THERMODYNAMICS:

It is the science of the relations between

heat, Work and the properties of the systems.

How to adopt these interactions to

our benefit?
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 Analogy
All currencies are not equal
Like US$ or UK£ etc. have a better purchasing power
than Indian Rupee or Thai Baht or Bangladesh Taka

Similarly, all forms of energy are not the same.

Human civilization has always attempted to obtain

 Shaft work
 Electrical energy
 Potential energy

to make life easier

 Examples

If we like to
 Rise the temperature of water in kettle
 Burn some fuel in the combustion chamber of an
aero engine to propel an aircraft.
aircraft
 Cool our room on a hot humid day.
 Heat up our room on a cold winter night.
night
 Have our beer cool.

What is the smallest amount of electricity/fuel we

can get away with?
with
On the other hand we burn,

- Some coal/gas in a power plant to generate

electricity.
- Petrol in a car engine.

What is the largest energy we can get out of

these efforts?

Thermodynamics finds solutions to some of

these questions
 Definitions

 In our study of thermodynamics, we will choose a small

part of the universe to which we will apply the laws of
thermodynamics. We call this subset a SYSTEM.
SYSTEM

 The thermodynamic system is analogous to the free body

diagram to which we apply the laws of mechanics, (i.e.
Newton’s Laws of Motion).

 The system is a macroscopically identifiable collection of

matter on which we focus our attention
(eg: the water kettle or the aircraft engine).
The rest of the universe outside the system close
enough to the system to have some perceptible effect
on the system is called the surroundings.

The surfaces which separates the system from the

surroundings are called the boundaries as shown in fig
below (eg: walls of the kettle, the housing of the
engine).
 Types of System
Closed system - in which no mass is permitted to cross the
system boundary i.e. we would always consider a system
of constant mass.We do permit heat and work to enter or
leave but not mass.

No mass entry or exit

Open system- in which we permit mass to cross the system
boundary in either direction (from the system to surroundings
or vice versa). In analysing open systems, we typically look at
a specified region of space, and observe what happens at the
boundaries of that region.
Most of the engineering devices are open system.
Isolated System - in which there is no interaction between
system and the surroundings. It is of fixed mass and
energy, and hence there is no mass and energy transfer
across the system boundary.
Macroscopic and Microscopic Approaches

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In macroscopic approach,
approach certain quantity of matter is
considered,without a concern on the events occurring at the
molecular level.These effects can be perceived by human
In microscopic approach, the effect
eg:ofpressure,
approach molecular
senses or measured by instruments. temperature
motion is Considered. eg: At microscopic level the pressure of a
gas is not constant, the temperature of a gas is a function of the
velocity of molecules. Most microscopic properties cannot be
measured with common instruments nor can be perceived by
human senses
 Property
It is some characteristic of the system to which some physically
meaningful numbers can be assigned without knowing the
history behind it.These are macroscopic in nature. Invariably
the properties must enable us to identify the system.

THERMODYNAMIC PROPERTY

INTERNAL PROPERTY EXTERNAL PROPERTY

Categories of Properties

Extensive property:
whose value depends on the size or extent of the system
(upper case letters as the symbols). eg: Volume,Mass
(V,M).If mass is increased, the value of extensive property
also increases.
Intensive property:
whose value is independent of the size or extent of the
system. eg: pressure, temperature (p, T).
Specific property:

It is the value of an extensive property per unit mass of

system. (lower case letters as symbols) eg: specific volume,
density (v, ρ). It is a special case of an intensive property.

Most widely referred properties in

thermodynamics:
Pressure; Volume; Temperature; Entropy; Enthalpy;
Internal energy
State:
It is the condition of a system as defined by the values of all its
properties. It gives a complete description of the system.
Any operation in which one or more properties of a system
change is called a change of state.

Phase:
It is a quantity of mass that is homogeneous throughout in
chemical composition and physical structure.
e.g. solid, liquid, vapour, gas.

Phase consisting of more than one phase is known as

heterogeneous system .
Path And Process
The succession of states passed through during a change of
state is called the path of the system. A system is said to
go through a process if it goes through a series of changes
in state.

