1.

Basic Concepts
1. Introduction
The economic prosperity of a nation is measured in terms of energy produced. It is due to energy that man dominates the universe.
Thermodynamics is a science of energy. It is based on observations in nature. It predicts the real behaviour of process in home and industry.
Thermodynamics is useful to all branches of engineering.
Earlier attempts to produce energy by perpetual motions were discarded by the laws of thermodynamics. Heat can easily be produced by burning
the fuels. How much energy is converted into work? How to reduce the consumption of fuels? What is possibility of utilization of new sources of energy?
Thermodynamics has been developed to answer above questions.
Thermodynamics is a Greek word. ‘Thermo’ means heat and ‘dynamics’ means mechanical power. Thermodynamics converts heat into
mechanical energy. Precisely, thermodynamics may be defined as a science which deals with energy transformation from one form to another and
relationship among the properties of the system. In steam power plants, gas turbines, cars, motor cycles, scooters etc, heat is converted into work. In
domestic refrigerators, air conditioning plants, cold storage, ice plants and liquefaction plants, work is converted into heat. Solar energy is converted into
heat in solar collectors and into electrical energy in solar cells. Optimal design of thermal power plant or a domestic refrigerator can be obtained by
applying the knowledge of thermodynamics. Even the metabolism of human body can be studied by utilizing the principles of thermodynamics.
The pillars of thermodynamics are its four laws. These are zeroth, first, second and third law of thermodynamics. From zeroth law, temperature is
defined. The first law is essentially the law of conservation of energy and defines energy. 2nd law predicts the direction of heat flow from a higher
temperature to a lower temperature.

1.2 Thermodynamic System, Surroundings, Boundary and Universe

Thermodynamic system is defined as a definite quantity of matter or volume in space upon which attention is focused during a analysis in
thermodynamics. Everything external to a system is called the surroundings. The layer separating the system and the surroundings is called the boundary.
The combination of the system and its surrounding is called the universe.
 Fig. 1.1 Gas between a cylinder and piston

Fig. 1.1 shows a gas contained between a cylinder and piston. The gas confined within the dashed lines is the fixed quantity of matter so called the system.
The dashed lines represent the boundary. Everything outside the dashed lines is known as the surroundings. Here gas and everything outside the gas is
called the universe. Therefore, universe is nothing but combination of system and surroundings. The system is further classified into closed system, open
system and isolated system.

1.2.1. Closed System

In closed system, we pay attention on the fixed quantity of matter. A closed system is the system in which mass does not cross the boundary but
energy in the form of heat and work crosses the boundary. Fig. 1.2 represents a gas confined between a piston and cylinder.
 Fig. 1.2 Closed system
When the gas is heated, heat Q is supplied to the system and work W is done by gas. In the process piston moves up and boundary rises also. In the
diagram, it is observed that heat and work are crossing the boundary but mass of gas is confined within the boundary. Therefore, the system is closed
system. It should be noted that in closed system boundary also moves. To conclude
1. A closed system has a fixed mass or quantity of matter.
2. The mass does not cross the boundary of the system.
3. Energy, either in the form of heat or work or both can cross the boundary.
4. Boundary can also move.

1.2.2. Open System

In open system, we pay attention on a specified volume in space. Open system is the system in which both mass and energy cross the boundary.
The popular examples of open system are the air compressor and steam turbine.
Fig. 1.3 displays an air compressor.
 Fig. 1.3 Example of an Open ystem

In this system, air enters at low pressure and leaves at high pressure. Work is done the system by a motor and heat is lost to the surroundings. So to
conclude, an open system is a fixed volume system in which mass and energy can cross the boundary. To summarize
1. The open system has a fixed volume called control volume.
2. Both heat and work can be flow across the boundary.
3. Mass can also enter and leave the control volume.

1.2.3 Isolated system

An isolated system is the system in which neither mass nor energy can cross the boundary. A thermal flask, with closed cover and well insulated
all around, can be considered as an isolated system. In the thermal flask, almost no heat is lost to the surrounding and its contents are confined within the
closed space.
1.3 Property, State, Equilibrium, Process and Cycle

1.3.1 Property
 A property is any measurable quantity or characteristics to describe the physical condition of the system. In short, a property is a quantity to
describe the system. These properties may be temperature, pressure, volume, density, internal energy, entropy, enthalpy etc. Thermodynamic properties
are further divided into intensive and extensive types.
1. Intensive property
Intensive property is the property of a system which is independent of the mass of the system. The examples of intensive property are temperature,
pressure, density, specific volume etc. These are generally denoted by small letters i.e. t, p, ρ, υ etc.
2. Extensive property
Extensive property is the property of a system which is dependent on the mass of the system. The examples of extensive properties are volume,
mass, kinetic energy, potential energy etc. These are generally denoted by capital letters i.e. V, M,K.E, P.E. etc.
The ratio of extensive property to the mass of the system is known as specific property. Specific property is a intensive property. If we divide
volume, V, by mass, m, we get specific volume. Specific volume is a internal property.
1.3.2 State
State is a condition or position in which a thermodynamic system exists. Condition or position is specified by its properties. At a particular state,
all the properties have fixed values.

