Scope of Thermodynamics

• The name Thermodynamics stems from the Greek words

therme (Heat) and dynamics (Power).
• Thermodynamics is the science dealing with energy and
its transformation.
– Clearly depicting the early efforts to convert heat into
power.
– Born in 19th century to describe the operation of steam
engines.
– Principles of thermodynamics are generalized - 4 laws
– Applications are in all fields- Chemical, mechanical,
metallurgical, aerospace etc.
– Laws have no proofs, validity lies in the absence of
contrary experience
 Definition of Thermodynamics
Thermodynamics is a fundamental subject that describes the
basics governing the occurence of physical processes and also
establishes the relationship between the different physical
properties that can be affected by these processes.

Engineering Thermodynamics is the subject that deals with

the study of the science of thermodynamics and the
usefulness of this science in the design of each & every
process, device or system involving the effective utilization
of energy and matter for the benefit of mankind.
 Limitations..
• Does not establish the rates of chemical or
physical process
Whether a specified change will take place
in a reasonable period of time or not
• Rates depend on driving force and
resistance
• Driving force – thermodynamic variables
Resistance is not
Thermodynamics remains a powerful and
universal tool.
• Macroscopic View: A certain quantity of
matter is considered without the events
occurring at the molecular level being taken
into account
• The system can be specified by the properties
that can be directly sensed or measured (eg
pressure) – Classical thermodynamics
• Microscopic View: We analyze the behavior of
certain quantity of matter from its molecular
actions – Statistical thermodynamics
• System: is a certain quantity of matter or
region in a space on which the attention is
placed or study is conducted and it is bounded
by a boundary.
• Process: If a system experiences changes in
state, then it is called as process E.g reaction,
distillation etc.
Types of system
Open system : Energy transfer and mass transfer take place.
Eg: Pump, compressor, turbine, plug flow reactor.
Closed system: Only energy transfer take place but no mass
transfer. Eg: Earth’s atmosphere, inflated baloon, batch reactor
Isolated system: Neither energy transfer nor mass transfer take
place. Eg: Thermas Flask
Type of boundary Interactions
Open All interactions possible
Mass
Closed Matter cannot enter or leave
Only certain species can enter or
Semi-permeable
leave Interactions possible
Work
Insulated Heat cannot enter or leave
Rigid Mechanical work cannot be done*
Heat
Isolated No interactions are possible**
* By or on the system
** Mass, Heat or Work
Surroundings: Every thing apart from system is called as
surroundings
More practically, we can consider the ‘Surrounding’ as
the immediate neighbourhood of the system (the part of
the universe at large, with which the system ‘effectively’
interacts).
Universe: Both system and surrounding together is called
as universe
Boundary: The layer which separates system and
surroundings is called boundary. It may be physical or
imaginary, rigid or movable.
Control mass system: Mass of the system is fixed
by its quantity and identity i.e no mass interaction
across the system but there may be energy
interaction (if system defined as certain quantity of
matter).
Control volume: The volume occupied by a system
is fixed. Boundary of control volume is called
control surface. Energy and mass transfer can take
place (If system defined as region or space).
Mass flow in = mass flow out (steady state control
volume)
 Thermodynamic properties..
• In thermodynamics, properties are the
quantities used to determine the state of a
system. The characteristic features of the
system by which its physical condition may be
defined is specified by the thermodynamic
properties.
• State: is the term used to denote the present
conditions of the system. When all the properties
of a system have definite values, the system is
said to exist at a definite state.
• Requirement to fix the state of the system
 All the properties should be uniform throughout
the system
 The properties should not change continuously
(invariant) with time, at least for a moment.
• The state of system can be represented by a point
in a thermodynamic diagram.
• Cycle: A series of process (state changes) in which
the initial and final states are the same is called
as a cycle.
 Thermodynamic properties..
• Types of properties
– Extensive properties: These depend upon mass of
the system. Eg: mass, volume etc.
If system contracts to a point, property0
– Intensive properties: These do not depend upon
mass of the system. Eg: pressure, temperature,
time, etc.
If system contracts to a point, propertyfinite value
Specific extensive properties i.e. extensive
properties per unit mass = intensive properties
Eg, specific volume, specific internal energy etc
 Thermodynamic Equilibrium:
 A system is said to be in thermodynamic
equilibrium when there is no change in
macroscopic property, if the system is isolated
from the surroundings.
 Macroscopic properties remain uniform and
invariable with time even though the
microscopic activity does not cease.
How is it achieved?
 When the system is isolated
 When the system properties are same as that of
the surroundings (Dead state)
 Thermodynamic equilibrium
Thermodynamic equilibrium -If the conditions for
the following three types of equilibrium are satisfied
1) Thermal Equilibrium
• Concept of temperature
• Zeroth law of thermodynamics
2) Mechanical Equilibrium
3) Chemical Equilibrium
Temperature

