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: www.wikipedia.com

Aristotle
Nature abhors a vacuum
Empty or unfilled spaces are unnatural as they go against
the laws of nature and physics

Otto von Guericke

Designed and built the world's first vacuum pump

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: www.wikipedia.com

Source: www.wikipedia.com; www.google.com

 1656 - English scientist Robert Hooke, built an air pump

- Using this pump, Boyle and Hooke noticed a correlation between pressure, temperature,
and volume
(Boyless 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
Source: www.wikipedia.com; www.google.com

Steam Digester

 1697 Thomas Savery an engineer built the first engine (based on Papin's designs)
1700s 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: www.wikipedia.com; www.google.com

 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: www.wikipedia.com; www.google.com

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
Source: www.wikipedia.com; www.google.com

Applications of Thermodynamics

Air-conditioning
systems

Airplanes

The human body

Car radiators

Power plants

Source: Yunus A. Cengel and Michael A. Boles Thermodynamics: An Engineering Approach, McGraw Hill, 8th Edition

Refrigeration systems

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: www.britannica.com/biography/William-Thomson-Baron-Kelvin

Lord Kelvin (1824 1907)

Forms of Energy
Energy
Heat

Low Grade

High Grade

Macroscopic
Kinetic

Work

Microscopic

Potential
Sensible

(translational + rotational + vibrational)

Latent

Chemical

(Atomic Bonds)

(inter molecular phase change)

Atomic

(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

Cube with
1m3Air
2.4 1025
Molecules

Due to collision the position velocity and energy

changes for each molecules
The behavior of the gas is described by
summing up the behavior of each molecule
To specify position and velocity,
we need three coordinates x, y and z

1.4 1026 equations

Statistical Approach
On the basis of statistical considerations and probability
theory
we deal with average values for all particles under
consideration
Macroscopic Approach
- Reducing the number of variables to a few that can be
handled
Concerned with the gross or average effects of many
molecules
These effects can be perceived by our senses and measured
by instruments

Gas exerts pressure

on the walls due to
change in momentum of
the molecules as they
collide with the wall

Container

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

Continuum
The limit in which discrete 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)

Heat In

Thermodynamic
System
A quantity of fixed
mass under
investigation

Work Out

Surroundings
Everything external to the system

Universe
Combination of system and surroundings

Open System
a system in which mass
crosses boundary, energy
transfer in and out

Closed System
a system with fixed
mass, no mass transfer,
energy may transfer in
and out

Isolated System
A system in which there
are no interactions
between system and
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 potentially variable mass, open

Source: Yunus A. Cengel and Michael A. Boles Thermodynamics: An Engineering Approach, McGraw Hill, 8th Edition

Control Volume

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 Properties

If you cant measure it, you cant improve it Lord Kelvin

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
Intensive property is independent
of the amount of mass, examples
are: Temperature, pressure,
specific volume, and density

Extensive Property
The value of an extensive property
varies directly with the mass, examples
are: Mass and total volume

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

of the system.
Examples of extensive variables are internal
energy, enthalpy, heat capacity at constant
pressure, heat capacity at constant volume,
entropy, Helmholtz energy, Gibbs energy,
volume
For a system consisting of several parts, an
extensive property of the ensemble of the
parts is the sum of the corresponding
extensive property of each of the parts
Extensive properties of a system containing
a pure species are proportional to the
number of moles of the species present

An Intensive variable has a uniform value in

different subdivisions of a system
Examples of intensive variables are pressure,
temperature, identical in all points of the
system, Molar variables or partial molar
variables, specific mass, mole fractions, molar
heat capacity at constant pressure, have the
same values in all points of one phase of the
system.
They may differ from one phase to another.

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
P1T1V1

State 2
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
For a state variable, X , (XF XI) is
independent of the path used for the
process. The intermediate states of the
system are irrelevant

Cyclic Process
Consider a thermodynamic change of a
system to some intermediate state via
path 1. Then along path 2, bring the
system back to its initial state. This
process is a cyclic process

Path 1

I
Initial State

Path 1

Final State

Initial State

Path 2

Int.
Path 2

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
There is no volume change

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

is

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

1
3

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
completely specified

Pressure

a
Process
a -b

Cycle

1-2-1
1
Volume
Cycle
a series of state changes such that the
final state is identical with the initial state

A process is completely specified by the end states,

the path, and the interactions that take place at
the boundary
Reversible Process
When a system undergoes changes in such a manner
it is able to retain its original condition by following
the same thermodynamic path in the reverse
direction, it is then said to have undergone a
reversible process
Irreversible process
When the system is unable to reach the original
condition by retracing its path or attain the
original conditions along other thermodynamic
paths, then the process is said to be an
irreversible process
A process becomes irreversible due to the friction

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

Final State
Weight
Piston
Initial State
System Boundary

Pressure

A quasi-static process is also reversible process

Final State
Piston

Multiple
Weights

Such a process is locus of all the

equilibrium points passed through by
the system
1

Dots indicate
equilibrium states

dp

Initial State
Every state passed through by the
system will be an equilibrium state

dv

Volume

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 Equilibrium
Characterized by equal
forces (pressure)

Thermal Equilibrium
Characterized by
equal temperature

Chemical Equilibrium
Characterized by equal
chemical potentials

Non-equilibrium thermodynamics: branch of thermodynamics which considers systems

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