Introduction to Engineering Thermodynamics

Science blasts many doubts, foresees what is not obvious It is

the eye of everyone, one who hasn't got it, is like blind ||

Dr. Rohit Singh Lather, Associate

Professor
 Thermodynamics – A Philosophy
• Thermodynamics is the science that primarily deals with energy
• In its origins, thermodynamics was the study of engines
• First century AD - Heron of Alexandria, first recognized thermal engineer

Reaction engine
First recorded steam engine

Hero of Alexandria Aeolipile

• 1593 - Galileo develops a water thermoscope

thermoscope

Source: [Link]
 Aristotle
“Nature abhors a vacuum” Otto von Guericke
Designed and built the world's first vacuum pump
Empty or unfilled spaces are unnatural as they go against
the laws of nature and physics

• 1650 - Otto von Guericke designed and built the world's first vacuum pump and created
the world's first ever vacuum known as the Magdeburg hemispheres, a precursor of the engine

Magdeburg hemispheres : Large copper hemispheres, with mating rims, were used to demonstrate
the power of atmospheric pressure. The rims were sealed with grease and the air was pumped
out
Source: [Link]
Source: [Link]; [Link]
• 1656 - English scientist Robert Hooke, built an air pump
- Using this pump, Boyle and Hooke noticed a correlation between pressure, temperature,
and volume
(Boyles’s Law - pressure and volume are inversely proportional)

• 1679 – Denis Papin conceived of the idea of a piston and a cylinder engine after watching steam
release valve of steam digester rhythmically move up and kept the machine from exploding, which
was a closed vessel with a tightly

Air Pump Steam Digester

Source: [Link]; [Link]
• 1697 – Thomas Savery an engineer built the first engine (based on Papin's designs)

• 1700’s – Industrial Revolution

• 1712 - Thomas Newcomen built another engine

- Early engines were crude and inefficient, but attracted the attention of the leading scientists of the time

• 1760s - Joseph Black Professor at the University of Glasgow develops calorimetry

- Developed the fundamental concepts of heat capacity and latent heat
- Joseph Black with James Watt (employed as an instrument maker), performed
experiments together, but it was Watt who conceived the idea of the external
condenser which resulted in a large increase in steam engine efficiency
• 1780s - James Watt improves the steam engine

• 1824 – Sadi Carnot, the "father of thermodynamics", published ”Reflections on the motive power of
fire”, a discourse on heat, power, energy and engine efficiency
- The paper outlined the basic energetic relations between the Carnot engine, the Carnot
cycle and motive power. Discusses idealized heat engines
- Marked the start of thermodynamics as a modern science
Source: [Link]; [Link]
• 1849 -Lord Kelvin coined the word “thermodynamics”

• 1850 - Rudolf Clausius came up with the term “entropy”

• 1850s - The first and second laws of thermodynamics emerged simultaneously in the, primarily out of
the works of William Rankine, Rudolf Clausius, and William Thomson (Lord Kelvin)

• 1859 – William Rankine - first thermodynamic textbook

• 1871 - James Maxwell formulated the Statistical Mechanical branch of thermodynamics

• 1875 - Ludwig Boltzmann precisely connected entropy and molecular motion

Source: [Link]; [Link]

 Thermodynamics and its branches
Classical Thermodynamics
• Description of the states of thermodynamical systems at near-equilibrium, using macroscopic,
empirical properties directly measurable in the laboratory
• Deals with exchanges of energy, work and heat based on the laws of thermodynamics

Statistical Mechanics (Statistical Thermodynamics)

• Emerged with the development of atomic and molecular theories
• Relates the microscopic properties of individual atoms and molecules to the macroscopic, bulk properties of
materials that can be observed on the human scale, thereby explaining thermodynamics at the microscopic level

Chemical
Thermodynamics
• Study of the interrelation of energy with chemical reactions or with a physical change of state within the confines of
the laws of thermodynamics
Treatment of equilibrium
• Equilibrium thermodynamics is the systematic study of transformations of matter and energy in systems as they
approach equilibrium
• Non-equilibrium thermodynamics is a branch of thermodynamics that deals with systems that are
not
in thermodynamic equilibrium
 Applications of Thermodynamics

Air- conditioning Airplanes

systems

The human
body

Car Power
Refrigeration
radiators plants
systems

Source: Yunus A. Cengel and Michael A. Boles Thermodynamics: An Engineering Approach, McGraw Hill, 8th Edition
 Introduction
We introduce here classical thermodynamics
• “Thermodynamics” is of Greek origin, and is translated as the combination of therme: heat and
dynamis: power
• Thermodynamics is based on empirical observation
• The word “thermo-dynamic,” used first by Lord Kelvin
• Study of the relationship between heat, work, and other forms of
energy
• Describes what is possible and what is impossible during
energy conversion processes
• Describes the "direction" of a process
• Studies the effects of temperature on physical systems at
the macroscopic scale
• All of these things accurately describe thermodynamics
• Thermodynamics is the study of energy conversion, most typically
through terms of heat and work

