ME-2201 Fundamentals of Mechanical Engineering

LAWS OF THERMODYNAMICS

M L Palash
PhD. & M. Eng. (KU, Japan), M. Sc. (DU, Bangladesh)

Department of Electrical and Electronic Engineering (EEE)

University of Dhaka
 Laws of thermodynamics

❑The first law, also known as Law of Conservation of Energy, states

that energy cannot be created or destroyed in an isolated system.
❑The second law of thermodynamics states that the entropy of any
isolated system always increases.
❑The third law of thermodynamics states that the entropy of a
system approaches a constant value as the temperature
approaches absolute zero.

❑The Zeroth law, States the concept of thermal equilibrium which

states that if two bodies are in thermal equilibrium with a third
body, they are also in thermal equilibrium with each other.

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Temperature and the Zeroth Law of Thermodynamics

Consider two systems S1 and S2

which are separated by an
adiabatic wall, and a third system
S3 is in communication with both
the systems.
If systems S1 and S2 are individually in thermal equilibrium with a third
system S3, then the systems S1 and S2 will also be in thermal
equilibrium with each other, even though they are not in contact.
The zeroth law serves a basis for the validity of temperature
measurement, by replacing the third system by a thermometer. The
zeroth law can be restated as two systems are in thermal equilibrium
if both have the same temperature reading even if they are not in
contact.
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 Temperature Scale

➢ All temperature scales are based on some easily reproducible states

such as the freezing and boiling points of water, which are also
called the ice point and the steam point, respectively.
➢ A mixture of ice and water that is in equilibrium with air saturated
with vapor at 1 atm pressure is said to be at the ice point, and a
mixture of liquid water and water vapor (with no air) in equilibrium
at 1 atm pressure is said to be at the steam point.
Scale Ice point Steam point
Celsius 0°C 100°C
Fahrenheit 32°F 212°F

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 Measurement of Temperature

Sensing device should have one measurable quantity that changes

with temperature
For example:
• Change in dimension with temperature: Mercury-Glass
thermometer
• Change in electrical resistance with temperature:
Thermistor
• Change in emf with temperature: Thermocouples
• Change in intensity and color of emitted radiation:
pyrometer

In thermodynamics, it is very desirable to

have temperature scale that is independent
of the properties of any substance or
substances. Only two reference point is not
acceptable.

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 Thermocouple
• Electro-magnetic Force is generated at the junction is a function of temperature of two
dissimilar metals.
• This generated emf is calibrated in temperature scale to measure temperature.

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 Constant-volume Gas Thermometer

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 Thermodynamic Temperature Scale
In thermodynamics, it is very desirable to have temperature scale that is independent of
the properties of any substance or substances. Only two reference point is not acceptable.

Kelvin scale:

• The temperature unit on this scale is the kelvin,

which is designated by K.
• The lowest temperature on the Kelvin scale is
absolute zero, or 0 K.
• Then it follows that only one nonzero reference
point needs to be assigned to establish the slope
of this linear scale.
• Using nonconventional refrigeration techniques,
scientists have approached absolute zero kelvin
(they achieved 0.000000002 K in 1989)

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 Energy Balance and First Law of Thermodynamics

Energy is defined as the capacity to do work. It is a scalar quantity. It is

measured in kJ in SI units, and kcal in MKS units.

Adiabatic

Temperature drop Temperature raise

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 Sources of Energy

▪ Transitional Energy: The energy in motion, i.e., wind energy, hydel energy, etc.
▪ Capital Energy The energy derived from fuels existing in the earth, i.e., fossil
fuels, nuclear fuels, etc.
▪ Celestial Energy The energy coming from outer atmosphere, i.e., sun, moon, etc.
▪ Stored Energy The energy existing in various masses, i.e., flywheel, tides,
geothermal, hydraulic energy, etc.

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 Forms of Energy: Thermodynamic Point of View

In thermodynamic analysis, all forms of energy can be put into two

groups:
(a) Stored energy, and
(b) Transit energy.
(a) Stored Energy: The stored form of energy can further be classified as
(i) Macroscopic forms of energy: potential energy and kinetic energy,
(ii) Microscopic forms of energy: internal energy.
(b) Transit energy: It means energy in transition. It is the energy possessed
by a system, which is capable of crossing the boundaries. Heat energy and
work transfer are transit forms of energy.