Consequently: A system may undergo changes in some or

all of its properties. A process can be construed to be the
locus of changes of state Processes in thermodynamics are
like streets in a city eg: we have north to south; east to
west; roundabouts; crescents.
 Types of Processes
•Isothermal (T)
•Isobaric (p)
•Isochoric (v)
•Isentropic (s)
•Isenthalpic (h)
•Isosteric (concentration)
•Adiabatic (no heat addition or removal)
As a matter of rule we allow one of the properties to remain a
constant during a process. Construe as many processes as we can
(with a different property kept constant during each of them)
Complete the cycle by regaining the initial state
Quasi-Static Processes
In thermodynamics a quasistatic process is a process that happens
infinitely slowly. In practice, such processes can be done by
performing them "very slowly".
A quasistatic process often ensures that the system will go through a
sequence of states that are infinitesimally close to equilibrium, in
which case the process is typically reversible. An example of this is the
slow heat exchange between two bodies at two finitely different
temperatures, where the heat exchange rate is controlled by an
approximately adiabatic partition between the two bodies no matter
how slowly the process takes place, the states of the two bodies are
never infinitesimally close to equilibrium.
Equilibrium State
A system is said to be in an equilibrium state if its properties
will not change without some perceivable effect in the
surroundings.
Equilibrium generally requires all properties to be uniform
throughout the system.
There are mechanical, thermal, phase, and chemical
equilibria
Nature has a preferred way of directing changes.

- water flows from a higher to a lower level

- Electricity flows from a higher potential to a lower one
- Heat flows from a body at higher temperature to the one at
a lower temperature
 Types of Equilibrium

Between the system and surroundings, if there is no

difference in

 Pressure Mechanical equilibrium

Potential Electrical equilibrium
Concentration of species Species equilibrium
Temperature Thermal equilibrium

No interactions between them occur.

They are said to be in equilibrium.
Thermodynamic equilibrium implies all those together.
A system in thermodynamic equilibrium does not deliver anything.
Definition Of Temperature and Zeroth Law
Of Thermodynamics
Temperature is a property of a system which determines the
degree of hotness.
eg: A hot cup of coffee is at a higher temperature than a block of
ice. On the other hand, ice is hotter than liquid hydrogen.
Thermodynamic temperature scale is under evolution.
when two systems are at the same temperature they are in
thermal equilibrium (They will no exchange heat).

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 Zeroth Law

“If two thermodynamic systems are in thermal equilibrium with a

third, they are also in thermal equilibrium with each other.”
other

All temperature measurements are based on this LAW.

 TEMPERATURE SCALES

Three temperature scales are in common use in science and

industry. Two of those scales are SI metric:

The degree Celsius (°C) scale was devised by dividing the

range of temperature between the freezing and boiling
temperatures of pure water at standard atmospheric conditions
(sea level pressure) into 100 equal parts.

The kelvin (K) temperature scale is an extension of the degree

Celsius scale down to absolute zero, a hypothetical
temperature characterized by a complete absence of heat
energy.
The degree Fahrenheit (°F) non-metric temperature scale was devised
and evolved over time so that the freezing and boiling temperatures of
water are whole numbers, but not round numbers as in the Celsius
temperature scale.

Some baseline temperatures in the three temperature scales:

 First law of thermodynamics
“The first law of thermodynamics is often called the Law of
Conservation of Energy. This law suggests that energy cannot be
created nor destroyed .It can only be transferred from one system to
another in different forms. “
Alternate statement:

When a closed system undergoes a cycle the cyclic

integral of heat is equal to the cyclic integral of work.

Mathematically
δQ = δW

- For a process we can have Q=0 or W=0

- We can extract work without supplying heat(during a process)
but sacrificing the energy of the system.
- We can add heat to the system without doingwork(in process)
which will go to increasing the energy of the system.
- Energy of a system is an extensive property
 Engineering Implications
When we need to derive some work, we must expend
thermal/internal energy.

The first law introduces a new property of the system called

the energy of the system.

HEAT and WORK are not properties because they depend on the
path and end states.