 Temperature is a measure of the ‘intensity of heat’. It is the property of

the system by virtue of which the ‘Heat flows’ (energy is transferred as
heat) from a body at higher temperature to one at lower temperature.
 It is a property used to measure the degree of relative hotness or coldness
of a body
 It is a thermodynamic property that determines whether or not a
system is in thermal equilibrium with other systems.
 But, temperature comes in two important ‘technical’ contexts in TD:
1 it is a measure of the average kinetic energy (or velocity) of the
constituent entities (say molecules) that give rise to the temperature of a
body.
2 it is the parameter which determines the distribution of species (say
molecules) across various energy states available.
 Thermal equilibrium..
When two bodies are in contact, so that the heat can
flow between them, the bodies are said to be in thermal
equilibrium if no heat transfer takes place between
them( both the temperatures are equal).
 When no heat exchange occurs between various
points within the system and the temperature is uniform
throughout.

10C Heat flow

A direction B
500C
 Thermal equilibrium..
Thermal equilibrium is the equilibrium states achieved
by two (or more) systems characterized by the restricted
values of the thermodynamic properties of the systems,
after they have been in communication with each other
through a diathermic wall (Which allows heat to flow).
 Zeroth law
When two bodies or systems are in thermal
equilibrium with the third one, then they are
in thermal equilibrium with each other.
 Thermometry
• Thermometry is the device of measuring
temperature with scientific precision
• Zeroth law allows us to build thermometers
which are devices that indicate the change in
temperatures by the change in some physical
properties of the thermometric fluid.
• Such properties are called thermometric
properties
 Commonly used thermometric
properties
1) Volume of gas and liquids (thermometers)
2) Pressure of gases at constant volume
(constant volume gas thermometers)
3) Electrical resistance of solids (thermistors)
4) Electromotive forces of two dissimilar metals
(thermocouples)
5) Intensity of radiation (pyrometers)
 Temperature scale
Celsius Kelvin Fahrenheit Rankine

1000C 373.15 K 2120F 671.670R Steam point

00C 273.15 K 320F 491.670R Ice point

-273.150C 0K 459.670F 00R Absolute Zero

Ice Point - Freezing point of water saturated with air at standard atmospheric
pressure
Steam Point - boiling point of pure water at standard atmospheric pressure
Absolute zero – The temperature at which a thermodynamic system has the
lowest energy. It corresponds to -273.15 C on celsius scale
 Mechanical equilibrium
It is the equilibrium with respect to work transfer
between the system and the surroundings. i.e No
imbalance in the properties of the system that will cause
work transfer.

If the pressure of the system and the surrounding is

same then there is no mechanical work transfer and the
system is in Mechanical equilibrium.

It is the absence of any unbalanced force within the

system itself and also between the system and
surroundings
 Chemical equilibrium
It is the equilibrium with respect to Chemical
reaction and mass transfer between the system
and the surroundings.
No imbalance in the properties of the system
that will cause species amount to change with
respect to time and space.
If there is no mass transfer between the phases,
no diffusion of mass within the phase and no
chemical reaction between the constituents
If all the three equilibriums are attained , then
the system is in thermodynamic equilibrium.
 Thermodynamic process
• System interacts with the surroundings in
terms of mass and energy transfer and goes
from one equilibrium state to another
equilibrium state with the natural process
• All natural process are non equilibrium in
nature and vary with time.
Thermodynamic concept of energy

