Presented by:

Mr. P.K.Gupta
Asst.Prof. Mechanical Engineering
JIET,DAT. Jodhpur
 Basic Concepts of Thermodynamics
After going through this unit. We would be able
to understand the following:
Thermodynamic system and its types
Thermodynamics properties
Quasi-static process
Zeroth, I, II, and III law of thermodynamics
Concept of entropy
 WHAT IS THERMODYNAMICS?

• Thermodynamics is branch of science which deals with energy transfer

& its effects on properties (physical & chemical) of the substance.

• Amount of heat or work transfer taking place while arriving one

state from another is the main concern in thermodynamics.

• The word “ Thermodynamics” are derived from the Greek word

Therme means “Heat” & Dynamics means “Power”

Thermodynamics deals with three E’s

• Energy
• Entropy
• Equilibrium
Basic terms used in thermodynamics:

Thermodynamic System: Thermodynamic System is defined as

quantity of matter and region in space (control volume) on which
our thermodynamic study is focused. It enclosed by an imaginary or
real surface which may be rest
or in motion.

Surroundings: Everything external to

the system is the surroundings.

(That part of the surrounding which is affected by the system is

known as the immediate surroundings.)
 CLOSED SYSTEM: It is a type of system in which only energy
interaction & no mass interaction take place.
EX. Piston – cylinder arrangement without valve.

OPEN SYSTEM: The system which can exchange both mass and
energy with its surroundings is called an open system. In such a
system, flow type of processes occur.
EX. Piston – cylinder arrangement with valve.
Most of the engineering devices are open system.
ISOLATED SYSTEM: It is a type of system in which neither energy
nor mass interaction takes place.

Ex. Hot coffee or tea kept in a well insulated thermos flask,

Universe.

UNIVERSE: Combination of system and surrounding is called

universe.

ADIABATIC SYSTEM: A system which is thermally insulated from its

surroundings is called an adiabatic system.
It can ,however, exchange work with its surroundings. If it does
not, it becomes an isolated system.
BOUNDARY: It is real or imaginary surface that separates system from the
surroundings. It can be fixed or movable.
 Thermodynamics properties
Extensive Property: Properties which depends on the mass of
the system or in other words, value for the whole system is the
sum of its values of the various subsystems or parts.
Example: Volume (V), Energy (E), Enthalpy, Entropy.

Intensive Property: These properties have values that are

independent of the size or amount of mass of the system. These
have fixed value. If a given phase system in equilibrium is
divided into n parts, then the value of given intensive property
will be the same for each of the subsystems.
Example: Temperature, Pressure, Density, Velocity etc.
STATE: In any system, only two independent properties are
necessary to define completely the state of the fluid.

EQUILIBRIUM: The word equilibrium implies a state of balance. In

an equilibrium state there are no unbalanced potentials or driving
forces within the system.

THERMODYNAMIC PROCESS:
Any change that a system undergoes from
one equilibrium state to another is called
a process, and the series of states through
Which a system passes during a process is
called the path of the process.
To describe a process completely, one should specify
the initial and final states of the process, as well as
the path it follow and interaction with surroundings.
REVERSIBLE AND IRREVERSIBLE PROCESSES:
A thermodynamic process (state i → state f ) is said to be
reversible if the process can be turned back such that both
the system and the surroundings return to their original
states, with no other change anywhere else in the universe.

Examples of Reversible Process

Here, we have listed a few examples of
Reversible Process:
 Extension of springs
 Slow adiabatic compression or
expansion of gases
 Electrolysis (with no resistance in the electrolyte)
 The frictionless motion of solids
Irreversible Processes
An irreversible process can be defined as a process in which the
system and the surroundings do not return to their original
condition once the process is initiated.
Taking an example of an automobile engine, that has travelled a
distance with the aid of fuel equal to an amount ‘x’. During the
process, the fuel burns to provide energy to the engine,
converting itself into smoke and heat energy. We cannot
retrieve the energy lost by the fuel and cannot get back the
original form.
Examples of Irreversible Processes
A few examples of Irreversible Processes are:
Relative motion with friction
Throttling
Heat transfer
Diffusion
Electricity flow through a resistance
Nature has a preferred way of directing changes.

eg:

 water flows from a higher to a lower level

 Electricity flows from a higher potential to a lower one

 Heat flows from a body at higher temperature to the one at a

lower temperature

 Momentum transfer occurs from a point of higher pressure to a

lower one.

