FD3404

PRINCIPLES OF THERMODYNAMICS

LECTURE NOTES

UNIT 1 – BASIC CONCEPTS

COURSE INSTRUCTOR

HEMAMALINI S, M. Tech.,

Teaching Assistant

2023

SREE SASTHA INSTITUTE OF ENGINEERING AND TECHNOLOGY

(SSIET)

CHEMBARAMBAKKAM, CHENNAI - 600123

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 UNIT I - BASIC CONCEPTS
SYLLABUS: Basic concepts - concept of continuum, comparison of microscopic and macroscopic
approach. Path and point functions. Intensive and extensive, Total and specific quantities. System
and their types. Thermodynamic Equilibrium State, path and process. Quasi-static, reversible and
irreversible processes. Heat and work transfer, definition and comparison, sign convention.
Displacement work and other modes of work. P-V diagram.

THERMODYNAMICS
Thermodynamics is the science of energy transfer. It also studies the effect of energy transfer on the
physical properties of substances.
William Thomson in 1749, coined the term ‘Thermodynamics’. The name thermodynamics was
derived from the Greek word, ‘therme’ means heat and ‘dynamics’ means power.
Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation
to energy, entropy, and the physical properties of matter and radiation. It is the study of the
relationship between heat, work, temperature and energy.
Definition:
The study of the flow of heat or any other form of energy into or out of a system as it undergoes a
physical or chemical transformation is called Thermodynamics.
The behaviour of these quantities is governed by the four laws of thermodynamics which convey a
quantitative description using measurable macroscopic physical quantities but may be explained in
terms of microscopic constituents by statistical mechanics.
Scope of Thermodynamics:
1. Most of the important laws of Physical Chemistry, including the van’t Hoff law of lowering
of vapour pressure, Phase Rule and the Distribution Law can be derived from the laws of
thermodynamics.
2. It tells whether a particular physical or chemical change can occur under a given set of
conditions of temperature, pressure and concentration.
3. It also helps in predicting how far a physical or chemical change can proceed, until the
equilibrium conditions are established.
Limitations of Thermodynamics:
1. Thermodynamics is applicable to macroscopic systems consisting of matter in bulk and
not to microscopic systems of individual atoms or molecules. It ignores the internal
structure of atoms and molecules.
2. Thermodynamics does not bother about the time factor. That is, it does not tell anything
regarding the rate of a physical change or a chemical reaction. It is concerned only with the
initial and the final states of the system.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 Fig: Applications of Thermodynamics

SYSTEM, SURROUNDINGS AND BOUNDARY

A thermodynamic system refers to that part of the universe in which observations are made, and the
remaining universe constitutes the surroundings. The surroundings contain everything other than the
system. The system and the surroundings together make up the universe.

The universe = The system + The surroundings

The exchange of energy between the system and surroundings usually takes place in the form of heat
(or) work (or) both.

Fig: Thermodynamic System

System – A thermodynamic system is defined as the quantity of matter or region in space that is of
the system.

Surroundings – The mass or region outside the system is called the surroundings.

Boundary – The surface that separates the system and surroundings is called the boundary.

Types of Systems:-

Thermodynamic systems are classified as:

1. Open systems
2. Closed systems
Hemamalini S, M.Tech., Department of Food Technology, SSIET
 3. Isolated Systems

1. Open System:

If the thermodynamic system has the capacity to exchange both matter and energy with its
surroundings, it is said to be an open system.

Examples:

• Consider a beaker in the presence of reactants in an open beaker. Here the boundary is an
imaginary surface enclosing the beaker and reactants.

• A steam turbine, a pool filled with water, where the water can enter or leave the pool.

• A stove top, because heat and water vapour can be lost at air.

2. Closed System

A system which has the ability to exchange only energy with its surroundings and cannot exchange
matter is known as a closed system.

Examples:

• Reactants placed in a closed vessel made of materials like steel, copper, and silver are an
ideal example of a closed system since the material of the vessel is conducting in nature.
• A cylinder in which the valve is closed is an example of a closed system. When the cylinder
is heated or cooled, it does not lose its mass.

