

 Fan power = 120 W = 0.12 kW

Time interval = 30 min = 1800 s

Q1-2 = 0

To find: T2 (after 30 min)

Formula: Energy balance equation is Q1-2 = (U2 – U1) + W1-2

(U2 – U1) = m CV (T2 – T1)

Assumption: CV of air = 0.718 kJ/kg K

Calculation: Substituting the terms in the energy balance equation,

0 = (U2 – U1) + [- (0.8 + 0.12) 1800]

Therefore U2 – U1 = 0.92 x 1800 = 1656 kJ = m CV (T2 – T1) = 60 x 0.718 (T2 – T1)

Or T2 – T1 = 1656 / 60 x 1800 = 38.44

T2 = T1 + 38.44 = 298 + 38.44 = 336.44 K = 63.44o C

3. Heat and Work – Thermodynamic processes

3.1 Calculate the total work done for process 1-2-3 shown in figure below when the system consists
of 2 kg of nitrogen. (300 kJ) 1
500kPa
400kPa 3

100kPa
2

0.5 m3/kg 1.0 m3/kg

Formula: Work done = Area under the process curve on the PV diagram

Calculation: w1-2 = Area under line 1-2 = 100 (1 – 0.5) + ½ ( 1 – 0.5) x ( 500 – 100)

= 50 + 100 = 150 kJ/kg

W1-2 = m x w1-2 = 2 x 150 = 300 kJ

W2-3 = 0, since curve 2-3 is a vertical line ( constant volume process)

Therefore W1-3 = 300 kJ

3.2 A rigid tank contains 10 kg of air at 350 kPa and 27oC. The air is now heated until its pressure
doubles. Determine a) the volume of the tank and b) the amount of heat transfer.

Given: m = 10 kg

P1 = 350 kPa P2 = 2 x P1 = 700 kPa

T1 = 27 + 273 = 300 K

To find: V = V1 = V2 = ? (since tank is rigid, its volume remains constant),

Q1-2 = ?

Assumption: Air is an ideal gas and for air, CV = 0.718 kJ/kg K and R = o.287 kJ/kg K

Formula: The ideal gas equation of state is P V = m R T and for a constant volume change of state,

P1 / T1 = P2 / T2

Heat transfer, Q1-2 = m CV (T2 – T1) for a constant volume process

Calculation and results:

P1 V1 = m R T1 Therefore, V = V1 = m R T1 / P1 = 10 x 0.287 x 300 / 350 = 2.46 m3

P1 / T1 = P2 / T2 Therefore, T2 = P2 T1 / P1 = 700 x 300 / 350 = 600 K

Q1-2 = m CV (T2 – T1) = 10 x 0.718 (600 – 300) = 2154 kJ

3.3 2 kg of air occupies 1.5 m3 at 700 kPa. Its temperature becomes 600 K when it undergoes a
reversible non-flow constant pressure process. Evaluate (i) work done during the process, (ii) final
volume and (iii)initial temperature. Also show the process on the P-V coordinates. Take R = 0.287
kJ/kg K.

Given: m = 2 kg

V1 = 1.5 m3

P1 = P2 = 700 kPa ( constant pressure process)

T2 = 600 K

To find: W1-2, V2, and T1

Formula: For an ideal gas, PV = mRT and P1V1/T1 = P2V2/T2 ie., V1/T1 = V2/T2, since P is
constant

W1-2 = P(V2 – V1) for a constant pressure process

Calculation: T1 = P1V1/mR = 700 x 1.5 / 2 x 0.287 = 1829.27 K

 V2 = V1T2/T1 1.5 x 600 / 1829.27 = 0.49 m3

W1-2 = P (V2 – V1) = 700 (0.49 – 1.5) = -707 kJ ( work is done on the system)