(a) Initial state before heating (b) Final state after heating

Fig. 1.4 Initial and final state of a system

Fig. 1.4 shows a gas contained between a cylinder and piston. Before heating at state 1, temperature, pressure, specific volume and internal energy are t1,
p1, v1 and u1. After heating at state 2, temperature, pressure, specific volume and internal energy are t2,p2, v2 and u2. So it can be said that gas can exist in
different states. Thus in present example, change in property, dt,
 2

∫dt
1
dt = t2 – t1

It means that t to be property, dt is an exact differential.

1.3.3 Thermodynamic Equilibrium

A system is said to be in thermodynamic equilibrium if the properties of system are same at all the points and do not change with time. The
important properties are temperature, pressure and chemical composition. If the temperature of the system is same at all the points and does change with
time, it is said to be in thermal equilibrium. If pressure of the system is same at all the points and does not change with time, it is said to be in mechanical
equilibrium. If the chemical concentration of the system is same at all the points of the system and does not change with time, if it said to be in chemical
equilibrium.
To attain thermodynamic equilibrium, all the three types of equilibrium, the thermal, the mechanical and the chemical equilibrium must exist.
When system goes from one state to another, and deviation from equilibrium is very small or infinitesimal, it is said to be in quasi-equilibrium.

1.3.4 Process & Cycle

Process is as the path of the successive equilibrium states through which the system passes when it changes its position from state 1 to state 2.
When a system executes one or more processes in such a way that initial and final states of the system are identical, it is said to have executed a cycle.

Fig.1.5 Process and Cycle on p- v diagram

In Fig. 1.5, system undergoes a number of processes and finally returns to initial state 1. 1-2, 2-3, 3-4 and 4-1 are processes and 1-2-3-4-1 is a cycle.

1.4 Work and Heat

1.4.1 Work
 Thermodynamics is a science of transformation of energy from one form to another form. In popular sense energy is the capacity of doing work.
Work is denoted by W. In mechanics, it is defined as the product of force and distance moved in the direction of force. This definition can be used to find
the work to lift a weight, to stretch a spring or a wire. But this definition can not be applied in the study of thermodynamics which deals with system and
surroundings. To calculate work done in thermodynamics, the forces acting on the boundary and its displacement must be known. A broad definition of
work is given in thermodynamics. Work is said to be done by a system on the surroundings if sole effect external to the system could be the raising of a
weight. It can be shown that the definition of work by thermodynamics is more general than given by mechanics.
Fig. 1.6(a) depicts a storage battery as a system with a resistor.

(a) Battery (b) Battery with motor

Fig. 1.6 Flow of current from a battery as work

A current is flowing in the circuit. According to the definition of work as given by mechanics no force is moving any distance. So no work has been done
by the system. But by the definition of thermodynamics, work is being done. In Fig. 1.6(b), if resistor is replaced by a motor having 100% efficiency,
motor can raise the weight and work is done.
In Fig.1.6 (b), if system includes both battery and motor, the work done by this new system on surroundings will be zero.
If work is done by a system, it is considered positive. If work is done on the system, it is taken to be negative. Work is a transient phenomenon. It
only occurs across the boundary when system changes its state. In the definition of work, the weight is not to be actually raised, but it should be possible
to raise the weights by introducing certain changes. In Fig.1.6, resistor was replaced by weight and motor.

1.4.2 Work Done in a Quasistatic Process

 Let us consider a gas contained between cylinder and piston as shown in Fig.1.7(a). Gas is heated, its temperature and pressure increase and piston
is raised up and boundary increased. The process is shown on p-v diagram in Fig. 1.7 (b).