3. Isolated System

A system which cannot exchange matter or energy with the surroundings is known as an isolated
system. The zeroth law of thermodynamics states that thermodynamic processes do not affect the
total energy of the system.

Examples:

• Reactants are present in a thermos flask or an insulated vessel, where neither energy nor
matter is exchanged with the environment.

• If the piston and cylinder arrangement in which the fluid like air or gas is being compressed
or expanded is insulated, it becomes an isolated system.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 Fig: Types of thermodynamic systems
Types of systems based on phase:-
Phase – A quantity of matter homogeneous throughout in chemical composition and physical
structure is called phase. There are three types of phase, viz., solid, liquid and gas.

Based on phases, systems are classified as:

1. Homogeneous system
2. Heterogeneous system

1. Homogeneous system

A system consisting of a single phase and it is uniform throughout the system (or) the one whose
chemical composition and physical properties are the same in all parts of the system or change
continuously from one point to another is known as homogeneous system.

Example: a system containing only water.

2. Heterogeneous system

A system containing more than one phase and it is not uniform throughout the system (or) the one
whose chemical composition and physical properties are different in all parts of the system is known
as heterogeneous system.

Example: a system containing both ice and water.

MACROSCOPIC AND MICROSCOPIC APPROACH

The study of thermodynamics is classified into two categories. They are:
1. Macroscopic approach
2. Microscopic approach

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 Table: Difference between macroscopic and microscopic approach
S. No. Macroscopic Approach Microscopic Approach
1 In the macroscopic approach, a certain The matter is considered to be comprised
quantity of matter is considered without of a large number of tiny particles known
considering the events occurring at the as molecules, which move randomly in a
molecular or atomic level. disordered fashion. The effect of
molecular motion is considered.
2 An analysis is concerned with the overall Knowledge of the structure of matter is
behaviour of the system. In other words, it essential in analysing the behaviour of the
only deals with the effects of these atomic or system i.e., the behaviour of matter can be
molecular events that are perceived by studied by combining the effects of the
human sense. individual atoms or molecules.
3 This approach is used in the study of This approach is used in the study of
classical thermodynamics. statistical thermodynamics.
4 A few properties are required to describe Large numbers of variables are required
the system. to describe the system.
5 The properties like pressure, temperature, The properties like velocity, momentum,
etc. needed to describe the system, can be kinetic energy, etc. needed to describe the
easily measured. system, cannot be measured easily, since
each atom/molecule has a certain
position, velocity and energy at a certain
time and it changes continuously because
of collision between molecules.
6 The properties of the system are their The properties are defined for each
average values. molecule individually.
7 This approach requires simple No. of molecules is very large so it
mathematical formulas for analysing the requires an advanced statistical and
system. mathematical method to explain any
change in the system
8

Fig: Microscopic approach

Fig: Macroscopic approach

CONCEPT OF CONTINUUM
Concept of continuum brings together the macroscopic and microscopic approach to
thermodynamics.
“The concept of the continuum is a kind of idealization of the continuous description of matter
where the properties of the matter are considered as continuous functions of space variables.”
Matter is made up of many atoms or molecules which are tightly packed, but still, there are empty
spaces between them and mass distribution is not uniform. But the concept of the continuum assumes
a continuous and uniform distribution of mass throughout (or) within the matter or system.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

Describing a fluid flow quantitatively makes it necessary to assume that flow variables (pressure,
velocity, etc.) and fluid properties vary continuously from one point to another. Mathematically
descriptions of flow on this basis have proved to be reliable and treatment of fluid medium as a
continuum has firmly become established.
For example:
Let us consider a small mass, 𝛿m contained in a small volume, 𝛿V. The average mass density of the
system within 𝛿V is given by 𝛿m/𝛿V.