To sum up:
I law for a cycle: δQ = δW
I law for a process is Q-W = ΔE
For an isolated system Q=0 and W=0.
Therefore ΔE=0
 Perpetual Motion Machines-First Kind
A perpetual motion machine of the first kind is one which produces
power without energy uptake. Such a machine would, once started,
operate indefinitely. This is forbidden by the law of conservation of
energy.

The above engine is not possible.

Perpetual motion machine of the
second kind is not possible.
 II Law of Thermodynamics
There are many ways of formulating the 2nd Law
of Thermodynamics.
Kelvin-Planck Statement
“It is impossible to construct a heat engine which
will operate continuously and convert all the
heat it draws from a reservoir into work”
Implications
II Law applies only for a cycle - not for a process!!

!!There is nothing like a 100% efficient heat engine!!

All processes in nature occur unaided or spontaneously in one
direction. But to make the same process go in the opposite
direction one needs to spend energy.
Heat flows from a body at higher temperature to a body
at lower temperature

Possible
A hot cup of coffee left in a room becomes cold. We
have to
expend energy to rise it back to original temperature

Fluid flows from a point of Water on a tank down from

higher pressure or potential spontaneously. To get it
back to the tank you have to spend energy

Inference
All processes occur unaided in one direction
but to get them go in the other direction there is an
expenditure - money, energy, time, peace of mind? ….
Clausius Statement

“It is impossible to construct a heat pump which

will transfer heat from a low temperature
reservoir to a high temperature reservoir
without using external work.”

Not possible
The existence of a magic fridge which is forbidden by the First
Law of Thermodynamics. Heat goes into the fridge, heat goes out,
no energy is destroyed. So we are in genuine need of a second law
to say that this can't be done.
The Clausius statement implies the Kelvin-Planck statement
Suppose that we violated the Kelvin-Planck statement and constructed a
magic heat engine. Then we could take its work output and use it to
power fridge, which draws heat from a cooler thermal reservoir and
discharges this heat into the thermal reservoir that the magic heat
engine runs off, Then this combined system of the fridge and the magic
heat engine is a magic fridge, since it moves heat from a lower
temperature to a higher temperature while having no other effect on its
environment - in particular, without having an external power source.
 Entropy

“A measure of the disorder or randomness in a

closed system.”
Quantitatively symbolized by S, is defined by the differential
quantity

dS = δQ / T,

where
δQ is the amount of heat absorbed in a reversible
process in which the system goes from one state to another
T is the absolute temperature. Entropy is one of the
factors that determines the free energy of the system.
 - Spontaneous changes occur with an increase in entropy
- It is an extensive state function
- It accounts for the effects of irreversibility in thermodynamic
systems.

Whenever energy (in whatever form) is out of equilibrium with its surroundings, a
potential exists for producing change that, following the second law, is
spontaneously minimized.
 Carnot Cycle
- The most efficient heat engine cycle allowed by physical laws
- It consists of two isothermal processes and two adiabatic processes.
- To approach the Carnot efficiency, the processes involved in the
heat engine cycle must be reversible and involve no change in entropy.
- The Carnot cycle is an idealization
 Carnot cycle is a four stage reversible sequence consisting of
1. adiabatic compression
2. isothermal expansion at high temperature
3. adiabatic expansion
4. isothermal compression at low temperature
5. back to stage 1 and continue.

The efficiency of a perfect engine is given by

Note that the efficiency of a perfect heat engine, following a Carnot cycle, is always
less than 100%. Real heat engines involve losses to friction, among other things.
When energy is lost to friction, it is irrecoverable. Thus the real heat engine is less
efficient that the Carnot cycle engine.
Importance of the Carnot's Cycle

- The Carnot's cycle is important since it describes an optimal

system, where heat energy is used at its best.

- It can be used to describe theoretical limits of the transformation of

heat into physical work.

- One of the consequences of the second law of thermodynamics is

that heat cannot be transformed completely in work. Heat is a type
of energy that has high entropy.. Thus, this gives a limit on the
amount of energy that can be tranfered from heat to work.
Carnot's cycle is a physical expression of the consequence of the
2nd law of thermodynamics for engines and other related physical
systems.