Sir William Thomson a.k.a

Source: [Link]/biography/William-Thomson-Baron-Kelvin Lord Kelvin (1824 – 1907)
 Forms of Energy

Energy
Heat Low Grade High Work
Grade

Macroscopic Microscopic
Kinetic Potential

Sensible Chemical
(translational + rotational + vibrational) (Atomic Bonds)

Latent Atomic
(inter molecular phase change) (bonds within nucleolus of atoms)

Summation of all the microscopic energies is called Internal

Energy

E= U+KE+PE
(kJ)
 Macroscopic vs.
• Microscopic
The behavior of a system may be investigated from either a microscopic or macroscopic point of
view

Understanding microscopic point of view

Statistical Approach
• On the basis of statistical considerations and
probability theory
Cube with • wedeal with average values for all particles
1m3Air under
consideration
2.4 × 1025
Molecules
Macroscopic
Due to collision the position velocity and energy
changes for each molecules - Approach
Reducing the number of variables to a few that can
be handled
The behavior of the gas is described by summing
up the behavior of each molecule
• Concerned with the gross or average effects
of many
To specify position and velocity, we molecules
need three coordinates x, y and z • These effects can be perceived by our senses and measured
1.4 × 1026 equations by instruments
 Gas exerts pressure
on the walls due to
change in
momentum of the Container
molecules as they
collide with the wall

• From a macroscopic point of view, we are concerned not with the action of the individual molecules
but with the time-averaged force on a given area, which can be measured by a pressure gauge
• Macroscopic observations are completely independent of our assumptions regarding the nature of
matter
• We are always concerned with volumes that are very large compared to molecular dimensions and,
therefore, with systems that contain many molecules
• Because we are not concerned with the behavior of individual molecules, we can treat the substance
as being continuous, disregarding the action of individual molecules
 Continuu
• The limit in which discretem
changes from molecule to molecule can be
ignored and distances and times over which we are concerned are much
larger than those of the molecular scale
• This will enable the use of calculus in our continuum thermodynamics
 Definitions
System Boundary
Interface separating system and surroundings (fixed or moving)

Thermodynami
c System
A quantity of fixed
mass under Work
investigation Out
Heat In

Surroundings
Everything external to the system

Universe
Combination of system
and surroundings
 Open System Closed System Isolated System
a system in which mass a system with fixed A system in which there
crosses boundary, energy mass, no mass transfer, are no interactions
transfer in and out energy may transfer in between system and
and out surroundings, no mass
and energy transfer
 system → fixed mass

constant mass, but possible variable volume

Source: Yunus A. Cengel and Michael A. Boles Thermodynamics: An Engineering Approach, McGraw Hill, 8th Edition
 Control
• Volume
Control Volume: fixed volume over which mass can pass in and out of its boundary
• The mass within a control volume may or may not be constant
- If there is fluid flow in and out there may or may not be accumulation of mass within the
control volume

Control Volume
control volume → potentially variable mass, open
Source: Yunus A. Cengel and Michael A. Boles Thermodynamics: An Engineering Approach, McGraw Hill, 8th Edition
 A control volume can involve fixed, moving, real and imaginary boundaries

Source: Yunus A. Cengel and Michael A. Boles Thermodynamics: An Engineering Approach, McGraw Hill, 8th Edition
 Thermodynamic
If you can’t measure it, you can’t improve it – Lord Kelvin
Properties
Property - A property of a system is any observable (macroscopic) characteristics of the system.
The properties we shall deal with are measurable in terms of numbers and units of measurements (eg.
Pressure, density, temperature etc.)
Thermodynamic properties can be divided into two
general classes, intensive and extensive properties

Intensive Property Extensive Property

Intensive property is independent The value of an extensive property
of the amount of mass, examples varies directly with the mass, examples
are: Temperature, pressure, are: Mass and total volume
specific volume, and density

Thus, if a quantity of matter in a given state is divided into two equal parts, each part will have the same
value of intensive property as the original and half the value of the extensive property

When all the properties of a system have definite values,

the system is said to exist at a definite state
• An Extensive variable depends on the size • An Intensive variable has a uniform value in
of the system. different subdivisions of a system
• Examples of extensive variables are internal
energy, enthalpy, heat capacity at constant • Examples of intensive variables are pressure,
pressure, heat capacity at constant volume, temperature, identical in all points of the
entropy, Helmholtz energy, Gibbs energy, system, Molar variables or partial molar
volume variables, specific mass, mole fractions, molar
heat capacity at constant pressure, have the
• For a system consisting of several parts, an same values in all points of one phase of the
extensive property of the ensemble of the system.
parts is the sum of the corresponding
extensive property of each of the parts • They may differ from one phase† to another.