• Two forms of energy

Energy in storage : eg Internal energy, PE, KE
etc
Energy in transit: eg Heat transfer and work
transfer
 Fundamental or Base Units
The fundamental dimensions are primitives, recognized through
our sensory perception and not definable in terms of anything
simpler.
• Kilogram – mass – kg
• Metre – Length – m
• Second – time – s
• Kelvin – temperature – K
• Mole – Amount of substance – mol
• Ampere – electric current – A
• Candela – Luminous intensity – cd
• Radian – Phase angle – rad
• Steradian – solid angle - sr
 Derived Units
• Force acting on a body is defined by newton’s second
law of motion
Force = ma
Unit-Newton
Newton is defined as the force when applied to a mass of
1 kg produces acceleration of 1m/s2
Force = ma/gc
1 kgf is defined as the force which accelerates 1 kg mass
at 9.8066 m/s2
gc = 9.80665 kg m/kgf s2
1kgf = 9.80665 kg m/s2
1kgf = 9.80665 N
• Weight : It is the force of gravity on a body.
• W=mg, g=9.80665 m/s2
• Units: N or kgf
• Pressure – Normal force exerted by a system against a unit
area
• P = F/A
• Units: bars, atm, Pa
One atmosphere is the average pressure exerted by the
earth’s atmosphere at mean sea level
• 1 bar = 105Pa, 1 Pa = 1N/m2
• 1 atm = 101.325 kPa = 1.01325 bar
• 1 torr = 1mm Hg at 273.15K = 133.322 Pa
Absolute pressure = Gauge pressure + barometric pressure.
Work – is performed whenever a force acts through a distance
dW = F dl, where F is the component of force acting along the line of
displacement dl.
Convention – Positive when displacement is in the same direction as
the applied force and negative when they are in opposite direction.
Eg: Compression or expansion of fluid in a cylinder resulting from the
movement of a piston.
Force exerted by piston = Piston area x pressure of the fluid
Displacement = total volume change/Piston area

Compression – piston moves into cylinder, applied force and

displacement in same direction, work +ve, -ve sign used (Volume
change is –Ve)

Expansion – piston moves out of the cylinder, applied force and

displacement in opposite direction, work -ve, -ve sign used (Volume
change is +Ve)
 Energy
• Kinetic Energy-Energy possessed by a body by virtue
of its motion

Work done on a body in accelerating it from an initial

velocity u1 to a final velocity u2 is equal to the
change in kinetic energy of the body
• Potential Energy - Energy possessed by a body by
virtue of its position

• Work done on a body in raising it is equal to

the change in the quantity mgZ
 Heat
• Heat flows from higher temperature to lower
temperature.
• Like work, heat exists as energy in transit.
• Driving force for transfer of heat – temperature difference
• 1 BTU is 1/180th quantity of heat which when transferred
to one pound mass of water raised its temperature from
ice point or 320F to steam point or 2120F at standard
atmospheric pressure.
• 1thermochemical calorie is 1/100th quantity of heat which
when transferred to one kg mass of water raised its
temperature from ice point or 00C to steam point or
1000C at standard atmospheric pressure.
• 1 Btu = 1054.35 J
 Energy Conservation
• For a freely falling body

• Potential energy of configuration – when a

spring is compressed, work is done by an
external force. Because the spring can later
perform this work against a resisting force, the
spring possess the capacity to do work
 Phase rule
• For any system at equilibrium, the number of
independent variables that must be arbitrarily fixed to
establish its intensive state of the system is given by
[Link] Gibbs in 1875.