700 kPa

2 PV Diagram 1
3.4 A piston-cylinder device containing carbon dioxide gas undergoes an isobaric process from 100
kPa and 25o C to 100o C. Determine the work and the het transfer associated with this process in
kJ/kg. Take CP as 0.846 kJ/kg K. V
0.49 m3 1.5 m3
Given: m = 1 kg

P = P1 = P2 = 100 kPa

T1 = 25o C = 298 K

T2 = 100o c = 373 K

CP = 0.846 kJ/kg K

To find: W1-2 and Q1-2

Assumption: CO2 is an ideal gas and its molar mass, M = 44 kg/kmol

Formula: R = R’/M, W1-2 = mR (T2 – T1) and Q1-2 = mCP (T2 – T1) for a constant pressure process

Calculation: R = R’/M = 8.314/44 = 0.189 kJ/kg K

W1-2 = mR(T2 – T1) = 1 x 0.189 (373 – 298) = 14.2 kJ/kg

Q1-2 = mCP (T2 – T1) = 1 x 0.846 ( 373 – 298) = 63.45 kJ/kg

3.5 In an isothermal process 8 m3 of air at a pressure of 2 bar is compressed to a pressure of 10 bar.

Calculate the amount of work done on air.

Given: V1 = 8 m3

P1 = 2 bar = 200 kPa

P2 = 10 bar = 1000 kPa

To find : W1-2

Assumption: air is an ideal gas

Formula: In an isothermal process with an ideal gas, W1-2 = P1V1ln(P1/P2)

Calculation: W1-2 = P1V1ln(P1/P2)

= 200x8xln(200/1000)

= -2574.4 kJ (work is done on the system)

3.6 A piston-cylinder device contains 5 kg of air at 400 kPa and 30 o C. During a quasi-equilibrium
isothermal expansion process 15 kJ of boundary work is done by the system and 3 kJ of paddle wheel
work is done on the system. What is the heat transfer during the process? Also find the final pressure
and volume.

Given: m = 5 kg

P1 = 400 kPa

T1 = 30oC = 303 K = T2

W1-2 Boundary = 15 kJ

W1-2 Paddle = -3 kJ

To find: Q1-2, P2, V2

Assumptions: Air is an ideal gas and Rair = 0.287 kJ/kg K

Formula: Ideal gas equation is PV = mRT

W1-2Boundary = P1V1ln(P1/P2)

Calculation: Energy balance equation is Q1-2 = (U2 – U1) + W1-2

But (U2 – U1) = 0 for an isothermal process.

Therefore, Q1-2 = W1-2 = W1-2 Boundary + W1-2 Paddle = 15 – 3

= 12 kJ

P1V1 = mRT1 or V1 = mRT1/P1 = 5x0.287x303/400 = 1.087 m3

W1-2Boundary = P1V1ln(P1/P2)

15 = 400x1.087x ln(P1/P2)

ln(P1/P2) = 15/(400x1.087) = 0.0345

P1/P2 = 1.035
P2 = 400/1.035 = 386.5 kPa

V2 = mRT2/P2 = 5x0.287x303/386.5 = 1.125 m3

3.7 A frictionless piston-cylinder device contains 2 kg of nitrogen at 100 kPa and 300 K. Nitrogen is
then compressed slowly adiabatically until it reaches a final temperature of 360 K. Calculate the work
input during this process. Take, for nitrogen, adiabatic index as 1.4 and the molar mass 28 kg/kmol.

Given: m = 2 kg

P1 = 100 kPa

T1 = 300 K

T2 = 360 K

γNitrogen =1.4

MNitrogen = 28 kg/kmol

To find: W1-2

Assumption; Nitrogen is an ideal gas

Formula: W1-2 = mR(T1 – T2)/(γ – 1) and R = R’/M

Calculation: RNitrogen = 8.314/28 = 0.297 kJ/kg K

W1-2 = mR(T1 – T2)/(γ – 1)

= 2x0.297(300 – 360)/(1.4 – 1)

= 89.1 kJ

3.8 Air at 50 kPa and 15o C is expanded adiabatically to 10 kPa. Calculate the change in internal
energy and work done. If the same expansion is isothermal, find the corresponding values.