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 Internal Energy
Internal energy is defined earlier as the sum of all the
microscopic forms of energy of a system. It is related to
the molecular structure and the degree of molecular
activity and can be viewed as the sum of the kinetic and
potential energies of the molecules.

➢ The molecules of a gas move through space with some

velocity, and thus possess some transitional kinetic energy.
➢ The atoms of polyatomic molecules rotate about an axis,
and the energy associated with this rotation is known as
rotational kinetic energy.
➢ The atoms of a polyatomic molecule may also vibrate about
their common center of mass, and the energy associated
with this back-and-forth motion is the vibrational kinetic
energy.
➢ Electrons also spin about their axes, and the energy
associated with this motion is the spin energy.

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 Internal Energy (cont.)
➢ The portion of the internal energy of a system associated with the kinetic
energies of the molecules is called the sensible energy.
➢ The average velocity and the degree of activity of the molecules are proportional
to the temperature of the gas. Therefore, at higher temperatures, the molecules
possess higher kinetic energies, and as a result the system has a higher internal
energy.
➢ The internal energy is also associated with various binding forces between the
molecules of a substance, between the atoms within a molecule, and between
the particles within an atom and its nucleus. (Strongest in solids).
➢ If sufficient energy is added to the molecules of a solid or liquid, the molecules
overcome these molecular forces and break away, turning the substance into a
gas. (Phase change process). The energy required for this process is known as
latent energy.
➢ The internal energy associated with the atomic bonds in a molecule is called
chemical energy.
➢ The tremendous amount of energy associated with the strong bonds within the
nucleus of the atom itself is called nuclear energy.

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 Work
❑ Work, in thermodynamics, is defined as any other transfer of energy into or out
of a system.
❑ Thermodynamic systems can perform different types of work:
➢ the work of expansion against external pressure
➢ the work of increasing a surface area against surface tension
➢ the work of displacing a body in a gravitational field
❑ A common model for calculating the work, W is
W =  dY
ζ(zeta) is the external force acting on the body and Y is state parameter of the
system conjugate the force ζ. Compression
Expansion

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 Heat

❑ Heat is a form of energy that can be transferred from one object to

another or even created at the expense of the loss of other forms
of energy.
❑ Energy transfer by heat flow can’t be directly measured, but the
physical meaning comes from the relation with the temperature
(T).
❑ Heat can be transferred in a number of ways with or without
media.
❑ Heat can be transferred by creating temperature gradient.
❑ Energy transfers by heat are induced as a result of a temperature
difference in the direction of decreasing temperature.
❑ The amount of heat transfer depends on the process and it is a
path function.

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 Heat

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 Heat

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 Sign convention for Heat & Work

The quantity of heat which increases
the energy content of a system is
positive and any heat transfer that
decreases the energy content of a
system is negative.
Work produced by a car engine, hydraulic
motor, steam, and gas turbines is positive
and work consumed in operation of a
compressor, a pump, a refrigerator, a fan,
etc., is negative.

For quick thinking: HeaT inTo the system and Work By the system are positive

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 Enthalpy
The sum of the internal energy U and the product of pressure p and volume V
appears frequently in many thermodynamic analyses. Therefore, it is convenient to
give a name to this combination, enthalpy.
It is also called total enthalpy and is designated by H. By definition,

H = U + pV
Since U, p and V all are properties, the enthalpy is also a property of the system.
It is measured in units of internal energy, i.e., kJ in SI units.
The enthalpy for unit mass system is referred as specific enthalpy and is denoted by
h (kJ/kg),

h = u + p

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 First Law of Thermodynamics

❑ Energy cannot be created or destroyed in an isolated system.