If we plot 𝛿m/𝛿V and 𝛿V, we will find that for large values of 𝛿V, we have

𝛅𝐦
𝛒 =
𝛅𝐕
𝛅𝐦
𝛒 = 𝐥𝐢𝐦
𝛅𝐕 → 𝟎 𝛅𝐕

But for very low values of 𝛿V, the value of 𝛿m/𝛿V fluctuates. It is because of the molecular
movement in and out of the volume, 𝛿V. The smallest volume which may be regarded as a continuum
is 𝛿V'.
The density of the system at a point is thus defined as,
𝛅𝐦
𝛒 = 𝐥𝐢𝐦
𝛅𝐕 →𝛅𝐕′ 𝛅𝐕
Similarly, the fluid velocity at point P is defined as the instantaneous velocity of the centre of gravity
of the smallest continuous volume 𝛿V'.

THERMODYNAMIC EQUILIBRIUM STATE, PATH, PROCESS AND CYCLE

Let a quantity of gas at pressure p1 and volume V1 be filled in the cylinder as shown in figure.
Consider its initial state 1. Now, this gas changes from state 1 to state 2. So, it has pressure p2 and
volume V2.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 Fig: System explaining the thermodynamic state, path, process and cycle
Thermodynamic State / Thermodynamic Equilibrium State:
The thermodynamic state of the system is defined by specifying values of a set of measurable
properties sufficient to determine other properties. It is a condition of the system specified by its
properties (any two independent properties from pressure, volume and temperature).
The fundamental properties of pressure, temperature, volume, mass and composition are state
variables/ state functions/ thermodynamic functions.
Process:
The process is defined as any change that a system undergoes from one equilibrium state to another
equilibrium.
Path:
The series of states through which a system passes during the process is called a path.
Cycle:
Consider a system undergoes one more process 2-1, i.e., this gas changes its state from state-2 to
state-1. So, it has a pressure p1 and volume V1 as shown in the figure above.
“If a system undergoes two or more processes and returns to its initial state at the end of all
processes, the system is said to have undergone a cycle”.
POINT AND PATH FUNCTION
The point (or) state function and path function are discussed below.
Table: Difference between point/state function and path function
S. No. Point / State Function Path Function
1 The property of the system which does The quantities that are dependent on the
not depends on the path of the process, path of the process are called path function.
but depends on the states (two end There are certain quantities which cannot be
condition of process) of the process is located on the graph but are represented by
known as point function or state function. the area of the graph.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 2 Its values are based on the state of the
Its values are based on how that particular
system (i.e. pressure, volume,
thermodynamic state is achieved.
temperature etc.)
3 No matter by which process the state is
Different processes to obtain a particular
obtained, its values will always remain
state will give us different values.
the same.
4 Only initial and final states of the process We need to know exact path followed by
are sufficient the process
5 Its values are independent of the path Its values are dependent on the path
followed followed
6 It is an exact or perfect differential It is an inexact or imperfect differential.
7 Its cyclic integral is always zero Its cyclic integral may or may not be zero
8 It is property of the system It is not the property of the system
9 Its examples are density, enthalpy, Its examples are Heat, work etc.
internal energy, entropy etc

INTENSIVE AND EXTENSIVE PROPERTIES

Thermodynamic quantities are classified into intensive and extensive properties. The intensive and
extensive properties are explained below.
Table: Difference between intensive and extensive properties
S. No. Intensive Properties Extensive Properties
1 An intensive property is a property that An extensive property is a property that
does not depend on the mass of the depends on the system size or the amount of
substance (or) system matter in the system
2 It is an independent property It is a dependent property
3 The size does not change The size changes
4 It cannot be computed It can be computed
5 It can be easily identified It cannot be easily identified
6 It is helpful for the identification of It is helpful for describing the samples.
samples.
7 It can be observed easily It cannot be observed easily
8 It changes the physical behaviours It changes the nature of the substance
9 Examples: colour, ductility, conductivity, Examples: length, mass, weight, volume,
odour, melting point, boiling point, etc. etc.

TOTAL AND SPECIFIC QUANTITIES

Total quantities: A total quantity refers to all the quantities (intensive and extensive) involved in
that particular system.
Specific quantities: A specific quantity refers to an intensive quantity obtained by dividing an
extensive quantity of interest by mass.
volume of the mixture V
Example: Specific volume , v = =
total mass of the mixture m

Hemamalini S, M.Tech., Department of Food Technology, SSIET

THERMODYNAMIC EQUILIBRIUM

Thermodynamic equilibrium is an axiomatic concept of thermodynamics. The word ‘equilibrium’

means ‘state of balance’ i.e., there is no unbalanced potentials within the system.