Given: P1 = 50 kPa P2 = 10 kPa

T1 = 15oC = 288 K

To find: for adiabatic expansion: (U2 – U1) and W1-2

For isothermal expansion: (U2 – U1) and W1-2

Assumption: air is an ideal gas, γair = 1.4 and Rair = 0.287 kJ/kg-K

Formula: For an ideal gas Pv = RT

For an adiabatic process W1-2 = (P1V1 – P2V2)/(γ – 1) and (U2 – U1) = -W1-2 since Q1-2 = 0

For an isothermal process W1-2 = P1V1ln(P1/P2) and (U2 – U1) = 0

Calculation:

Adiabatic process: P1v1 = RT1

v1 = RT1/P1 = 0.287x288/50 = 1.653 m3/kg

P1v1γ = P2 v2γ

v2/v1 = (P1/P2)1/γ = (50/10)1/1.4 = 3.155

v2 = 3.155x1.653 = 5.215 m3

W1-2 = (P1V1 – P2V2)/(γ – 1) = (50x1.653 – 10x 5.215)/(1.4 – 1) = 76.25 kJ/kg

(U2 – U1) = -W1-2 = -76.25 kJ/kg

Isothermal process: W1-2 = P1V1ln(P1/P2)

= 50x1.653 ln(50/10) = 133.07 kJ/kg

(U2 – U1) = 0

3.9 A gas expands in a cylinder according to the relation PV1.3 = constant from an initial state of 0.3
m3 and 1000 kPa to a final state of 101 kPa. Calculate the work done on the piston by the gas pressure.

Given: P1 = 1000 kPa P2 = 101 kPa

V1 = 0.3 m3 n = 1.3

To find: W1-2

Formula: W1-2 = (P1V1 – P2V2)/(n – 1)

Calculation: P1v1n = P2 v2n

v2/v1 = (P1/P2)1/n = (1000/101)1/1.3 = 5.83

v2 = 5.83x0.3 = 1.75 m3

W1-2 = (P1V1 – P2V2)/(n – 1)

= (1000x0.3 – 101x1.75)/(1.3 – 1) = 411.17 kJ

3.10 A mass of gas is compressed in a quasi-static polytropic process (PVn = C) from 80 kPa, 0.1 m3
to 0.4 MPa, 0.3 m3. Find the work done and the heat transferred during the process. Assume γ = 1.4.

Given: P1 = 80 kPa P2 = 0.4 MPa = 400 kPa

V1 = 0.1 m3 V2 = 0.03 m3 γ = 1.4

To find: W1-2 and Q1-2

Formula: n = (lnP2/P1)/(lnV1/V2)
 W1-2 = (P1V1 – P2V2)/(n – 1)

Q1-2 = [(γ – n)/(γ – 1)]W1-2

Calculation: n = (lnP2/P1)/(lnV1/V2) = (ln400/80)/(ln0.1/0.03) = 1.336

W1-2 = (P1V1 – P2V2)/(n – 1)

= (80x0.1 – 400x0.03)/(1.336– 1) = -11.9 kJ

Q1-2 = [(γ – n)/(γ – 1)]W1-2

= [(1.4 – 1.336)/(1.4 – 1)] (-11.9) = - 1.904 kJ

3.11 A piston-cylinder device contains helium gas initially at 150 kPa, 20o C and 0.5 m3. The helium
is now compressed in a polytropic process to 400 kPa and 140o C. Determine the heat loss or gain
during the process. For helium M = kg/kmol, CP = 5.1926 kJ/kg K, and CV = 3.1156 kJ/kg K.