Fig. 1.7 (a) Gas executing a quasistatic process Fig. 1.7 (b) P-V diagram

Fig.1.7 Work done in a quasistatic process

Gas is executing a quasistatic process 1-2. Let p be pressure exerted by gas, dl the distance moved by piston and A area of cross-section of the piston. The
work done by gas when piston moves small distance dl,

δW = p Adl = p dv

As piston moves from state 1 to state 2, total work done

2

W = ∫ 1
p dv ………. (1.1)

It is observed in Fig.1.7 (b) that work done during process 1-2 is area under the curve
1-2. This area depends on the path 1-2 followed by the gas. If we change the path, area will change, so the work. Therefore, it can be concluded that work
is a path function and does not depend on the states. The work done in different processes is under mentioned.
1. Work Done in Constant Pressure (Isobaric) Quasistatic Process

Fig. 1.8 Work done in constant pressure process

2

W12 = ∫
1
p dv = p (v2 – v1) ……. (1.2)

2. Work Done in a Constant Volume (Isochoric) Quasistatic Process

Fig. 1.9 Work done in a constant volume process

W12 = ∫
1
p dv = 0 ……… (1.3)

3.Work Done in an Isothermal Quasistatic Process

 3. Fig. 1.10 Work done in an isothermal process
2

W12 = ∫
1
p dv

For an isothermal process, pv = C = p1v1 where C is a constant

2 2
p1v1
W12 = ∫
1
p dv = ∫
1
v
dv

2
dv v2
= p1v1 ∫
1
v
= p1 v1 ln
v1
v2
W12 = p1v1 ln ……………………………. (1.4)
v1

4. Work Done in a Polytropic Quasistatic Process

 Fig. 1.11 Work done in a polytropic process

W12 = ∫1
p dv

For a polytropic process,

pvn = p1v1n = p2v2n = C where n is a index of polytropic process.

n
p v
Now p = 1 n 1
v
2 2
dv
∫ p dv ∫p
n
So W12 = = 1 v1
1 1 vn
v2
n v −n +1
W12 = p1 v 2 =  
 − n +1 v1

[v ]
n
p1 v1 −n +1 −n +1
= 2 −v1
1 −n
n − n +1 n −n +1
p2 v2 v2 − p1v1 v1
=
1−n
p 2 v 2 − p1v1
=
1 −n
 p1 v1 − p 2 v 2
W12 = ………..(1.5)
n −1

1.4.3 Work Done in Non-equilibrium Process

It was discussed in last article that work done in a quasistatic process or quasi equilibrium is give by the area under p-v diagram or ∫ p dv .For non-
1
2

quasistatic processes, is not given by ∫p

1
dv . It will be clear from the examples given below.

1.Work Done by Rotating Paddle on a Gas

Fig.1.12 Non-quasistatic process

Fig.1.12 shows a gas contained in a container work is done by a rotating paddle on the gas. The paddle is rotated by a motor to which electric power is
2

supplied. The work done on the gas is equal to the power supplied to the motor. In this example work is done on the gas by the paddle but ∫ p dv
1
is

zero as there is no change in volume of the gas. This is because process is not quasistatic. The paddle is rotating with a high speed so deviation from the
equilibrium is not infinitesimal.

2. Work Done against Vacuum

 Fig.1.13. Work done against Vacuum

Fig. 1.13 represents a insulated chamber. Half volume of chamber contains a gas and in other half vacuum exists. Partition is removed and gas occupies
2

the entire volume. It is observed that now ∫ p dv

1
is not zero but work done is zero. In this example the process is not quasistatic so expression of work
2

done equal to ∫ p dv
1
is not applicable to this system. When partition is removed, gas fills the entire volume rapidly, so change in properties is abrupt

and not the minute as required in quasistatic process. The process is not in equilibrium state. The work done by the gas is zero can be explained in two
ways. From mechanics point of view, work done is zero because vacuum leads to zero or no force, so work done against no force is zero. The
thermodynamically, boundary of the system is changing within the system, volume is doubled, but no work is done on the surroundings outside the system
so, work done is zero.

1.4.4 Heat

Fig. 1.14. Heat transfer between water and a metallic piece

Fig. 1.14. shows a hot metallic piece dropped in a bucket of cold water. It is observed that as time passes, the temperature of metallic piece decreases and
temperature of water
increases till equilibrium temperature is reached. In the process energy is transferred from the hotter body to the cold body. This energy which is
transferred by virtue of temperature difference is called heat. Thermodynamically, this energy cannot be called work.
Heat is a form of energy which is transferred from one system to another system or to the surrounding by virtue of temperature difference.
 Like work, heat is transient phenomenon. Heat is never contained by a system. Heat transfer occurs when there is change in temperature within the
system or between the system and the surroundings. If heat is transferred to the system, it is taken to be positive. If heat is transferred from a system to the
surrounding, it is considered to be negative.
Like work, heat is a path function. Heat transfer between state 1 and state 2 depends on the path followed between the two states. Heat transfer, Q,
2

is not a property and not an exact differerential. Therefore, it is denoted by δQ and not by dQ. ∫δ Q is denoted by Q12 and not by Q1 – Q2.
1
So to conclude both work and heat are transient phenomena, boundary phenomena and path functions.