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System:

A thermodynamic system is defined as a quantity of matter or a region in space which is

selected for the study.

Suroundings:

The mass or region outside the system is called surroundings.

Boundary:

The real or imaginary surfaces which separates the system and surroundings is called
boundary. The real or imaginary surfaces which separates the system and surroundings is
called boundary.

Types of thermodynamic system:

On the basis of mass and energy transfer the thermodynamic system is divided into three
types.

1. Closed system
2. Open system
3. Isolated system

Closed system: A system in which the transfer of energy but not mass can take place across
the boundary is called closed system. The mass inside the closed system remains constant.

For example: Boiling of water in a closed vessel. Since the water is boiled in closed vessel so
the mass of water cannot escape out of the boundary of the system but heat energy
continuously entering and leaving the boundary of the vessel. It is an example of closed
system.

Open system: A system in which the transfer of both mass and energy takes place is called
an open system. This system is also known as control volume.
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For example: Boiling of water in an open vessel is an example of open system because the
water and heat energy both enters and leaves the boundary of the vessel.

Isolated system: A system in which the transfer of mass and energy cannot takes place is
called an isolated system.

For example: Tea present in a thermos flask. In this the heat and the mass of the tea cannot
cross the boundary of the thermos flask. Hence the thermos flak is an isolated system.

Control Volume:

 It’s a system of fixed volume.

 This type of system is usually referred to as "open system” or a "control volume"
 Mass transfer can take place across a control volume.
 Energy transfer may also occur into or out of the system.
 Control Surface- It’s the boundary of a control volume across which the transfer
of both mass and energy takes place.
 The mass of a control volume (open system) may or may not be fixed.
 When the net influx of mass across the control surface equals zero then the mass of
the system is fixed and vice-versa.
 The identity of mass in a control volume always changes unlike the case for a control
mass system (closed system).
 Most of the engineering devices, in general, represent an open system or control
 volume.

Fig.: Control volume

Example:
Heat exchanger - Fluid enters and leaves the system continuously with the transfer of heat
across the system boundary.
Pump - A continuous flow of fluid takes place through the system with a transfer of
mechanical energy from the surroundings to the system
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Microscopic Approach:
 The approach considers that the system is made up of a very large number of
discrete particles known as molecules. These molecules have different velocities are
energies. The values of these energies are constantly changing with time. This
approach to thermodynamics, which is concerned directly with the structure of the
matter, is known as statistical thermodynamics.
 The behavior of the system is found by using statistical methods, as the number of
molecules is very large. So advanced statistical and mathematical methods are
needed to explain the changes in the system.
 The properties like velocity, momentum, impulse, kinetic energy and instruments
cannot easily measure force of impact etc. that describe the molecule.
 Large numbers of variables are needed to describe a system. So the approach is
complicated.
Macroscopic Approach:
 In this approach a certain quantity of matter is considered without taking into
account the events occurring at molecular level. In other words, this approach to
thermodynamics is concerned with gross or overall behavior. This is known as
classical thermodynamics.
 The analysis of macroscopic system requires simple mathematical formula.
 The value of the properties of the system are their average values. For examples
consider a sample of gas in a closed container. The pressure of the gas is the average
value of the pressure exerted by millions of individual molecules.
 In order to describe a system only a few properties are needed.

S.No Macroscopic Approach Microscopic Approach

In this approach a certain quantity of The matter is considered to be

matter is considered without taking comprised of a large number of tiny
into account the events occurring at particles known as molecules, which
molecular level. moves randomly in chaotic fashion.
The effect of molecular motion is
1
considered.

Analysis is concerned with overall The Knowledge of the structure of

behavior of the system. matter is essential in analyzing the
2 behavior of the system.
This approach is used in the study of This approach is used in the study of
3 classical thermodynamics. statistical thermodynamics.
A few properties are required to Large numbers of variables are
4 describe the system. required to describe the system.
The properties like pressure, The properties like velocity,
temperature, etc. needed to describe momentum, kinetic energy, etc.
the system, can be easily measured. needed to describe the system,
5 cannot be measured easily.
The properties of the system are their The properties are defined for each
6 average values. molecule individually.
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This approach requires simple No. of molecules are very large so it

mathematical formulas for analyzing requires advanced statistical and
the system. mathematical method to explain any
7 change in the system.

Thermodynamic Equilibrium:

A thermodynamic 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.
An isolated system always reaches in the course of time a state of thermodynamic
equilibrium and can never depart from it spontaneously.
Therefore, there can be no spontaneous change in any macroscopic property if the system
exists in an equilibrium state. A thermodynamic system will be in a state of thermodynamic
equilibrium if the system is the state of Mechanical equilibrium, Chemical equilibrium and
Thermal equilibrium.
 Mechanical equilibrium: The criteria for Mechanical equilibrium are the equality of
pressures.
 Chemical equilibrium: The criteria for Chemical equilibrium are the equality of
chemical potentials.
 Thermal equilibrium: The criterion for Thermal equilibrium is the equality of
temperatures.
State:

The thermodynamic state of a system is defined by specifying values of a set of measurable

properties sufficient to determine all other properties. For fluid systems, typical properties
are pressure, volume and temperature. More complex systems may require the
specification of more unusual properties. As an example, the state of an electric battery
requires the specification of the amount of electric charge it contains.