Given: P1 = 150 kPa P2 = 400 kPa

V1 = 0.5 m3

T1 = 20oC = 293 K T2 = 140oC = 413 K

γ = CP/CV = 5.1926/3.1156 = 1.667 for helium

To find: Q1-2

Assumption: helim is an ideal gas

and its M = 4 kg/kmol

For helium, R = R’/M = 8.314/4 = 2.0785 kJ/kg-K

Formula: Ideal gas equation is PV = mRT

Polytropic index, n = (lnP2/P1)/(lnV1/V2)

Q1-2 = [(γ – n)/(γ – 1)] [mR(T1 – T2)/(n – 1)]

Calculation: mass, m = P1 V1/R T1 = 150x0.5/(2.0785x293) = 0.123 kg

V2 = mRT2/P2 = 0.123x2.0785x413/400 = 0.264 m3

n = (lnP2/P1)/(lnV1/V2) = (ln400/150)/(ln0.5/0.264) = 1.535

Q1-2 = [(γ – n)/(γ – 1)] [mR(T1 – T2)/(n – 1)]

= [(1.667 – 1.535)/(1.667 – 1)] [0.123x2.0785(293 – 413)/(1.535 – 1)]

= -11.35 kJ (heat loss)

3.12 A piston-cylinder device contains 0.15 kg of air initially at 2 MPa and 350o C. The air is first
expanded isothermally to 500 kPa, then compressed polytropically with a polytropic exponent of
1.2 to the initial pressure, and finally compressed at the constant pressure to the initial state.
Determine the boundary work for each process and the net work of the cycle.

P 1 3

Given: m = 0.15 kg

P1 = 2 MPa = 2000 kPa = P3 P2 = 500 kPa

T1 = 350oC = 623 K =T2

Process 2-3: polytropic compression, n = 1.2

To find: W1-2, W2-3, W3-1, and Wnet for the cycle

Assumption: air is an ideal gas and the ideal gas equation is PV = mRT and Rair = 0.287 kJ/kg-K

Work done, W1-2 = P1V1ln(P1/P2) for isothermal process 1-2

W2-3 = (P2V2 – P3V3)/(n – 1) for isentropic process 2-3

W3-1 = P3 (V1 – V3) for isobaric process 3-1

Calculation: P1V1 = mRT1 Or V1 = mRT1/P1 = 0.15x0.287x623/2000 = 0.0134 m3

W1-2 = P1V1ln(P1/P2) = 2000x0.0134xln(2000/500) = 37.15 kJ

For isothermal process 1-2, P1V1 = P2V2 Or V2 = P1V1/P2 = 2000x0.0134/500 = 0.0536 m3

P2V2n = P3V3n Or (V3/V2)n = P2/P3 Or V3 = V2(P2/P3)1/n = 0.0536 (500/2000)1/1.2 = 0.0169 m3

W2-3 = (P2V2 – P3V3)/(n – 1) = (500x0.0536 – 2000x0.0169)/(1.2 – 1) = -142.2 kJ

W3-1 = P3 (V1 – V3) = 2000 (0.0134 – 0.0169) = -7 kJ

Wnet = W1-2 + W2-3 + w3-1 = 37.15 – 142.2 – 7 = -112.05 kJ

3.13 One kg of hydrogen gas undergoes a polytropic process from an initial condition of 100 kPa and
30o C to the final condition of 500 kPa and 3.5 m3. Calculate (i) initial volume, (ii) polytropic index
(iii) work done. Take CP = 14.3 kJ/kg-K, Cv = 10.2 kJ/kg-K and R = 4.1 kJ/kg-K.

