Thermodynamics

202041

S.E-Semester I

Dr A. B. Kanase-Patil
Asso. Professor
Department of Mechanical Engineering
SCOE, Vadgaon
 Thermodynamics
Thermodynamics = Thermo + Dynamics
(Heat) (Power)
 Unit: I Laws of thermodynamics (6 Hrs)

 Introduction of thermodynamics, Review of basic definitions, Thermodynamic

properties and their units.
 Zeroth law of thermodynamics, Macro and Microscopic Approach.
 State Postulates
 First law of thermodynamics, Joules experiment, Applications of first law to
flow and non flow processes and cycles. Steady flow energy equation and its
application to different devices.
 Limitations of First law, Second Law of thermodynamics, Equivalence of
Clausius and Kelvin Plank Statement, PMM I and II, Review of Heat engine,
heat pump and refrigerator.
 Concept of Reversibility and Irreversibility.
 Thermodynamics and Energy

What is Thermodynamics?
• The science of energy
• In its broader sense, thermodynamics includes all aspects of
energy and energy transformations
• e.g. power generation, refrigeration, relationships among the
properties of matter

Conservation of Energy
• One of the most fundamental laws of nature
• Energy can change form, but the total amount of energy
must remain the same i.e. energy cannot be created or
destroyed
Applications of Thermodynamics:
Classical Thermodynamics
• The macroscopic (macro mean big or total)
approach.
• Does not require knowledge of the behavior
of individual particles.
• Provides a direct and easy way to the
solution of engineering problems.

Statistical Thermodynamics
• The microscopic (micro means small) or
molecular approach.
• Based on the average behavior of large
groups of individual particles.
• The goal is the understanding and prediction
of macroscopic phenomena and the
calculation of macroscopic properties from
the properties of individual molecules.
 Revision of basic concepts
System & Surroundings
SYSTEM :
Quantity of matter or region in space,
chosen for study.
SURROUNDINGS
SURROUNDINGS :
Mass or region outside the SYSTEM.

BOUNDARY :
SYSTEM Real / Imaginary surface that separates the
SYSTEM from SURROUNDINGS.

BOUNDARY :

Fixed / Movable
BOUNDARY
Shared by both,
SYSTEM and SURROUNDINGS
No Thickness
No Mass / Volume
 Close System

GAS
2 kg
GAS
3 m3
2 kg
1 m3

CLOSED System
with Moving Boundary

Also known as CONTROL MASS

 Open System
BOUNDARY of OPEN System is known as
CONTROL SURFACE
Real Boundary

In Out

Imaginary Boundary

e.g. Water Heater, Car Radiator,

Also known as CONTROL VOLUME Turbine, Compressor
 Isolated System

Mass NO
m = const.
E = const.
Energy NO

ISOLATED
System
mass = constant
Volume = constant
Energy = constant
 Boundary Surrounding

Energy Energy
in System Out

Surrounding
Mass Transfer = 0 Boundary

Closed System/ Energy Energy

Control Mass in Out
System
Mass
Mass
Out
in

Surrounding
Open System/ Boundary
Control Volume
System

Mass Transfer = 0
Energy Transfer = 0
Isolated System
 Properties of System

Any characteristic of a System is known as its PROPERTY.

e.g. Pressure (P), Volume (V), Temperature (T) and mass (m), etc.
also Viscosity (μ), Electric Resistance (R), Thermal Conductivity (k), etc.

Intensive : Independent on mass of system.

- e.g. Velocity (c), Elevation (h), etc.

Extensive : Dependent on mass of system.

- e.g. Pressure (P), Density (ρ), etc.

Specific : Extensive properties per unit mass.

- e.g. Sp. Vol (v=V/m), Sp. Enthalpy (h=H/m), etc.
 Properties of a System
Property
• Any characteristic of a system
• E.g. temperature, pressure, volume

Intensive Property
• Independent of the size of the system
• E.g. temperature, pressure, density

Extensive Property
• Value depends on the size (or extent) of
the system
• E.g. mass, volume, total energy

Specific Properties
• Extensive properties per unit mass
• E.g. specific volume,
specific energy
 State & Equilibrium

Assume a System NOT undergoing any change.

