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INTRODUCTION
1.1

Definition and Scope of Engineering Thermodynamics

Thermodynamics is defined as the study of energy, its forms and transformations, and the
interactions of energy with matter. Hence, thermodynamics is concerned with
the concept of energy,
the laws that govern the conversion of one form of energy into another,
the properties of the working substance or the media used to obtain the energy
conversion.
In engineering or applied thermodynamics the scope is restricted to the study of heat and
work and the conversion of one into the other. Thermodynamic laws are applied to work
producing and work absorbing devices in order to understand their functioning and
improve their performance.
Thermodynamics has extremely wide range of applications. For example it is used by the
mechanical engineer in the design of energy converting devices such as steam and gas
turbines, internal combustion engines, fuel cells, thermoelectric generators as well as
refrigerators and air-conditioning equipment.

1.2

Value of Energy to Society

The availability of energy and people's ability to harness that energy in useful ways have
transformed our society and the energy requirements of almost all countries are ascending
up inexorably. It is very hard to imagine the present life without electricity and other
forms of energy. The energy available and consumed data exhibit the perspective picture
of the economic condition and scope and the level of advancement of living people's
civilization.
A few hundred years ago, the greatest fraction of the population struggled to subsist by
producing food for local consumption. Now, in many countries a small fraction of the
total work force produces abundant food for the entire population, and much of the
population is freed for other pursuits. We are able to travel great distances in short times
by using a choice of conveyances; we can communicate instantaneously with persons
anywhere on earth; and we control large amounts of energy at our personal whim in the
form of automobiles, electric tools and appliances, and comfort conditioning in our
dwellings. All these changes are as results of the development of the science and
application of thermodynamics, our ability to obtain energy, transform it, and apply it to
society's needs.

1.3 Macroscopic versus Microscopic Viewpoint

There are two points of view from which the behavior of matter can be studied: the
macroscopic and the microscopic. The description of a system or matter using a few of its
measurable bulk properties constitutes a point of view called macroscopic. For example,
consider a diesel engine cylinder with air in it. The air occupies a certain volume for each
piston the position. The volume for any position is easily measured. The temperature and

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pressure are also easily measured. The state or condition of the system (air in the
cylinder) is completely described by means of the above large scale characteristics or
properties of the system. Such properties are called macroscopic point of view. Different
system requires different properties for complete description of the state. Some common
attributes of such description are: (a) These characteristics do not involve any
assumptions about the structure of the material, (b) these are readily measured, and (c)
Only few such properties are required to completely describe the system.
In the above example the air in the cylinder is assumed to consist of a very large number
of particles (all having the same mass) and each moving with an independent velocity
when a microscopic point of view of is adopted. The description of the position of each
molecule requires three coordinates and the three velocity components. At least six
variables are required to describe the state of each molecule. To describe the state of all
molecules is almost impossible. The pressure due to the air is assumed to be caused by
the moving molecules striking the wall. To determine the pressure, the change in
momentum of all the molecules striking the wall per unit area should be summed up.
Similarly to find the internal energy of the system, the kinetic energy of all the molecules
should be summed up. Though microscopic study of a system may provide data for fixing
the state, it is very complex for ordinary purposes. The macroscopic point of view is
sufficient as far as applied thermodynamics is concerned.
All the results of classical or macroscopic thermodynamics can, however, be derived from
the microscopic and statistical study of matter.

1.4 Concepts and Definitions

Before the basic structure of thermodynamics can be outlined, it is necessary to define
some of the fundamental concepts thoroughly.

1.4.1 System and Surroundings

Whenever a change is to be analyzed it is necessary to specify the region under study in
order to avoid any confusion. In thermodynamics defining the boundary around the
region of consideration does this. This boundary may be real or imaginary, moreover, it
may be fixed or it may change in shape as well as volume. Everything within the
boundary is called the system, while the region external to the boundary is called the
surroundings. All transfers of mass and energy between the system and surroundings are
evaluated at the boundary.