Given: m = 1 kg

P1 = 100 kPa P2 = 500 kPa

T1 = 30oC = 303 K V2 = 3.5 m3

PVn = Constant

To find out: V1, n, W1-2

Assumption: hydrogen is an ideal gas

Formula: Ideal gas equation is PV = mRT

Polytropic index, n = (lnP2/P1)/(lnV1/V2)

Work done, W1-2 = (P1V1 – P2V2)/(n – 1)

Calculation: P1V1 = mRT1

V1 = mRT1/P1 = 1x4.1x303/100 = 12.423 m3

n = (lnP2/P1)/(lnV1/V2) = (ln500/100)/(ln12.423/3.5) = 1.27

W1-2 = (P1V1 – P2V2)/(n – 1)

= (100x12.423 –500x3.5)/(1.27– 1) = -1880.37 kJ (work is done on the gas)

3.14 2 kg of an ideal gas occupies a volume of 0.3 m3 at 10 bar pressure and 500 K temperature.
When this gas expands polytropically (PV1.2 = C) the internal energy decreases by 300 kJ. Presuming
the adiabatic exponent γ = 1.4, determine (i) specific gas constant, (ii) final temperature and pressure
of the gas, (iii) heat and work interactions across the system boundary.

Given: m = 2 kg

V1 = 0.3 m3 P1 = 10 bar = 1000 kPa T1 = 500 K

PV1.2= Constant

(U2 – U1) = -300 kJ

γ = 1.4

To find: R, P2, T2, Q1-2, W1-2

Formula: Ideal gas equation is PV = mRT and CV = R/(γ – 1)

Work done, W1-2 = mR(T1 – T2)/(n – 1)

Change in internal energy, (U2 – U1) = m CV (T2 – T1)

Energy balance equation is Q1-2 = (U2 – U1) + W1-2

T2/T1 = (P2/P1)(n-1)/n

Calculatin: P1V1 = mRT1

R = P1V1/(mT1) = 1000x0.3/(2x500) = 0.3 kJ/kg-K

CV = R/(γ – 1) = 0.3/(1.4 – 1) = 0.75 kJ/kg-K

(U2 – U1) = m CV (T2 – T1) = 2x0.75 (T2 – 500) = -300 (given)

T2 – 500 = -200 Or T2 = 300 K

T2/T1 = (P2/P1)(n-1)/n

300/500 = (P2/1000)(1.2-1)/1.2

P2/1000 = (300/500)1.2/0.2 = 0.0469

P2 = 1000x0.0469 = 46.9 kPa

W1-2 = mR(T1 – T2)/(n – 1) = 2x0.3 (500 –300)/(1.2 – 1) = 600 kJ

Q1-2 = (U2 – U1) + W1-2 = -300 + 600 = 300 kJ

3.15 A spherical balloon of 0.5 m diameter contains air at a pressure of 500 kPa. The diameter
increases to 0.55 m in a reversible process during which pressure is proportional to diameter.
Determine the work done by the air in the balloon during this process.

Given: D1 = 0.5 m D2 = 0.55 m

P1 = 500 kPa P α (proportional to) D

To find: W1-2

Assumption: the balloon is considered a closed system

Formula: Volume, V = (4/3) π r3 for a sphere

Work done in a polytropic process, W1-2 = (P1V1 – P2V2)/(n – 1)

Calculation: V1 = (4/3) π r13 = (4/3) π(D1/2)3 = 0.065 m3

V2 = (4/3) π (D2/2)3 = 0.087 m3

V α D3 ie., D α V1/3

P α D Or P α V1/3 Or P/V1/3 = Constant ie., PV-1/3 = C

Or PV-0.33 = C
Therefore, for the polytropic process, n = -0.33

Pα D ie., P/D = constant

P1/D1 = P2/D2 Or P2 = P1D2/D1 = 500x0.55/0.5 = 550 kPa

W1-2 = (P1V1 – P2V2)/(n – 1) = (500x0.065 – 550x0.087)/(-0.33 – 1) = 11.54 kJ

4. Air Standard Cycles

4.1 An engine operating on Carnot cycle between temperature limits of 20o C and 800o C rejects heat
at the rate of 200 kJ/s. Determine i) the ideal thermal efficiency of the cycle and ii) the power output
of the engine.