❑ It is the relation of energy balance and is applicable to any
kind of system (open or closed) undergoing any kind of
process.
❑ The 1st Law of Thermodynamics relates Work and Heat.

dE = Q + W
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 First Law of Thermodynamics: Examples
Process that involves only heat transfer but no work interaction:

In absence of other effects, the decrease of total

energy of the potato becomes equal to the amount
of heat transferred to its surroundings. Therefore,
the principle of conservation of energy can be
expressed as:

−E = −Q
Hot potato losing its energy as heat
at its boundary

In the absence of any work interaction between a system and its surroundings, the amount
of net heat transfer is equal to the change in the energy of a system.

Q = E Where W =0
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 First Law of Thermodynamics: Examples
Well-insulated room, heated by an electric heater

• Electrical work done increases the energy of the

room.
• Since the room is adiabatic and cannot have any
heat interaction with its surroundings, the
conservation of energy principle dictates that
electrical work done on the room must be equal
to increase in energy of the room.
Electrical work increases the
−W = E energy in a room

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 First Law of Thermodynamics: Examples

Total energy: E = U + PE + KE

For stationary system KE = 0 PE = 0
So, E = U
U = Q − W
Q = W + E E = Q − W

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 Mechanism of Energy Transfer
The energy can be transferred to or from a system in three forms: heat, work and mass flow.

Esystem = (Qin − Qout ) + (Win − Wout ) + ( Emass ,in − Emass ,out )

For a closed system:  W =  Q

For multiple process: W =  Q

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 First Law of Thermodynamics: Numerical Examples

Example 2.14 (Rathore): A system undergoes a cyclic process composed of four processes 1–2,
2–3, 3–4, and 4–1. The energy transfer is tabulated below:

Task: Complete the table and power output of the system.

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 Perpetual Motion machine and the reality
➢ Steam is generated by a resistance heater inside the boiler
➢ Part of the electricity generated by the plant is to be used for the resistance heating
and pump work
➢ The rest of the electricity is supplied outside of the plant

Does it violate the first law of thermodynamics?

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 Property diagrams: T-q diagram of water

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 Saturation Pressure and Saturation Temperature
Saturation temperature (Tsat ): The temperature at which the boiling and condensation of
fluid take place.
Saturation Pressure (psar) : Pressure at Tsat

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 Compressed Liquid and Saturated Liquid

Vaporization: It is the process that involves a change of phase from liquid to vapor when the
latent heat of phase change is supplied to saturated water.
Evaporation: It is the process of vapor generation only at the free surface of the liquid. The
molecules at the free surface extract their latent heat of phase transformation from the
surrounding medium and break away as vapor from the liquid surface and escape to the
surrounding atmosphere.
Boiling: It is the phenomenon of vapor formation in the whole mass of liquid when heat
is supplied.
Steam: It is the gas phase of water.
Saturated steam: The steam is about to condense.
Saturated liquid: The liquid is about to vaporize.
Wet steam: Mixture of dry steam and water particles as moisture.
Compressed liquid: Liquid existing at a temperature lower than the saturation temperature.
Superheated steam: The steam exists at a higher temperature than its saturation temperature.
Dryness fraction: It is a measure of the quality of wet steam.
Degree of superheat: Temperature rise of superheated steam above its saturation temperature.

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 T-ν diagram of water at 1 atm pressure

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T-ν diagram of water at different
pressure

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T-ν equilibrium diagram of water

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P-ν equilibrium diagram of water

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P-T equilibrium diagram of water
The p–T diagram of a pure substance is generally called the phase diagram since it shows
solid, liquid, and vapor regions of a pure substance simultaneously.
Every single phase of a pure substance is separated by saturation lines. The sublimation line
separates the solid and vapor regions, the vaporization line separates the liquid and
vapor regions and the fusion line separates the solid and liquid regions.

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 Critical Point and Triple Point
If the pressure of liquid water is continuously increased to such a state where the saturated
liquid state and the saturated vapor state become identical then the saturation line takes the
form of a point, called a critical point.

The intersection point of the sublimation line, fusion line, and vaporization line on the phase
diagram (p–T ) is known as the triple point.