“A system is said to be in exist in a state of thermodynamic equilibrium when no change in any

macroscopic property is registered, if the system is isolated from its surroundings” (or) “A system is
said to be in a state of thermodynamic equilibrium if the value of properties is the same at all points
in the system”.

An isolated system always reaches in course of time a state of thermodynamics equilibrium and can
never depart from it spontaneously. Therefore, there can be no spontaneous changes in any
macroscopic property if the system exists in equilibrium state. Thermodynamics mainly studies the
properties of physical systems that are found in equilibrium states.

A system will be in a state of thermodynamic equilibrium, only if the conditions for the types
of equilibrium viz., thermal, mechanical and chemical equilibrium are satisfied.

The types of thermodynamic equilibrium are discussed below:

1. Thermal equilibrium
2. Mechanical equilibrium
3. Chemical equilibrium

1. Thermal equilibrium

If the temperature of the system does not change with time and has same value at all points of the
system, then the system is said to be in thermal equilibrium.

Example: If the system exists in thermal equilibrium, then the system maintains same temperature at
all points and time.

Fig: a. (left side) Non-thermal equilibrium system b. (right side) Thermal equilibrium system

2. Mechanical equilibrium

A system is in mechanical equilibrium if there are no unbalanced forces within the system or between
surroundings. The pressure in the system is same at all points and does not change with respect to
time.

Example: If the system exists in mechanical equilibrium, then the system maintains same pressure at
all points and time.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 Fig: Mechanical equilibrium

3. Chemical equilibrium

A system is in chemical equilibrium if its chemical composition does not change with time and no
chemical reaction takes place in system.

When anyone of the condition for the three types of equilibrium are not satisfied, a system is said to
be in a non-equilibrium state.

Example: If the system exists in chemical equilibrium, then there will be no chemical reaction and
same composition at all points and time occurs.

Fig: Chemical equilibrium

THERMODYNAMIC PROCESSES
Thermodynamic process is a process in which the thermodynamic state of a system is changed. The
states of a thermodynamic system can be changed by interacting with its surrounding through work
and heat. When changes occur in a system, it is said that the system is undergoing a process.
“A thermodynamic process involves a change from one type of equilibrium microstate to another
type of system” (or) “A process occurs when the system undergoes a change in a state or an energy
transfer at a steady state is known as thermodynamic process”.

Fig: Basic thermodynamic processes

Hemamalini S, M.Tech., Department of Food Technology, SSIET
Types of thermodynamic processes:-

There are nine thermodynamic processes, including:

1. Isothermal process
2. Isobaric process
3. Isochoric process
4. Adiabatic process
5. Cyclic process
6. Reversible process
7. Irreversible process
8. Quasi-static process
9. Non-quasi static process
10. Isentropic Process
11. Polytropic Process
12. Throttling Process

1. Isothermal process (ΔT = 0 & T = constant)

“When a system transitions from one state to another, its temperature remains constant, then the
process is said to be an isothermal process”. Some heat transfer does take place but it is typically at
an extremely slow rate which enables it to attain thermal equilibrium.

The heat transfer into or out of the system typically must happen at such a slow rate to continually
adjust to the temperature of the reservoir through heat exchange. In each of these states, the thermal
equilibrium is maintained.

Fig: Isothermal Process

Since, W = ∫PdV 1
From Gas Law,

PV = nRT
nRT
P= V 2
Substituting equation 2 in 1, we get

VB dV
W = nRT ∫VA V

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 𝐕𝐁
W = nRT ln 𝐕𝐀

If VB > VA, the work done will be positive.

If VB < VA, the work done is negative.

Internal energy is constant in such systems because the temperature is constant, ΔU = 0. Therefore,
according to the first law of thermodynamics,

Q = ΔU + W

Therefore, Area under the curve = Q = W

Table: Characteristics of isothermal processes

Example - Hot water in a thermos flask, if we remove a certain quantity of water from the flask but
keep its temperature constant at 50 degrees Celsius.