Given: TH = 800o C = 1073 K

TL = 20o C = 293 K

QL = 200 kJ/kg

To find; ηth and Woutput

Formula: ηCarnot = 1 – TL / TH = 1 – QL / QH and Wout = QH - QL

Calculation:

ηth = 1 – TL / TH = 1-293/1073 = 0.727 = 72.7%

ηth = 1 – QL / QH Or QL / QH = 1 - ηth Or QH = QL / (1 - ηth) = 200 / 0.273 = 732.6 kJ/s

Power output = Woutput / s = (QH – QL) /s = 732.6 – 200 = 532.6 kJ/s (kW)

4.2 The compression ratio of an Otto cycle is 8.8. The minimum pressure and temperature are 0.95
bar and 25o C. The amount of heat added to the air per cycle is 1400 kJ/kg. On the basis of air standard
cycle, determine i) maximum temperature of the cycle and ii) the air standard efficiency. Take CV =
0.718 kJ/kg and γ = 1.4.

Given: P1 = 0.95 bar = 95 kPa

T1 = 25o C = 298 K

r = 8.8

Q2-3 = 1400 kJ/kg

CV = 0.718 kJ/ kg – K

γ = 1.4

To find: T3 and ηOtto

Formula: ηOtto = 1 – 1 / rγ-1

 T1 V1γ-1 = T2 V2γ-1

Q2-3 = CV (T3 – T2) kJ/kg

r = V1/V2

Calculation: T1 V1γ-1 = T2 V2γ-1 Or T2 = T1 (V1/V2)γ-1

= 298 (V1/V2)γ-1

= 298 (8.8)1.4-1

= 298 x 2.387

= 711.23 K

Q2-3 = CV (T3 – T2) kJ/kg

1400 = 0.718 (T3 – 711.23)

T3 = 1400/0.718 + 711.23 = 2661 K = 2388o C

ηOtto = 1 – 1 / rγ-1

= 1 – 1 / 8.8γ-1 = 1 – 0.419 = 58.1%

4.3 The compression ratio of an Otto cycle is 9. Determine, for an initial condition of 1 bar and 313
K, the pressure and temperature at the end of compression and cycle efficiency.

Given: r = V1/V2 = 9

P1 = 1 bar = 100 kPa

T1 = 313 K

To find: ηOtto, P2 and T2

Assumption: γ = 1.4

Formula: ηOtto = 1 – 1 / rγ-1

T1 V1γ-1 = T2 V2γ-1

P1 V1γ = P2 V2γ

Calculation: ηOtto = 1 – 1 / rγ-1 = 1 – 1 / 91.4 = 58.48%

T2 / T1 = (V1/V2)γ-1 = rγ-1

T2 = T1 rγ-1 = 313 x 91.4-1 = 753.77 K

P2/P1 = (V1/V2)γ = rγ

P2 = P1 rγ =100 x 91.4 = 100 x 21.67 kPa = 21.67 bar

4.4 A petrol engine has a swept volume of 500 cc and a clearance volume of 60 cc. If the pressure
and temperature at the beginning of compression are 1.02 bar and 24o C and the maximum cycle
temperature is 1400o C, calculate the air standard efficiency and the mean effective pressure.