Set of properties to completely describe the condition of the system is known as its
STATE

m = 2 kg
m = 2 kg T1 = 25 ºC
T1 = 25 ºC V1 = 3 m3
V1 = 1 m3

STATE 1 STATE 2
 State & Equilibrium
EQUILIBRIUM : State of Balance

Thermal Equilibrium :
- NO Temperature Gradient throughout the system.

Mechanical Equilibrium :
- NO Pressure Gradient throughout the system.

Chemical Equilibrium :
- Chemical composition is constant
- NO reaction occurs.

Thermodynamic Equilibrium :
- If system is in thermal, mechanical and chemical equilibrium.
 Thermal Equilibrium
Thermal Equilibrium : NO change w.r.t. Temperature
NO Temperature Gradient.

HOT cup of tea / coffee cools off w.r.t. time.

COLD Drink warms up w.r.t. time.

When a body is brought in contact with another body at different temperature, heat
is transferred from the body at higher temperature to that with lower one; till both
attain a THERMAL EQUILIBRIUM.
 Path & Process

Any change a system undergoes from one equilibrium state to another is known as

PROCESS.

Series of states through which system passes during the process is known as its PATH.

State 2
Property B

Path State 2 State 1

State 1

Property A
 Path & Process

Process proceeds in such a manner that

system remains infinitesimally close to t=t1 t=0

equilibrium conditions at all times. Quasi-Static

It is known as QUASI-STATIC or

QUASI-EQUILIBRIUM Process.

t=t2t t=0
t2 < t 1
Non-Quasi-Static
 Path & Process

NOTE : Process Path is a

Quasi-Static CONTINUOUS line only if it is
Process Path having Quasi-Static Process.
Pressure

Non-Quasi-Static Process is
denoted by a DASHED line.
State 1 State 2
Non-Quasi-Static
Volume
Process Path

Pressure
State 1 State 2

Volume
 Path & Process

h=Const s=Const
Isenthalpic Isentropic
V=Const
Isochoric

Temperature (T)
Pressure (P)

T=Const
P=Const Isothermal
Isobaric

Volume (V) Enthalpy (h)/ Entropy (s)

 Cycle

State 2
CYCLE :

A system is said to have

undergone a cycle if it returns to its
Property B

ORIGINAL state at the end of the

process.

State 1 Hence, for a CYCLE, the

INITIAL and the FINAL states are
Property A identical.
Quasi-static (quasi-equilibrium) process
• A process that proceeds in a manner that the
system remains infinitesimally close to an
equilibrium state at all times
 Reversible / Irreversible Process
Reversible Process :
Process that can be reversed without leaving any trace on the
surroundings.
i.e. Both, System and Surroundings are returned to their initialstates at
the end of the Process.
This is only possible when net Heat and net Work Exchange between the
system and the surroundings is ZERO for the process.

t=t1 t=0
Quasi-Static Compression and Expansion

Pendulum
 Reversible / Irreversible Process

Most of the Processes in nature are IRREVERSIBLE.

i.e. Having taken place, they can not reverse themselves spontaneously and restore the

System to its original State.

e.g. Hot cup of coffee Cools down when exposed to

Surroundings.

But, Warm up by gaining heat from Surroundings.

i.e. w/o external Heat supply.
 Reversible / Irreversible Process
Why REVERSIBLE Process ?

1. Easy to analyse, as System passes through series of Equilibriums.

2. Serve as Idealised Model for actual Processes to be compared for analysis.
3. Viewed as Theoretical Limit for corresponding irreversible one.

Reversible Process leads to the definition of Second Law Efficiency; which is Degree
of Approximation (Closeness) to the corresponding Reversible Process.

( )Better the Design, ( )Lower the Irreversibilities; ( ) Second Law Efficiency.

 Temperature

TEMPERATURE :

- No EXACT Definition.

- Broad Definition : “Degree of Hotness / Cold”

- This definition is based on our physiological sensation.