2. Isobaric process (Δp = 0 & p = constant)

“A thermodynamics process in which the pressure of the system does not change with time is called
an isobaric process”. The heat transfer into or out of the system does work but also changes the
internal energy of the system.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 Fig: a. Example of isobaric process. b. Graphical representation of isobaric process

Since there are changes in internal energy (dU) and changes in system volume (∆V), engineers often
use the enthalpy of the system, which is defined as:

H = U + pV

In many thermodynamic analyses, it is convenient to use enthalpy instead of internal energy,

especially in the first law of thermodynamics.
Work done, W = PΔV

If ΔV = positive, the work done will be positive.

If ΔV = negative, the work done will be negative.

F
Since, P = (A ) and ΔV = ΔhA, we have

F
W = ( )ΔhA
A

Therefore, Area under the curve = W = FΔh

Table: Characteristics of isobaric processes

Example - Boiling of water to steam or the freezing of water to ice.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

3. Isochoric process / Isometric process / Isovolumetric process (ΔV = 0 & V = constant)

“The process during which the volume of the system remains constant is called an isochoric process”.
It describes the behavior of gas inside the container that cannot be deformed. Since the volume
remains constant, the heat transfer into or out of the system does not the p∆V work (W=0) but only
changes the system’s internal energy (the temperature).

According to the first law of thermodynamics,

ΔQ = ΔU + W

where Q = heat transferred and ΔU = change in internal energy.

Therefore, ΔQ = ΔU

Fig: Graphical representation of isochoric process

Table: Characteristics of isochoric processes

Example - Heating of gas in a closed cylinder.

4. Adiabatic process (ΔQ = 0 & Q = constant)

“An adiabatic process is a thermodynamic process in which there is no heat transfer into or out of
the system”. The system can be considered to be perfectly insulated. In an adiabatic process, energy
is transferred only as work. The assumption of no heat transfer is very important since we can use
the adiabatic approximation only in very rapid processes. There is not enough time for the transfer
of energy as heat to take place to or from the system in these rapid processes.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 Fig: Graphical representation of adiabatic process

According to the first law of thermodynamics,

ΔQ = ΔU + W

For adiabatic process,

ΔU = -W = Area under the curve

So, if work done is negative internal energy increases and vice versa.

Mathematically this process is represented as

W = ∫PdV 1

We have, PVγ = K (constant)

K
P = Vγ

Substituting P in 1, we get
VB dV
W = K ∫VA Vγ

𝟏−𝛄 𝟏−𝛄
(𝑽𝑩 − 𝑽𝑨 )
Area under the curve = W = K( )
𝟏−𝛄

Table: Characteristics of isochoric processes

Hemamalini S, M.Tech., Department of Food Technology, SSIET

5. Cyclic Process
“A process that eventually returns a system to its initial state is called a cyclic process”. After a cycle,
all the properties have the same value they had at the beginning. For such a process, the final state is
the same as the initial state, so the total internal energy change must be zero.
It must be noted, according to the second law of thermodynamics, not all heat provided to a cycle
can be transformed into an equal amount of work. Some heat rejection must take place. The thermal
efficiency, ηth, of any heat engine as the ratio of the work it does, W, to the heat input at the high
temperature, QH. ηth = W/QH.

Fig: Graphical representation of cyclic process

6. Reversible Process
In thermodynamics, “a reversible process is defined as a process that can be reversed by inducing
infinitesimal changes to some property of the system”. In so doing, it leaves no change in either the
system or surroundings.
During the reversible process, the system’s entropy does not increase, and the system is in
thermodynamic equilibrium with its surroundings.
7. Irreversible Process

In thermodynamics, an irreversible process is defined as “a process that cannot be reversed, which

cannot return both the system and the surroundings to their original conditions”.
During irreversible process the entropy of the system increases.
Table: Difference between reversible and irreversible process
S.No. Reversible Process Irreversible Process
1 A reversible process is a process that can be An irreversible process is a process that
reversed to obtain the initial state of the cannot be reversed to obtain the initial state
system of the system
A +B ⇌ C + D A → B +C
2 It takes place in infinite number of It takes place infinite times
infinitesimally small steps and it would
take infinite times to occur
3 Infinite changes occur in system Finite changes occur in system
4 It is imaginary as it assumes the presence It is real and can be performed actually
of frictionless and weightless piston
5 It is in equilibrium state at all stages of the It is in equilibrium state only at the initial
operation and final stages of the operation