• Extensive properties of a system containing a

pure species are proportional to the number
of moles of the species present
 State
• State is the condition of the system at an instance of time as described or measured by the
properties
OR
Each unique condition of a system is called a state

• At a particular state, all properties have fixed values

State 1 State 2
P1T1V1 P2T2V2
State functions the endpoints of your definite integral are all that matter: you
could parameterize any path you want between the endpoints and the
resulting integral is the same

Property and Non Property

An infinitesimal change in a state function is represented by an exact differential

 Change of a State Variable as the Result of a
Thermodynamic Process
General Process Cyclic
For a state variable, X , (XF – XI) is Process
Consider a thermodynamic change of a
independent of the path used for the system to some intermediate state via
process. The intermediate states of the path 1. Then along path 2, bring the
system back to its initial state. This
system are irrelevant process is a cyclic
process

Path 1 Path 1

I Path 2
F I Path 2
Int.
Initial State Final State Initial State Intermediate State

(XF – XI)path 1 = (XF – XI)path 2

Source: Introductory Thermodynamics,Pierre Infelta Swiss Federal Institute of Technology Lausanne,

Switzerland
The change of X is zero for a cyclic process
 • Example of a cyclic process: the initial state and final state
is identical Y
• There is no volume change 2

• The change of any state variable is zero for any

cyclic process

• A variable X is a state variable (or state function) if its

change for a cyclic process is zero 1
• X is also a state variable if its change for a general 3
process depends only on the initial and final states of the
system and not on the way the change is achieved. x
• The differential form dX is then called an exact
differential
• The line integral of an exact differential is independent
of the path of integration

Source: Introductory Thermodynamics,Pierre Infelta Swiss Federal Institute of Technology Lausanne, Switzerland
 Processes and
Cycles
• Change of State: implies one or more properties of the system has changed
- the changes are slow relative to the underlying molecular time scales
• Process: a succession of changes of state
- We assume our processes are all sufficiently slow such that each stage of the
process is near equilibrium
- isothermal: constant temperature
- isobaric: constant pressure
- isochoric: constant volume

• Path: The succession of states passed through during a change of state is called path of the
change of state
• Cycle: series of processes which returns to the original state. (A thermodynamic cycle is
defined as a series of state changes such that the final state is identical with the initial state)
- The cycle is a thermodynamic “round trip.”
 Process
Change of state, when the path is
A process is completely specified by the end states,
completely specified
the path, and the interactions that take place at the
boundary

a Reversible Process
When a system undergoes changes in such a manner
it is able to retain its original condition by following
Proces the same thermodynamic path in the reverse
Pressur

2 s a- direction, it is then said to have undergone a

b reversible process
e

Cycle b
Irreversible process
1-2-1
When the system is unable to reach the original
condition by retracing its path or attain the
1
original conditions along other thermodynamic
paths, then the process is said to be an
Volume
irreversible process
A process becomes irreversible due to the friction
Cycle
a series of state changes such that the final
state is identical with the initial state
 Quasi-Static Process
• Arbitrarily slow process such that system always stays stays arbitrarily close to thermodynamic
equilibrium
• Infinite slowness is the characteristics of a quasi-static process
• It is a succession of equilibrium states
• A quasi-static process is also reversible process

Such a process is locus of all the

equilibrium points passed through by

Pressur
the system
1

e
Final Final
State
Dots indicate
State Multipl equilibrium states
Piston
Weight Pisto e
n Weight dp
Initial State Initial State s
2
System
Boundary Every state passed through by the
system will be an equilibrium state dv Volum
 Thermodynamic Equilibrium
• Thermodynamic Equilibrium: state in which no spontaneous changes (macroscopic properties) are
observed with respect to time
- We actually never totally achieve equilibrium, we only approximate it
- It takes infinite time to achieve final equilibrium

Mechanical Thermal Equilibrium Chemical Equilibrium

Equilibrium Characterized by Characterized by equal
Characterized by equal equal temperature chemical potentials
forces (pressure)

Non-equilibrium thermodynamics: branch of thermodynamics which considers systems

often far from equilibrium and the time-dynamics of their path to equilibrium