- Hence, may be misleading. e.g. Metallic chair may feel cold than Wooden

chair; even at SAME temperature.

- Properties of materials change with temperature.

- We can make use of this phenomenon to deduce EXACT level of temperature.

 Temperature Scales
1. Celsius Scale ( ºC ) – SI System
2. Fahrenheit Scale ( ºF ) – English System
3. Kelvin Scale ( K ) – SI System
4. Rankine Scale ( R ) – English System

Celsius Scale and Fahrenheit Scale – Based on 2 easily reproducible fixed states,
viz. Freezing and Boiling points of water.
i.e. Ice Point and Steam Point

Thermodynamic Temperature Scale – Independent of properties of any substance.

- In conjunction with Second Law of Thermodynamics
Thermodynamic Temperature Scale – Kelvin Scale and Rankine Scale.
 Temperature Scales
Conversion Factors :

ºC K ºF R
Hot End

T ( K ) = T ( ºC ) + 273.15
0.01 273.16 32.02 491.69
T ( R ) = T ( ºF ) + 459.67

T ( ºF ) = 1.8 T ( ºC ) + 32

0Regenerator T ( R ) = 1.8 T ( K )
Pulse Tube
-273.15 0 -459.67
 Thermodynamics Temperature Scales

Thermodynamic (Absolute) Temperature Scale

• A scale that is independent of the properties of a system

Temperature Scales
• oC – Celsius, based on freezing and boiling points of water
• K – Kelvin, absolute scale

T  K   T  o C   273.15 T  K   T  o C 

Anders Celsius Lord Kelvin

 Pressure
Definition : Normal Force exerted by a fluid per unit Area.

SI Units :
1 Pa = 1 N/m2
1 kPa = 103 Pa
1 MPa = 106 Pa = 103 kPa
1 bar = 105 Pa = 0.1 MPa = 100 kPa
1 atm = 101325 Pa = 101.325 kPa = 1.01325 bar
1 kgf/cm2 = 9.81 N/m2 = 9.81 X 10-4 N/cm2 = 0.981 bar = 0.9679 atm

English Units :
psi = Pound per square inch ( lbf/in2)
1 atm = 14.696 psi
1 kgf/cm2 = 14.223 psi
 Pressure

Absolute Pressure : Actual Pressure at a given position.

Measured relative to absolute vacuum i.e. absolute zero pressure.

Pressure Gauges are generally designed to indicate ZERO at local atmospheric pressure.

Hence, the difference is known as Gauge Pressure.

i.e. P (gauge) = P (abs) – P (atm)

Pressure less than local atmospheric pressure is known

as Vacuum Pressure.

i.e. P (vacuum) = P (atm) – P (abs)

 Units & Conversion

Property Unit Conversion

Temperature Kelvin ( K), Celsius (oC) 1oC = 273 K

Pressure N/m2, bar, Pascal(pa), mm of Hg 1 bar = 10 5 Pa

1 atm = 1.01325 bars
= 760 mm of Hg
= 1.03 kgf/cm2
Volume m3, Litre 1 litre = 10-3 m3
Internal energy Joule (J), N.m 1J = 1 N.m
Enthalpy Joule (J)
Power Watt (W) or (kW) 1W = 1J/s
Horse power (HP) 1HP = 735.3W
 Heat & Work
Energy can cross the Boundary of the System in 2 forms : 1. Heat
2. Work
Heat is a form of Energy transferred between 2 Systems
( or a System and the surroundings ) by virtue of
Temperature Difference (∆T).
Heat i.e. Heat is Energy in TRANSITION.
CLOSED
Process involving no Heat Exchange is known as
System
Work
ADIABATIC Process.

Atmosphere 25ºC

25 ºC
Q=0 Heat, Q
Adiabatic 15 ºC
 Heat & Work

Possibilities of Adiabatic Process :

1. Perfect Insulation : Negligible Energy transfer through Boundary.

2. Both System and Surrounding at same temperature.

No Energy transfer due to absence of driving force (∆T).