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 6 All changes can be reversed when the After this type of process has occurred, all
process is carried out in reversible direction changes do not return to the initial stage by
themselves
7 It is extremely slow It proceeds at measurable speed
8 Work done by reversible process is greater Work done by irreversible process is
than the corresponding irreversible process smaller than the corresponding irreversible
process
9 Example Example

8. Quasi-static process

“When a system proceeds in such a way that, the system remains close to a thermodynamic
equilibrium state at all times, is called as quasi-static process”. It is referred to as slow process. The
word ‘quasi’ meaning ‘almost’. It has all of its states in equilibrium. It is a succession of equilibrium
systems.
Let us consider a system of gas contained in a cylinder. The system initially is in an equilibrium state
and described by properties p1, V1 and T1. The weights on the piston just balance the upward force
exerted by the gas. The weights on the piston are made up of many very small pieces of weight and
these weights are removed one by one very slowly from the top of the piston, till it reaches the state
which is described by properties p2, V2 and T2. If the piston is moved slowly, the molecule will
have sufficient time to redistribute. As a result, the pressure inside the cylinder will always be
uniform and will reduce at the same rate at all locations. So, every state passed through by the system
will be an equilibrium state. Such a process passes through all the equilibrium points is called quasi-
static process.

Fig: Quasi-static process

The characteristics of quasi-static process are:
• It is a reversible process.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 • The main characteristic of this process is a succession of equilibrium states.
• Infinitesimally slowness is the characteristic feature of a quasi-static process.
• It is an idealized process and is not a true representation of an actual process.
• All states of the system pass through equilibrium states.
• Many actual processes are closely approximate and they can be modelled as quasi-static
equilibrium with negligible zero.
• The quasi-static process produces maximum work or consumes less work, so these processes
serve as standards at which actual processes can be compared.
9. Non-Quasi static process
“If a process is carried out in such a way that at every instant the system departs finitely from the
thermodynamic equilibrium state, such a process is called non-quasi-static process”.
Let us consider a system of gas contained in a cylinder. The system initially is in an equilibrium state
and described by properties p1, V1 and T1. The weights on the piston just balance 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 and T2. But the
intermediate states passed through by the system are non-equilibrium states which cannot be
described by thermodynamic coordinates and it will not be possible to describe the path.

Fig: Non-Quasi-static process

But the intermediate states passed through by the system are no equilibrium states which cannot be
described by thermodynamic coordinates. Therefore, the p-v plot should be drawn in dotted line.
Table: Difference between entropy and enthalpy
S.No. Enthalpy Entropy
1 Enthalpy is the measure of total heat Entropy is the measure of the level of
content present in the thermodynamic disorder in a thermodynamic system
system under constant pressure
2 It is represented as, ΔH = ΔE + PΔV It is represented as, ΔS = ΔQ/T
where E is the internal energy, P is the where Q is the heat content and T is the
pressure and E is the energy. temperature.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 3 Enthalpy is a kind of energy Entropy is a property
4 It is the sum of the internal energy and the It is the measurement of the randomness of
flow of energy molecules.
5 It is denoted by the symbol H It is denoted by the symbol S
6 It was termed by a scientist named Heike It was termed by a scientist named Rudolf
Kamerlingh Onnes Clausius
7 Its unit is Jmol-1 Its unit is JK-1
8 It is applicable to related standard It does not have any limits or conditions
conditions
9 The system favours minimum enthalpy The system favours maximum entropy
10

10. Isentropic Process (ΔS = 0 & S = constant)

“An isentropic process is a thermodynamic process in which the entropy of the fluid or gas remains
constant”. It means the isentropic process is a special case of an adiabatic process in which there is
no transfer of heat or matter. It is a reversible adiabatic process. An isentropic process can also be
called a constant entropy process. In engineering, such an idealized process is very useful for
comparison with real processes.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 Fig: Graphical representation of isentropic process

Table: Characteristics of isentropic processes

11. Polytropic Process

A polytropic process is any thermodynamic process that can be expressed by the following equation:
pVn = constant
The polytropic process can describe gas expansion and compression, which include heat transfer.
The exponent n is known as the polytropic index, and it may take on any value from 0 to ∞, depending
on the particular process.