Property:

Properties may be extensive or intensive.

Intensive properties: The properties which are independent of the mass of thesystem.
For example: Temperature, pressure and density are the intensive properties.
Extensive properties: The properties which depend on the size or extent of the system are
called extensive properties.
For example: Total mass, total volume and total momentum.

Process:
When the system undergoes change from one thermodynamic state to final state due
change in properties like temperature, pressure, volume etc, the system is said to have
undergone thermodynamic process.
Various types of thermodynamic processes are: isothermal process, adiabatic process,
isochoric process, isobaric process and reversible process.
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Cycle:
Thermodynamic cycle refers to any closed system that undergoes various changes due to
temperature, pressure, and volume, however, its final and initial state are equal. This cycle
is important as it allows for the continuous process of a moving piston seen in heat engines
and the expansion/compression of the working fluid in refrigerators, for example. Without
the cyclical process, a car wouldn't be able to continuously move when fuel is added, or a
refrigerator would not be able to stay cold.
Visually, any thermodynamic cycle will appear as a closed loop on a pressure volume
diagram.
Examples: Otto cycle, Diesel Cycle, Brayton Cycle etc.

Reversibility:
Reversibility, in thermodynamics, a characteristic of certain processes (changes of a system
from an initial state to a final state spontaneously or as a result of interactions with other
systems) that can be reversed, and the system restored to its initial state, without leaving
net effects in any of the systems involved.
An example of a reversible process would be a single swing of a frictionless pendulum from
one of its extreme positions to the other. The swing of a real pendulum is irreversible
because a small amount of the mechanical energy of the pendulum would be expended in
performing work against frictional forces, and restoration of the pendulum to its exact
starting position would require the supply of an equivalent amount of energy from a second
system, such as a compressed spring in which an irreversible change of state would occur.

Quasi static process:

When a process is processing in such a way that system will be remained infinitesimally
close with equilibrium state at each time, such process will be termed as quasi static process
or quasi equilibrium process.
In simple words, we can say that if system is going under a thermodynamic process through
succession of thermodynamic states and each state is equilibrium state then the process will
be termed as quasi static process.
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Fig: Quasistatic process

We will see one example for understanding the quasi static process, but let us consider one
simple example for better understanding of quasi static process. If a person is coming down
from roof to ground floor with the help of ladder steps, then it could be considered as quasi
static process. But if he jumps from roof to ground floor then it will not be a quasi-static
process.
Weight placed over the piston is just balancing the force which is exerted in upward
direction by gas. If we remove the weight from the piston, system will have unbalanced
force and piston will move in upward direction due to force acting over the piston in upward
direction by the gas.

Irreversible Process:
The irreversible process is also called the natural process because all the processes occurring
in nature are irreversible processes. The natural process occurs due to the finite gradient
between the two states of the system. For instance, heat flow between two bodies occurs
due to the temperature gradient between the two bodies; this is in fact the natural flow of
heat. Similarly, water flows from high level to low level, current moves from high potential
to low potential, etc.
 In the irreversible process the initial state of the system and surroundings cannot be
restored from the final state.
 During the irreversible process the various states of the system on the path of
change from initial state to final state are not in equilibrium with each other.
 During the irreversible process the entropy of the system increases decisively and it
cannot be reduced back to its initial value.
 The phenomenon of a system undergoing irreversible process is called as
irreversibility.
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Causes of Irreversibility:
Friction: Friction is invariably present in real systems. It causes irreversibility in the process
as work done does not show an equivalent rise in the kinetic or potential energy of the
system. The fraction of energy wasted due to frictional effects leads to deviation from
reversible states.
Free expansion: Free expansion refers to the expansion of unresisted type such as expansion
in a vacuum. During this unresisted expansion the work interaction is zero, and without the
expense of any work, it is not possible to restore initial states. Thus, free expansion is
irreversible.
Heat transfer through a finite temperature difference: Heat transfer occurs only when there
exists temperature difference between bodies undergoing heat transfer. During heat
transfer, if heat addition is carried out in a finite number of steps then after every step the
new state shall be a non-equilibrium state.
Nonequilibrium during the process: Irreversibilities are introduced due to lack of
thermodynamic equilibrium during the process. Non-equilibrium may be due to mechanical
inequilibrium, chemical inequilibrium, thermal inequilibrium, electrical inequilibrium, etc.
and irreversibility is called mechanical irreversibility, chemical irreversibility, thermal
irreversibility, electrical irreversibility respectively. Factors discussed above are also causing
non-equilibrium during the process and therefore make process irreversible.