Figure 1.1: System, Surroundings, Boundary and Universe

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Hence, the system is a specified region wherein changes due to transfers of mass and
energy or both are to be studied. It is not necessary that the volume or shape of the system
should remain fixed.
A system and it surroundings together comprises a universe which can be defined as
totality of matter that exists.
The thermodynamic system may be classified into the following three groups: (a) Closed
system; (b) Open system; and (c) Isolated system.
If the mass within the boundary of the system remains constant, it is called a closed
system as shown in Figure 1.2. Thus a closed system does not permit any mass transfer
across its boundary but it permits transfer of energy. Closed system is sometimes also
referred to as control mass (CM).

Figure 1.2: Closed System

If both mass and energy cross the boundary of a system it is called an open system as
shown in Figure 1.3. An open system permits both mass and energy across the
boundaries, and the mass within the system may not remain constant. For thermodynamic
analysis of an open system, such an air compressor, attention is focused on a certain
volume in space surrounding the compressor, known as the control volume, bounded by a
surface called the control surface.

Figure 1.3: Open System and Control Volume

If neither mass nor energy is allowed to cross the boundary of a system it is called an
isolated system. Thus in an isolated system does not have transfer of either mass or
energy with the surroundings. Any closed rigid insulated box can be taken as an example
of an isolated system.

1.4.2 Property
A thermodynamic system would have many characteristics, directly or indirectly
measurable, which would serve to describe or identify the system. For example, mass,

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physical composition, temperature, pressure, volume, surface area, velocity, elevation and
electrical potential are some such characteristics. In addition a large number of other
characteristics of the system can be defined. These characteristics or quantities, the values
of which describe the system are called thermodynamic properties or thermodynamic
coordinates of the system.
The thermodynamic properties of a system may be divided into the following two general
classes: (a) Intensive properties, and (b) Extensive properties.
If the value of a property is independent of the mass of the system, it is called an intensive
property. The pressure, temperature, density, velocity, height, viscosity, etc. are examples
of intensive properties.
If the value of a property is proportional to the mass of the system, it is called an
extensive property. The volume, surface area, energies of all kinds, electric charge,
magnetization, etc. are examples of extensive properties.
The ratio of an extensive property to the mass is called the specific value of that property.
Thus, if the total energy of a system is denoted by E, and the mass by m, then the specific
total energy or total energy per unit mass is given by
. (1.1)
In general, capital letters will denote extensive properties, and small letters will be used to
represent the specific values of these properties.

1.4.3 Thermodynamic Equilibrium

While talking about the properties of a system we had assume implicitly made the
assumption that the value of a property is the same at all points in the system. Evidently it
is meaningless to speak of the temperature or the pressure of a system unless the
temperature or the pressure has the same value throughout the system. In other words, we
implied that the system is in a state of thermodynamic equilibrium.
Hence, a system is said to exist in a state of thermodynamic equilibrium when no change
in any macroscopic property is registered, if the system is isolated from its surroundings.
Therefore, there can be no spontaneous change in any macroscopic property if the system
exists in an equilibrium state. Thermodynamics studies mainly the properties of physical
systems that are found in equilibrium states.
A system will be in a state of equilibrium, if the conditions for the following three types
of equilibrium are satisfied: (a) mechanical equilibrium; (b) chemical equilibrium; and (c)
thermal equilibrium.
In the absence of any unbalanced force within the system itself and also between the
system and surroundings, the system is said to be in a state of mechanical equilibrium. If
an unbalanced force exists, either the system alone or both the system and the
surroundings will undergo a change of state till the mechanical equilibrium is attained.

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If there is no chemical reaction or transfer of matter from one part of the system to
another, such as diffusion or solution, the system is said to in a state of chemical
equilibrium.
A system is said to be in thermal equilibrium, when there is no temperature difference
between the parts of the system or between the system and surroundings.