• Where π = no. of phases

• N = no. of chemical species
• F = degrees of freedom
• N=1, π =3, triple point of water occurs at 273.16K and
0.0061 bar (F=0, system is invariant)
• F=1, steam and water in eqm at 101.325kPa can exist
only at 373.15K
1. How many degrees of freedom has each of the following
systems
a) Liquid water in equilibrium with its vapor
b) Liquid water in equilibrium with a mixture of water vapor
and nitrogen
c) A liquid solution of alcohol in water in equilibrium with its
vapor

a) 𝐹 = 2 − 𝚷 + 𝑁 = 2 − 2 + 1 = 1
b)𝐹 = 2 − 𝚷 + 𝑁 = 2 − 2 + 2 =2
c) 𝐹 = 2 − 𝚷 + 𝑁 = 2 − 2 + 2 =2
 Reversible Process
• A process is reversible if both the system and its surroundings
can be restored to their respective original states by reversing
the direction of the process. A process which does not satisfy
this criterion is an irreversible process
• A process is reversible when its direction can be reversed at
any point by an infinitesimal change in external conditions.
• An actual process that occur in nature are irreversible process.
• A process which takes place slowly and with infinitesimal
driving forces is called quasi-static or quasi equilibrium
process. It is a succession of equilibrium states.
• Every reversible process is a quasi-static process but converse
need not be true.
• For a piston cylinder
assembly, if driving force i.e.
the pressure differential
across the piston tends to
zero, the process can take
place in either direction i.e.
a reversal of the direction of
the process restores both
the system and
surroundings to the
respective original states
 Reversible process
• It is an ideal process and cannot be realized in actual.
• Frictionless.
• Is never more than differentially removed from equilibrium.
• Traverses a succession of equilibrium states.
• Is driven by forces whose imbalance is differential in
magnitude.
• Can be reversed at any point by a differential change in
external conditions.
• When reversed, retraces its forward path, and restores the
initial state of the system and surroundings.
• Work done,
 STATE AND PATH FUNCTIONS
• State functions: The properties of the substance that
describe the present state of the system and do not record
the previous history. They depend only on the initial and
final states of the system. Eg. Temperature, pressure
• Differential of a state function represents an infinitesimal
change in value. Integration results in finite difference
between two of its values.
eg

• Path functions: is defined as one whose magnitude

depends on the path followed during a process as well as
on the end states. Eg heat and work.
• The difference of heat and work are not changes but an
infinitesimal amounts. When integrated, their differentials
do not give finite changes but finite amounts
 Joule’s Experiment
• James Prescott Joule carried out experiments
during 1843-1849 which forms the basis for I law
of thermodynamics.
• Paddle Wheel Experiment
• Work and heat are same type of energy transfer.
• He found that the amount of work done on the
system is always equal to the energy transferred
as heat from the system to the surroundings,
when the system undergoes a cyclic change.
 Joules Experiment…