Heat:
It is the energy in transition between the system and the surroundings by virtue of the
difference in temperature Heat is energy transferred from one system to another solely by
reason of a temperature difference between the systems. Heat exists only as it crosses the
boundary of a system and the direction of heat transfer is from higher temperature to lower
temperature. For thermodynamics sign convention, heat transferred to a system is positive;
Heat transferred from a system is negative.

Work:
Thermodynamic definition of work: Positive work is done by a system when the sole effect
external to the system could be reduced to the rise of a weight.
Work done BY the system is positive and work done ON the system is negative.

Types of work interaction:

 Expansion and compression work (displacement work)
 Work of a reversible chemical cell
 Work in stretching of a liquid surface
 Work done on elastic solids
 Work of polarization and magnetization

Point and Path functions:

 Point function does not depend on the history (or path) of the system. It
only depends on the state of the system.
 Examples of point functions are: temperature, pressure, density, mass,
volume, enthalpy, entropy, internal energy etc.
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 Path function depends on history of the system (or path by which system arrived at
a given state).
 Examples for path functions are work and heat.
 Path functions are not properties of the system, while point functions are properties
of the system.
 Change in point function can be obtained by from the initial and final values of
the function, whereas path has to defined in order to evaluate path functions.

Zeroth Law of Thermodynamics:

The Thermodynamics Zeroth Law states that if two systems are at the same time in
thermal equilibrium with a third system, they are in equilibrium with each other.
If an object with a higher temperature comes in contact with an object of lower
temperature, it will transfer heat to the lower temperature object. The objects will approach
the same temperature and in the absence of loss to other objects, they will maintain a single
constant temperature. Therefore, thermal equilibrium is attained.

If objects ‘A’ and ‘C’ are in thermal equilibrium with ‘B’, then object ‘A’ is in thermal
equilibrium with object ‘C’. Practically this means all three objects are at the same
temperature and it forms the basis for comparison of temperatures.

Principles of Thermometry:

Thermometry is the science and practice of temperature measurement. Any measurable

change in a thermometric probe (e.g. the dilatation of a liquid in a capillary tube, variation
of electrical resistance of a conductor, of refractive index of a transparent material, and so
on) can be used to mark temperature levels, that should later be calibrated against an
internationally agreed unit if the measure is to be related to other thermodynamic variables.
Thermometry is sometimes split in metrological studies in two subfields: contact
thermometry and noncontact thermometry. As there can never be complete thermal
uniformity at large, thermometry is always associated to a heat transfer problem with some
space-time coordinates of measurement, given rise to time-series plots and temperature
maps.
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Constant Volume gas Thermometer:

When we heat a gas keeping the volume constant, its pressure increases and when we cool
the gas its pressure decreases. The relationship between pressure and temperature at
constant volume is given by the law of pressure. According to this law, the pressure of a gas
changes by of its original pressure at 0 oC for each degree centigrade (or Celsius) rise in
temperature at constant volume.
If Po is the pressure of a given volume of a gas at 0 oC and Pt is the pressure of the same
volume of the gas (i.e., at constant volume) at toC, then

Pt Po  Po

t
273
P P t
(1 )
t 
o 273

It consists of a glass bulb B connected to a tube A, through a capillary glass tube ‘C’. The
tube A is connected to a mercury reservoir R which is clamped on the board and can be
lowered or raised whenever required to keep the volume of the air constant. The capillary
tube C is provided with a three way stopper S and can be used to connect capillary and bulb
as well as to disconnect tube from bulb B. A pointer is provided such that the end P is
projecting inside from the upper part of A. A scale calibrated in 0 oC is provided between A
and R.
The whole apparatus is leveled by adjusting the leveling screws. By adjusting the stopper,
the bulb ‘B’ is filled with air or some gas and the pointer is adjusted so that tip of the pointer
just touches the level of mercury in the tube A. After filling the bulb, it is kept in an ice bath
for some time till the air inside the bulb attains the temperature of ice at which the mercury
level becomes stationary. Now the reservoir R is adjusted so that the level of mercury in the
tube A just touches the tip of the pointer P.
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The difference between the mercury levels in the two tubes is noted and let it be ho. If Po is
the pressure exerted by the air in the bulb, then
P o  P  h0

Now ice bath is removed and the bulb B is surrounded with steam.

Scales of Temperature:
There are three temperature scales in use Fahrenheit, Celsius and Kelvin. Fahrenheit
temperature scale is a scale based on 32 for the freezing point of water and 212 for the
boiling point of water, the interval between the two being divided into 180 parts.
The conversion formula for a temperature that is expressed on the Celsius (C) scale to its
Fahrenheit (F) representation is: F = 9/5C + 32.

Celsius temperature scale also called centigrade temperature scale, is the scale based on 0
for the freezing point of water and 100 for the boiling point of water.
Kelvin temperature scale is the base unit of thermodynamic temperature measurement in
the International System (SI) of measurement. It is defined as 1/ 273.16 of the triple point
(equilibrium among the solid, liquid, and gaseous phases) of pure water.