Fig: Graphical representation of polytropic process

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 Table: Characteristics of polytropic processes

8. Throttling Process – Isenthalpic Process (ΔH = 0 & H = constant)

“A throttling process is a thermodynamic process in which the enthalpy of the gas or medium remains
constant”. The throttling process is one of the isenthalpic processes. During the throttling process,
no work is done by or on the system (dW = 0), and usually, there is no heat transfer (adiabatic) from
or into the system (dQ = 0). On the other, the throttling process cannot be isentropic. It is a
fundamentally irreversible process. Characteristics of throttling process:
 No Work Transfer
 No Heat Transfer
 Irreversible Process
 Isenthalpic Process
Throttling of the wet steam is also associated with the conservation of enthalpy. But in this case, a
reduction in pressure causes an increase in vapor quality.

P-V DIAGRAMS

“The PV diagram models the relationship between pressure (P) and volume (V) for an ideal gas”.

A system can be described by three thermodynamic variables, namely pressure, volume, and
temperature. But temperature depends on the other two variables P & V, thus only two variables are
taken into consideration as they are independent.

Fig: PV Diagram

Hemamalini S, M.Tech., Department of Food Technology, SSIET

From the PV diagram, it is inferred that if volume increases, the piston moves up and the plot in the
graph moves right and vice-versa. If the pressure increases (compression), the piston moves down
and the plot in the graph moves up and vice-versa.
[Refer Thermodynamic process for PV Diagram and learn for isobaric, isochoric, isothermal
and adiabatic process (write equations and diagram appropriately)]

HEAT AND WORK TRANSFER

A closed system and its surroundings can interact in two ways. They are:
1. Heat Transfer and
2. Work Transfer
1. HEAT TRANSFER
Heat is a form of energy in transit. It is a boundary phenomenon since it occurs only at the boundary
of a system.
“The transfer of heat energy across the boundary of the system by virtue of temperature difference
only is called heat transfer”. The symbol of heat transfer is Q and the units on the rate of heat transfer
are Joule/second, also known as a Watt.
Heat transfer is given as,
Q = m C ΔT
Where, Q – heat transfer (heat supplied), m – mass of the system, C – specific heat capacity and ΔT
– temperature difference.
Unit of heat transfer (Q) is given as, SI unit – Joule (J), MKS system – calorie (cal) and for rate of
heat transfer, the unit is kW or W.
The temperature difference is the ‘potential’ or ‘force’ and the heat transfer is the ‘flux’.
Sign convention of heat transfer:-
Sign convention – A choice of the physical significance of signs (+/-) for a set of quantities in a case
where the choices of sign are arbitrary.
The direction of heat transfer is taken from high temperature system to low temperature system. Heat
flow into a system is taken as positive and heat flow out of a system is taken as negative.

Fig: Sign convention of heat transfer

Types of heat transfer:-
Heat transfer between the system and surroundings across the border occurs in three different modes,
they are:
Hemamalini S, M.Tech., Department of Food Technology, SSIET
 a. Conduction
b. Convection
c. Radiation