For each fluid fixed amount of work was required per unit mass for every
degree of temperature rise caused by stirring and original temperature of fluid
could be restored by transfer of heat through simple contact with a cooler
object 𝑑𝑊 = 𝐽 𝑑𝑄, → 𝐶𝑦𝑐𝑙𝑖𝑐 𝑖𝑛𝑡𝑒𝑔𝑟𝑎𝑙 𝑓𝑜𝑟 𝑐𝑙𝑜𝑠𝑒𝑑 𝑝𝑎𝑡ℎ
Where J=1Nm/J, in SI system
Where J is proportionality constant of Joule’s equivalent or mechanical
equivalent of heat.
 Internal Energy
• Internal Energy -Internal energy is defined as the energy associated with
the random, disordered motion of molecules internal to a substance.
• It refers to the invisible microscopic energy on the atomic and molecular
scale.
• It includes kinetic energy of translation, kinetic energy of rotation and of
internal vibration. It also includes potential energy resulting from
intermolecular forces.
• For example, a room temperature glass of water sitting on a table has no
apparent energy, either potential or kinetic. But on the microscopic scale
it is a seething mass of high speed molecules traveling at hundreds of
meters per second.
 Internal Energy
• The energy added to fluid is contained in the fluid
in the form of internal energy.
• It refers to the energy of molecules internal to
the substance.
• All molecules possess KE of translation, KE energy
of rotation and of internal vibration.
• Addition of heat increases the molecular activity
and thus causes an increase in its internal energy.
• Internal energy cannot be directly measured so
absolute values are unknown in thermodynamic
analysis.
 I law of thermodynamics
• Although energy assumes many forms, the
total quantity of energy is constant, and when
energy disappears in one form it appears
simultaneously in other forms.
• ∆(Energy of the system) + ∆(Energy of
surroundings) = 0
• ∆ signifies the finite changes in the quantity
enclosed in paranthesis
 I law of thermodynamics…
• I law -In the year 1851
• Zeroth law – In the year 1931 by [Link]
• Law of conservation of Energy- Energy can neither be created nor
destroyed.
• Although energy assumes many forms, the total quantity of energy
is constant and when energy disappears in one form, it appears
simultaneously in other forms.
• The total energy of an isolated system remains constant.
• In a system of constant mass, energy cannot be created or
destroyed by any physical or chemical change, but may be
transferred from one form of energy to the other form.
• The sum of all forms of energies in an isolated system is constant.
• He total sum of energy in system and surrounding is equal to a
constant value.
 Energy balance for closed system
• Since no streams enter or leave a closed system, no
internal energy is transported across the boundary of
the system.
• All energy exchange between a closed system and its
surroundings then appears as heat and work, and the
total energy change of the surroundings equals the net
energy transferred to or from it as heat and work.
• ∆(Energy of surroundings) = ±Q ±W
W and Q always refer to the system
Convention: +Ve into the system, -Ve out of the system
• Qsurr =-Q, Wsurr = -W
• ∆(Energy of surroundings) = Qsurr+Wsurr =-Q-W
• ∆(Energy of the system) + ∆(Energy of surroundings) = 0
• ∆(Energy of the system) =Q+W
=>total energy change of a closed system=net energy
transferrred into it as heat and work
If only internal energy changes take place in the system,
then
∆𝑈 𝑡 = 𝑄 + 𝑊
𝑈 𝑡 is the total internal energy change of the system
• For differential changes
• d𝑈 𝑡 = 𝑑𝑄 + 𝑑𝑊
• V t=mV or Vt=nV
• For a closed system of n moles
• ∆𝑛𝑈 = 𝑛∆𝑈 = 𝑄 + 𝑊
• d𝑛𝑈 = 𝑛𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊
For n=1
∆𝑈 = 𝑄 + 𝑊
Processes in TD We will deal with some of them in detail later on

 Here is a brief listing of a few kinds of processes, which we will encounter in TD:
 Isothermal process → the process takes place at constant temperature
(e.g. freezing of water to ice at –10C)
 Isobaric → constant pressure
(e.g. heating of water in open air→ under atmospheric pressure)
 Isochoric → constant volume
(e.g. heating of gas in a sealed metal container)
 Reversible process → the system is close to equilibrium at all times (and infinitesimal
alteration of the conditions can restore the universe (system + surrounding) to the original
state.
 Cyclic process → the final and initial state are the same. However, q and w need not be
zero.
 Adiabatic process → dq is zero during the process (no heat is added/removed to/from the
system)
 A combination of the above are also possible: e.g. ‘reversible adiabatic process’.
Reversible process ‘Reversible’ is a technical term (like many others) in the context of TD.

 A reversible process is one where an infinitesimal change in the conditions of the

surroundings leads to a ‘reversal’ of the process. (The system is very close to equilibrium
and infinitesimal changes can restore the system and surroundings to the original state).
 If a block of material (at T) is in contact with surrounding at (TT), then ‘heat will flow’
into the surrounding. Now if the temperature of the surrounding is increased to (T+T),
then the direction of heat flow will be reversed.
 If a block of material (at 40C) is contact with surrounding at 80C then the ‘heat transfer’
with takes place is not reversible.
 Though the above example uses temperature differences to illustrate the point, the
situation with other stimuli like pressure (differences) is also identical.
 Consider a piston with gas in it a pressure ‘P’. If the external pressure is (P+P), then the
gas (in the piston) will be compressed (slightly). The reverse process will occur if the
external (surrounding pressure is slightly lower).
 Maximum work will be done if the compression (or expansion) is carried out in a
reversible manner.
Reversible process NOT a Reversible process
Heat flow Heat flow Heat flow
direction direction direction
T T 40C

TT T+T 80C