 Mass transfer occurs from higher concentration to a lower one

Quasi-static Processes :
A quasi-static process is one in which

 The deviation from thermodynamic equilibrium is

infinitesimal.
 All states of the system passes through are
equilibrium states.
 If we remove the weights slowly one by one the pressure of the
gas will displace the piston gradually. It is quasistatic.
 On the other hand if we remove all the weights at once the
piston will be kicked up by the gas pressure.(This is unrestrained
expansion) but we don’t consider that the work is done - because
it is not in a sustained manner
 In both cases the systems have undergone a change of state.
 Another eg: if a person climbs down a ladder from roof to
ground, it is a quasistatic process. On the other hand if he jumps
then it is not a quasistatic process.
What is Zeroth Law of Thermodynamics?
DEFINITION
The Zeroth Law of Thermodynamics states that If two systems are in
thermal equilibrium with a third system separately then they are in thermal
equilibrium with each other.

EXAMPLE
When a body ‘A’ is in thermal equilibrium with another body ‘b’, and also
separately in thermal equilibrium with a body ‘C’, then body ‘B’ and ‘C’ will
also be in thermal equilibrium with each other. This statement defines the
zeroth law of thermodynamics. The law is based on temperature
measurement.

Zeroth Law of Thermodynamics: The double arrow represents thermal

equilibrium between systems. If systems A and C are in equilibrium, and
systems A and B are in equilibrium, then systems B and C are in equilibrium.
The systems A, B, and C are at the same temperature.
First law of thermodynamics
It states that, "The change in internal energy of a system is the sum of all
the energy inputs and outputs to and from the system similarly to how all
the deposits and withdrawals you make determine the changes in your
bank balance.”
This is expressed mathematically as:

Where ΔU is the change in the internal energy, Q is the heat added to

the system and W is the work done by the system.
Joule’s Experiment and the First law of thermodynamics

Work/Heat = Constant (J)

Internal Energy:
The internal energy of a thermodynamic system is the energy contained
within it. It is the energy necessary to create or prepare the system in any
given internal state. Internal energy U of a system or a body with well
defined boundaries is the total of the kinetic energy due to the motion of
molecules and the potential energy associated with the vibrational
motion and electric energy of atoms within molecules. Internal energy
also includes the energy in all the chemical bonds
Internal energy is a thermodynamic property of the system that refers to
the energy associated with the molecules of the system which includes
kinetic energy and potential energy.

Internal energy is a state function of a system and is an extensive

quantity.
A corresponding intensive thermodynamic property called specific
internal energy, commonly symbolized by the lowercase letter u, which is
internal energy per mass of the substance.
As such the SI unit of specific internal energy would be the J/g.
If the internal energy is expressed on an amount of substance basis then it
could be referred to as molar internal energy and the unit would be the
J/mol.
Internal Energy of a Closed System
For a closed system the internal energy is essentially defined by
ΔU = q + W
Where
ΔU is the change in internal energy of a system during a process
q is the heat
W is the mechanical work.
If an energy exchange occurs because of temperature difference
between a system and its surroundings, this energy appears as
heat otherwise it appears as work. When a force acts on a system
through a distance the energy is transferred as work. The above
equation shows that energy is conserved.
 The different components of internal energy of a system is given below.

Thermal energy Sensible heat Energy change of a system

associated with:
•Molecular, translation,
rotation, vibration.
•Electron translation and
spin.
•Nuclear spin of molecules.
Latent heat Energy required or
released for phase change,
change from liquid to
vapour phase requires
heat of vaporization.
Chemical energy Energy associated with the chemical bonds in a
molecule.
Nuclear energy The large amount of energy associated with the bonds
within the nucleus of the atom.
What is the significance of internal energy?
Internal energy is important for understanding phase
changes, chemical reactions, nuclear reactions, and many
other microscopic phenomena, as the possible energies
between molecules and atoms are important. Both objects
exhibit macroscopic and microscopic energy in vacuum.