NOTE : Adiabatic Process ≠ Isothermal Process

No Heat Transfer Energy content & temperature of the system can

be changed with help of Work.
 Heat & Work

Energy Transfer in from of Heat by 3 ways :

CONDUCTION : Transfer of Energy from a more energetic particle of a substance

to the adjacent less energetic one, as a result of interaction between them.

CONVECTION : Transfer of Energy between a solid surface and the adjacent fluid
that is in motion. It involved both, the combined effect of conduction and fluid
motion.

RADIATION : Transfer of Energy due to the emission of electromagnetic waves.

 Heat & Work

WORK : Work is the Energy transfer associated with a Force acting through a distance.
Denoted by J or kJ.

e.g. Raising Piston, Rotating Shaft, etc.

∆X

Force
 PdV Work
Area A Let the Piston be moving from
Thermodynamic Equilibrium State 1 (P1, V1)
P2 V2
P1 V1 to State 2 (P2, V2).
Let the values at any intermediate
Equilibrium State is given by P and V.
State 1 State 2

For an Infinitesimal displacement, dL, the Infinitesimal Work done is;

P1
dW = F * dL = P*A*dL = PdV
Quasi-Static
Similarly, for Process 1 – 2; we can say that;

Pressure
Process Path
V2 P2
W1 2   PdV
V1
V1 Volume V
2
 PdV Work
 Work is energy in transit
 It is boundary phenomenon.
 Work done is valid only if
 System is closed.
 Process is quasi static. i.e Frictionless & reversible.
 No viscous effect. V2
 For non quasi static process/Irreversible process W1 2   PdV
V1

Sign Convention :
Sp. Work = Work per unit Mass Heat Transfer TO a System : + ve
SURROUNDINGS
Heat Transfer FROM a System : - ve
w = W/m ( J/kg ) Qin
Work done BY a System : + ve
Qout
Power = Work per unit Time Work done ON a System : - ve
SYSTEM
Win
P = W/time ( J/sec OR W ) Win
 Heat & Work
Similarities between HEAT & WORK :

1. Both are recognized at the Boundary of the System, as they cross the
boundary. Hence both are Boundary Phenomena.
2. Both are associated with Process, not State. Heat and Work have NO meaning
at a State.
3. Both are Path Functions.
4. Systems possess energy, but not heat & work.

Dissimilarities between HEAT & WORK :

1. In heat transfer temp difference is required.
2. In a stable system there cannot be work transfer, however, there is no
restriction for the transfer of heat.
 Heat & Work

Path Function : Magnitude depends on the Path followed during the Process, as well
as the End States.
Path Functions have Inexact Differentials, designated by symbol δ.

Thus, a differential amount of Heat or Work is represented as δQ or δW; in stead of

dQ or dW.

Point Function : Magnitude depends on State only, and not on how the System
approaches that State.
Properties, on the other hand, are Point Functions, and have Exact Differentials,
designated by symbol d.
 Heat & Work
e.g. Small change in Volume, is represented as dV, and is given by;
2

 dV  V
1
2  V1  V

Thus, Volume change during Process 1 – 2 is always =

(Volume at State 2) minus (Volume at State 1). State 2
Regardless of path followed.

Pressure
HOWEVER, total Work done during Process 1 – 2 is;
2
State 1

 dW  W
1
12 ( NOT W )

i.e. Total Work is obtained by following the Process V1 Volume V2

Path and adding the differential amounts of Wok (δW)
done along it.

Integral of δW is ≠ ( W2 – W1 ).
 Specific Heat

Different materials require different amount of Energy for their temperatures to

increase thought unit quantity ( i.e. 1 ºC) for identical mass.

Hence, it is required to define a

Property to compare the ENERGY
1 kg 1 kg
STORAGE CAPACITY of different
Fe H2O
20 – 30 ºC 20 – 30 ºC substances.

4.5 kJ 41.8 kJ This Property is known as SPECIFIC

HEAT.
 Specific Heat
DEFINITION :
m = 1 kg
∆T = 1 ºC The Energy required to raise the temperature of a
Sp. Heat = 5 kJ/kg ºC unit mass of a substance by 1 degree.