Given: P1 = 1.02 bar = 102 kPa

T1 = 24o C = 297 K

T3 = 1400o C = 1673

V2 = 60 cc = 60 x 10-6 m3

V1 = 500 + 60 = 560 cc = 560 x 10-6 m3

To find: air standard η

Assumption: γ = 1.4, CV 0.718 kJ/kg-K and R = 0.287 kJ/kg-K for air

Formula: η = 1 – 1 / rγ-1,

η = Wnet/Qin, Wnet = Qin x η

MEP = Wnet/(V1 – V2),

T1 V1γ-1 = T2 V2γ-1 for an adiabatic process

m = P1V1/RT1 for an ideal gas

Calculation: r = V1/V2 = 560 x 10-6/60 x 10-6 = 9.33

η = 1 – 1 / rγ-1 = 1 – 1/(9.33)1.4-1 = 59.07%

T1 V1γ-1 = T2 V2γ-1

T2 = T1 (V1/V2) γ-1 = 297 (9.33) γ-1 = 725.62 K

η = Wnet/Qin, Wnet = Qin x η

Qin = m CV (T3 – T2) = 1 x 0.718 (1673 – 725.62) = 680.2 kJ/kg

Wnet = Qin x η = 680.2 x 0.5907 = 401.8 kJ/kg

m = P1V1/RT1 = 102 x 560 x 10-6 / 0.287 x 297 = 670.1 x 10-6 kg

MEP = Wnet/(V1 – V2) = 670.1 x 10-6 x 401.8 / (560 – 60) 10-6 = 538.5 kPa = 5.39 bar

4.5 Find the air standard efficiency of a diesel cycle if the clearance volume and the fuel cut-off are
5% of the stroke volume. Assume the index of isentropic compression and expansion as 1.4.

Given: V2 = 0.05 Vswept

V3 = V2 + 0.05 Vswept
 γ = 1.4

To find: ηDiesel

Formula: ηDiesel = 1 – 1 / rγ-1[(rcγ -1)/ γ(rc – 1)]

Calculation: r = V1/V2 = (V2 + VS)/V2 = (0.05 VS + VS)/ 0.05VS = 21

rc = V3/V2 = (V2 + 0.05 VS)/V2 = (0.05 VS+ 0.05 VS)/0.05 VS = 2

ηDiesel = 1 – 1 / rγ-1[(rcγ -1)/ γ(rc – 1)]

= 1 – 1 / 211.4-1[(21.4 -1)/ 1.4(2 – 1)]

= 1 – 0.3464 = 0.6536 = 65.36%

4.6 An engine working on Diesel cycle has a bore of 15 cm and a stroke of 25 cm. The clearance
volume is 400 cc and fuel injection takes place for the duration of 5% of stroke. Find the air standard
efficiency.

Given: d = 15 cm, l = 25 cm

V2 = 400 cm3

V2-3 = 5% of VS

To find: ηDiesel

Assumption: γ = 1.4

Formula: ηDiesel = 1 – 1 / rγ-1[(rcγ -1)/ γ(rc – 1)]

Calculation:

VS = ( π/4) x 152 x 25 = 4417.865 cm3

V2-3 = 0.05 x VS = 0.05 x 4417.865 = 220.893 cm3

V3 = V2 + V2-3 = 400 + 220.893 = 620.893 cm3

r = V1/V2 = (V2 + VS)/V2 =(400 + 4417.865)/400 = 12.045

rC = V3/V2 = 620.893/400 = 1.55

ηDiesel = 1 – 1 / 12.0451.4-1[(1.551.4 -1)/ 1.4(1.55 – 1)] = 59.35%

4.7 Calculate the loss in the efficiency of a Diesel cycle with a compression ratio of 16, if the cut-off
is delayed from 7% to 10%.

Given: r = 16

rC1 = 7% of initial volume and rC2 = 10% of initial volume

To find: η1 – η2

Assumption: γ = 1.4

Formula: ηDiesel = 1 – 1 / rγ-1[(rcγ -1)/ γ(rc – 1)]

Calculation: r = V1/V2 = 16 rC1 = V3/V2 = V3/V1 x V1/V2 = 0.07 x 16 = 1.12

rC2 = 0.1 x 16 1.6

η1 = 1 – 1 / 161.4-1[(1.121.4 -1)/ 1.4(1.12 – 1)] = 66.22%

η2 = 1 – 1 / 161.4-1[(1.61.4 -1)/ 1.4(1.6 – 1)] = 63.43%

Deterioration in efficiency = η1 – η2 = 66.22 – 63.43 = 2.79%