Fig: Types of heat transfer

a. Conduction
The transfer of heat between two bodies in direct contact is known as conduction.
Example: Ironing of clothes, heat conduction through sand, etc.
The rate of conduction can be calculated by the following equation,
𝐊 𝐀 (𝐓𝟏 – 𝐓𝟐 )
Q= 𝐝

where,
Q - transfer of heat per unit time
K - thermal conductivity of the body
A - area of heat transfer
T1 - temperature of the hot region
T2 - temperature of the cold region
d - thickness of the body
b. Convection
The transfer of heat between a wall and a fluid system is known as convection.
Example: Boiling of water, blood circulation in warm blooded animals, etc.
The rate of convection can be calculated by the following equation,
Q = hc A (Ts – Tf)
where,
Q – transfer of heat per unit time
hc – coefficient of convective heat transfer
A – area of heat transfer
Ts – surface temperature
Hemamalini S, M.Tech., Department of Food Technology, SSIET
Tf – fluid temperature
c. Radiation
The heat may be transferred between two bodies separated by empty space (or) gases through
electromagnetic waves is known as radiation
Example: UV rays emitted by sun to earth, microwave radiation emitted in oven
P = e σ A (Tr – Tc)4
where,
P – net power of radiation
e – emissivity
σ – Stefan-Boltzmann constant = 5.670374419 × 10−8 W / m2 K4
A – area of radiation
Tr – radiation temperature
Tc – surrounding temperature
2. WORK TRANSFER
The work is done by a force as it acts upon a body moving in the direction of the force. The action
of a force through a distance (or of a torque through an angle) is called mechanical work. Work is
done by a system if the sole effect on things external to the system can be reduced to the raising of
a weight.
Work = Force x Distance
The unit of work is Nm (or) Joule.
“The movement of work (mechanical energy) transferred between systems (or) between system
and surroundings is known as work transfer”.
Work transfer is given as,

Work transfer, W = P ΔV

Where, P – pressure and ΔV – difference in volume.

The rate at which the work (W) is done is called as power (P). The SI unit of power is J/s (or) W.
Sign convention of work transfer:-
When work is done by a system, it is arbitarily taken to be positive and when work is done on a
system, it is taken as negative.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

 Fig: Sign convention of work transfer
Types of work transfer:-
Work is one of the forms in which system and surroundings can interact with each other. There are
various types of work transfer which can get involved between them.
1. pdV work / Displacement work
2. Electrical work
3. Shaft work
4. Paddle wheel work / Stirrer work
5. Flow work
6. Work done in stretching a wire
7. Work done in changing the area of a surface film
8. Magnetization of a paramagnetic solid
1. pdV work / Displacement work
The work done on the gas (or) by the gas, due to the acting gas pressure during a change in volume.
When the force acts upon the system and it undergoes a change in its position i.e., displacement
occurs then displacement work is said to be done.
2. Electrical work
The work produced due to unit current flow across unit voltage for unit time.
When a current flows through a resistor, taken as a system, there is work transfer into the system.
This is because the current can drive a motor, the motor can drive a pulley and the pulley can raise
a weight.
3. Shaft work
Shaft work refers to energy transferred across the boundary by a rotating shaft.
4. Paddle wheel work / Stirrer work
It is the work produced to the enforcement of the torque (force that cause the machinery to turn
round/rotate) which causes the angular displacement of the stirrer.
Note: Refer book (Nag, P. K. (2008). Engineering thermodynamics. New Delhi.) pg.no. 49-51, 55-
59 / hand written notes.
Also study pdV work in various quasi static processes from book (Nag, P. K. (2008). Engineering
thermodynamics. New Delhi.) pg.no. 51, 52 / hand written notes.

Hemamalini S, M.Tech., Department of Food Technology, SSIET

COMPARISION OF HEAT AND WORK TRANSFER
Similarities:-
1. Both heat and work transfer are path function.
2. Both heat and work transfer are associated with process and not state.
3. Both heat and work transfer are inexact differential (partial derivative (∂).
4. Both heat and work transfer are boundary phenomena.
Differences:-
S.No. Heat Transfer (Q) Work Transfer (W)
1 Heat transfer is considered as a low-grade Work transfer is considered as a high-grade
energy. energy.
2 It occurs due to temperature difference. It occurs when there is a displacement of
body.
3 Heat supplied (or) absorbed by a system is Work supplied to a system is considered as
considered as positive. negative.
4 Heat has a disordered (random) motion. Work has an ordered motion.

REFERENCES
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Hemamalini S, M.Tech., Department of Food Technology, SSIET
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Hemamalini S, M.Tech., Department of Food Technology, SSIET