What factors affect internal energy?

The internal energy can be altered by modifying the
object’s temperature or volume without altering the
amount of particles inside the body. Temperature: As a
system’s temperature increases, the molecules will move
faster, thus have more kinetic energy and thus the internal
energy will increase.
Enthalpy
We now introduce a new property called enthalpy that is closely related to the
thermal internal energy U. Enthalpy is most useful in the analysis of processes
in open-systems which will be the subject of the next chapter. As a prelude, we
use a constant pressure process to demonstrate the usefulness of enthalpy as
a property.
Consider the piston-cylinder arrangement where the pressure, P of the gas
within the cylinder is maintained constant by keeping the weights on the piston
fixed. A small quantity of heat, δQ is supplied to the gas in a quasi-static
manner resulting in an increase in volume dV . The work done by the gas is
PdV . Applying the first law to this process we have
δQ = dU + PdV ----------------- (1)
Since the pressure is constant during the process we could rewrite Eq. as
δQ = d(U + PV ) ……………..… (2)
Now the quantity (U + PV) is a property because U, P and V are all properties
of the system. This new property is called enthalpy which is denoted by the
symbol H.
Hence we could write Eq. (2) in the form
δQ = d(U + PV) = dH …………… (3)
Change in enthalpy equals heat interaction for constant pressure processes.
However, being a property, the enthalpy is a function of the state of the system
and therefore independent of the processes undergone by the system.
Second Law Of Thermodynamics
The second law of thermodynamics states that the
total entropy of an isolated system can never decrease over time,
and is constant if and only if all processes are reversible

Entropy, the measure of a system's thermal energy per unit

temperature that is unavailable for doing useful work. Because
work is obtained from ordered molecular motion, the amount
of entropy is also a measure of the molecular disorder, or
randomness, of a system.
It is now clear that we can’t construct a heat engine with just
one +ve heat interaction

The above engine is not possible

Perpetual motion machine of the second kind is a machine
which produces work from a single heat source. In this kind of
perpetual motion machine, there is only one heat reservoir,
and it is being spontaneously cooled generating work without
heat transfer to a cooler reservoir
 Second law of thermodynamics:
There are two sub laws in second law to overcome all the
disadvantage of first law, they are
Kelvin-Plank statement
Clausius statement
Kelvin-Plank statement:
It states” All the heat energy given to an engine cannot be
converted into useful work, some amount of heat energy will be
rejected to the surroundings or sink.”

A thermal energy reservoir can be

considered as something in which even
if you add or take heat out from won't
have any change in its
temperature or it can be thought of as
a reservoir of infinite heat capacity.
Example - our atmosphere, ocean etc
Clausius statement:
the Clausius statement becomes: It is impossible to construct a
refrigerator that transfers heat from a cold reservoir to a hot
reservoir without aid from an external source. The Clausius
statement is related to the everyday observation that heat
never flows spontaneously from a cold object to a hot
object. Heat transfer in the direction of increasing
temperature always requires some energy input.
Both the Kelvin–Plank and Clausius statements of the
second law can be derived from the increase in entropy
principle, which states that the total entropy change for any
process is always greater than or equal to zero.

ΔS|Total ≥ 0

The implication of the word “total” is that it is possible for

entropy for a system to decrease when heat is transferred
out; however, the increase in entropy outside the system will
be greater than the entropy reduction within the
system. Physically entropy is a measure of the amount
of energy that is not available to produce work. Work and
mechanical energy are fully useable and therefore have no
associated entropy, and any process that generates entropy
is irreversible.
Third law of thermodynamics:
This statement is also referred to as the Nernst heat
theorem. The statement of Nernst was simplified by Planck.
He stated that not only the entropy change for processes
but also the actual entropy of each condensed substance
equals zero if the temperature approaches absolute zero.

According to this law, the entropy of a perfectly crystalline

substance is Zero at 0K temperature.
S0k = 0