1.4.4 Thermodynamic State

Each unique condition of system is called a state. Thus state of a system (when the system
is in thermodynamic equilibrium) is the condition of a system at an instant of time which
can be as described by the statement of its properties, such as pressure, volume,
temperature etc. The number of properties, which are required to describe a system,
depends upon the nature of the system.
It follows from the definition of state that each property has a single at each state. Stated
differently, all properties are state or point functions. Therefore all properties are identical
for identical states.
On the basis of the above discussion we can determine if a given variable is a property or
not by applying the following tests:
(a) A variable is a property if, and only if, it has a single value at each equilibrium state.
(b) A variable is a property if, and only if, the change in its value between any two
prescribed equilibrium states is single valued.

1.4.5 Thermodynamic Process

When a system changes from one equilibrium state to another equilibrium state, then the
path of successive states through which the system has passed is known as
thermodynamic process. In Figure 1.4, 1 2 represents a thermodynamic process.

Figure 1.4: Thermodynamic process or Cyclic process

When a process or processes are performed on a system in such a way that the final state
is identical with the initial state, it is the known as a thermodynamic cycle or cyclic
process. In Figure 1.4, 1 A 2 and 2 B 1 are processes whereas 1 A 2 B 1 is a
thermodynamic cycle.
Let us consider a system of gas contained in a cylinder as shown in Figure 1.5(a). The
system initially is in equilibrium state, represented by the properties P1, V1, T1. The
weight on the piston just balances the upward force exerted by the gas. If the weight is
removed, there will be an unbalanced force between the system and the surroundings, and
under gas pressure, the piston will move up till it hits the stops. The system again comes
to an equilibrium state, being described by the properties P2, V2, T2. But the intermediate
states passed through by the system are nonequilibrium states which cannot be described
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by thermodynamic coordinates. Figure 1.5(b) shows point 1 and 2 as the initial and final
equilibrium states joined by a dotted line, which has got no meaning otherwise.

Figure 1.5 (a): Transition between two equilibrium states by an unbalanced force
(b): Plot representing the transition between two equilibrium states

Hence, if a system passes through a sequence of non-equilibrium states during a process,

these states can not be located on any property diagram because each property does not
have a unique value in the entire system. Such a process is called an irreversible process.
It can always be assumed, however, that the system is in a state of equilibrium before and
after the process, so that irreversible processes may be represented on a property diagram
by a broken line joining the initial and final equilibrium states. The broken line indicates
the intermediate states visited by the system during the process are indeterminate.

Figure 1.6 (b): Infinitely slow transition of a system by infinitesimal force

(b): A quasi-equilibrium process
Now if the single weight on the piston is made up of many very small pieces of weights
as shown in Figure 1.6(a), 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, if the gas system is
isolated, the departure if the state of the system from the thermodynamic equilibrium state
will be infinitesimally small. So every state passed through by the system will be an
equilibrium state. Such a process, which is locus of all the equilibrium points passed
through by the system, is known as quasi-static or quasi-equilibrium process. Infinite
slowness is the characteristic feature of a quasi-static process. A quasi-static process is
thus a succession of equilibrium states and represented by a continuous line as shown in
Figure 1.6(b). A quasi-static process is also called a reversible process.

1.4.6 Some Common Properties

(a) Pressure
Because many systems studied in thermodynamics involve gases or vapors, pressure is a
useful property for describing the state of the system. Pressure is defined as the normal
force exerted per unit area on a real or a fictitious surface.
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With the restriction that area over which the force is applied must not smaller than some
minimum value , the mathematical definition of the local pressure is
. (1.2)
For engineering work, pressures are often measured with respect to atmospheric pressure
rather than with respect to perfect vacuum. The pressure relative to the atmosphere is
called gauge pressure. The pressure relative to a perfect vacuum is called absolute
pressure. Hence, the gauge pressure is related to the atmospheric pressure by
. (1.3)