5 kJ

Specific Heat at Constant Pressure (CP) :

The Energy required to raise the temperature of a unit mass of a substance by 1 degree,
as the Pressure is maintained CONSTANT.

Specific Heat at Constant Volume (CV) :

The Energy required to raise the temperature of a unit mass of a substance by 1 degree,
as the Volume is maintained CONSTANT.
 Specific Heat

CP is always greater than CV; as the

He Gas System is allowed to expand in case of

V = Const Const. Pr. and the Energy for this

P = Const
m = 1 kg m = 1 kg
∆T = 1 ºC ∆T = 1 ºC
expansion Work is also need to be

supplied.
3.12 kJ 5.19 kJ
CV = 3.12 kJ/kg.ºC CP = 5.19 kJ/kg.ºC
 Specific Heat
Consider a System with fixed mass and undergoing Const. Vol. Process (expansion /
compression).
First Law of Thermodynamics → ein – eout = ∆esystem
Since it is a Const. mass System;
Net amount of Change of Energy = Change in Internal Energy (u).

i.e. δein – δeout = du Hence, CV is change in Internal Energy of a

du  CV dT …by Definition of CV substance per unit change in temperature at

constant Volume.
 u 
 CV   
 T V
dh  C P dT …by Definition of CP Hence, CP is change in Enthalpy of a
substance per unit change in temperature at
 h 
 CP   
 T  P
constant Pressure.
 Specific Heats of Ideal Gases

h = u + Pv ….by Definition of Enthalpy

But, Pv = RT ….by Ideal Gas Law

Thus, h = u + RT

dh = du + R dT

CP dT = CV dT + R dT ….by Definition of CP and CV

CP = CV + R (kJ/kg.K)

Specific Heat Ratio, k ( or γ ) is given by;

CP
k ( or γ ) =
CV
 Zeroth Law of Thermodynamics

Observation
• When a body is brought into contact with
another body that is at a different
temperature, heat is transferred from the
body at higher temperature to the one at
lower temperature until both bodies attain
the same temperature (thermal equilibrium)

Zeroth Law of Thermodynamics

• If two bodies are in thermal equilibrium with a third body, they are also in
equilibrium with each other
• Cannot be concluded from the other laws of thermodynamics
• Serves as a validity of temperature measurement
• Restated: Two bodies are in thermal equilibrium if both have the same temperature
reading, even if they are not in contact.
 Zeroth Law of Thermodynamics
By replacing the Third Body with a Thermometer; the Zeroth Law can be stated as :
Two bodies are in Thermal Equilibrium, if both have same TEMPERATURE,
regarding even if they are not in contact with each other.

A B
25 ºC

25 ºC 25 ºC

i.e. Temp (A) measured by Thermometer and is known.

(A) is in Thermal Equilibrium with (B).
Then, Temp (B) is also known, even not in contact with Thermometer.
 Zeroth Law of Thermodynamics

- Formulated and labeled by R.H. Fowler in 1931.

- However, its significance is realized after half a century after formation

of First and Second Laws of Thermodynamics.

- Hence named as Zeroth Law of Thermodynamics.

Joule’s Experiment -
 First Law of Thermodynamics

Also known as Law of Conservation of Energy

Important due to its ability to provide a sound basis to study between different
forms of Energy and their interactions.

STATEMENT :
m = 2 kg PE = 10 kJ
KE = 0 Energy can neither be created nor
destroyed during a process; but can be only

Δz converted from one form to another.

PE = 7 kJ
KE = 3 kJ
m g Δz = ½ m ( v12 - v22 )
 First Law of Thermodynamics
This forms the basis for Heat Balance / Energy Balance.

“Heat and work are mutually convertible but since energy can neither be
created nor destroyed, the total energy associated with an energy conversion
remains constant”.

Total Energy _ Total Energy = Change in Total Energy

entering the System leaving the System of the System

( EIN ) ( EOUT ) ( ΔE )

Net change ( increase / decrease ) in the total Energy of the System during a Process
= Difference between Total Energy entering and Total Energy leaving the System
during that Process.