Figure 1.7: Relation between absolute, atmospheric and gauge pressure

This relation is used for pressures above atmospheric pressure, as shown in Figure 1.7(a).
For pressures below atmospheric pressure, the gauge pressure will be negative. This
negative gauge pressure is known as vacuum pressure. Therefore
. (1.4)
This relation is shown in Figure 1.7(b). The standard value of atmospheric pressure is
taken as 101.3 kPa (or 760 mm of Hg) at sea level.
(b) Specific Volume
Volume
is the space occupied by a substance and is measured in m3. This is an
extensive property. The specific volume ( ) of a substance is defined as the volume per
unit mass and is measured in m3/kg. Thus mathematical definition of specific volume is
. (1.5)
where is a minimum amount of mass that is large compared with the mass of the
individual molecules of which it is composed. Hence, specific volume is the reciprocal of
the density, i.e.,
. (1.6)
(c) Temperature
It is an intensive thermodynamic property, which determines the degree of hotness or the
level of heat intensity of a body. A body is said to be at a high temperature or hot, if it
shows high level of heat intensity in it. Similarly, a body is said to be at a low temperature
or cold, if it shows a low level of heat intensity.
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The temperature of a body is measured with the help of an instrument known as

thermometer. For most temperature measurements, it is convenient to define a scale that
is a linear function of some measurable quantity, at least over some range of temperature
between two fixed points. Hence all temperature scale are based on two fixed points
known as freezing point of water under atmospheric pressure or ice point and the boiling
point of water or steam point.
The two scales most useful in thermodynamics are so called absolutes scales. The
absolute scale for SI is the Kelvin scale. This scale is a one point scale based on the
second law of thermodynamics. The single point is the triple point of water, where ice,
liquid water, and water vapour coexist in a closed system in the absence of air. The
Kelvin scale replaced the original scale which was based on a linear function between two
selected points. The Kelvin unit does not use the degree symbol, but simply the symbol
K. The other absolute scale is called the Rankine scale. It is related to Kelvin scale by
. (1.7)
where a degree Rankine is denoted by 0R.
Two other commonly used scales are the Fahrenheit scale and the Celsius scale. The
Fahrenheit scale is also linear, and it was originally based on two define point: 320 as the
temperature at which a system of air-saturated water and ice coexist and 2120 as the
temperature of a system containing water and steam at a pressure of 1 atm. The symbol
for the Fahrenheit degree is 0F. This original definition has been replaced by the
following relations to the Kelvin scale:
. (1.8)
. (1.9)
where a degree on the Celsius scale is denoted by oC.
The Celsius scale was originally defined by a single point and a defined size for the
degree. The fixed point was the triple point of water, and it was defined to have a
temperature of 0.010C. The size of the degree chosen for Celsius scale comes from the
Kelvin scale and yields the temperature of the steam point to be 100.000C at 1 atm. This
original definition was replaced by the relation with Kelvin scale given in equation (1.8).
Figure 1.8 compares the various scales. Note that the size of 1 K is the same as 1 degree
on the Celsius scale; similarly, the size of the degrees on Rankine and Fahrenheit scales
are equal.
1.4.7

Equality of Temperature and Zeroth Law of Thermodynamics

Equality of Temperature
Let two bodies, one hot and one cold, be placed in contact with each other, while isolated
from all other bodies. In course of time, the hot body becomes colder, and the cold body
becomes hotter. In other words, both bodies experience a change in one or more of their
properties. Finally, all changes in the properties of the two bodies ceases and the bodies
are said to be in thermal equilibrium with each other or are at same temperature. Thus the
condition of equality of temperature is as follows:

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Two systems have equal temperatures if there are no changes in their properties when
they are brought in thermal contact with each other.

Figure 1.8: Comparison of temperature scales

Zeroth Law of Thermodynamics
It is a matter of experience that when two bodies are in thermal equilibrium with a third
body, they are in thermal equilibrium with one another. This statement, which is
sometimes called the Zeroth law of thermodynamics, is tacitly assumed in every
measurement of temperature. Thus, if we want to know if two bodies are at the same
temperature, it is not necessary to bring them into contact and see whether their
observable properties change with time, as described previously. It is necessary only to
see if they are individually in thermal equilibrium with a third body. The third body is
usually a thermometer.

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