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T-s equilibrium diagram of water

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T-s equilibrium diagram of water

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T-s equilibrium diagram of water

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 h-s diagram (Mollier)

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 Limitation of First Law of Thermodynamics

• The first law of thermodynamics states that during any cyclic

process, the net work transfer is always directly proportional to
heat transfer.
• Work and heat are mutually convertible one into another.
• A certain energy balance must be held when a system undergoes
a process.

Two limitations:
• No specification about the direction of heat and energy transfer
• Heat energy and mechanical work are not fully mutually
convertible

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 Is spontaneous process reversible?

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 Simple statement of 2nd Law

• The first law of thermodynamics does not place any restriction on the direction of
process
• Satisfying the first law does not ensure that the process will actually occur,
because it only keeps the account of energy in quantity during any process.
• The second law of thermodynamics takes into account the direction of process as
well as quality of energy

2nd Law
In any process, high-grade energy can only be converted to low-
grade energy

In thermodynamics:
Heat----------------low grade energy Net quantity of work can be converted in any
Work---------------High grade energy form of energy, but net quantity of heat cannot.

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 Heat Engine
Fortunately, there are some special devices that can convert Heat into
Work, called Heat Engine.
Examples: Internal combustion engine, steam and gas turbines

A heat engine is a device which operates in a cycle. It receives the

heat energy from a high temperature reservoir, converts some of the
heat energy into work and rejects the remaining heat to a low-
temperature reservoir.

These devices are operated in mechanical cycles, not in

thermodynamic cycles, since the working fluid does not undergo a
complete cycle.

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 Heat Engine

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 Heat Engine

1. It receives heat QH from the high-temperature

reservoir (source) at TH.
2. It converts the part of heat supplied into useful
work as Wnet.
3. It rejects the remaining heat QL to a low-
temperature reservoir (sink) at TL.

The net work output

For any cyclic heat engine

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 Thermal efficiency of heat engine

Thermal efficiency is the performance- measuring parameter of a heat

engine. In general, it is defined as the ratio of the desired output to the
energy input.
For a heat engine, the desired output is the net work Wnet, and the
energy input is the heat supplied QH. Thermal efficiency is denoted by
the symbol ‘ηth’.
Efficiency of real systems:
• Spark ignition internal
combustion engine: 30%
• Diesel engine: 32%
• Large gas/steam power
plant: 45%

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 Refrigerator

• A refrigerator is a device, operating in a cycle, that maintains a

body at lower temperature than its surroundings.
• A refrigerator extracts heat continuously from a controlled space,
and thus it is maintained at a lower temperature than its
surroundings.
• The working fluid in the refrigerator is called the refrigerant.

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 Refrigerator

• The refrigerant enters the compressor as

low pressure vapour and is compressed to
high pressure and temperature.
• In the condenser, the refrigerant vapour
passes through the long condenser coils,
where it rejects its latent heat to the
surroundings.
• The liquid refrigerant then enters a
capillary tube (an expansion device for
small refrigerators), where its pressure
reduces drastically due to throttling effect
and its temperature also reduces.

• This low-temperature and low pressure refrigerant then passes through the evaporator coils
( freezer), where it evaporates by absorbing heat from the refrigerated space to keep it at
low temperature.
• The cycle completes as the refrigerant re-enters the compressor.

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 Coefficient of performance of Refrigerator (COP)

• The performance of a refrigerator is measured in terms of the

coefficient of performance (COP)R.
• It is defined as the ratio of the desired output (refrigerating effect)
to the energy (work) input.

Consider an amount of heat QL is removed from the refrigerated space

at temperature TL. The work input to the compressor is Win and the
heat rejected at the condenser is QH.

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 Heat pump

• A heat pump is a device, operating in a cycle, that

maintains a space at a higher temperature than the
surroundings.
• The heat pump supplies heat continuously to the
controlled space, and thus maintained at a higher
temperature than its surroundings.
• The refrigerator and heat
pump are operated on the
same thermodynamic cycle,
but they differ in their
objectives

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 Statements of the second law of thermodynamics

Relating to the Heat engine: Kelvin-Plank Statement

“It is impossible to construct an engine which, while operating in a
cycle, produces no other effect except to extract the heat from a
single temperature reservoir and do equivalent amount of work”.
The engine receives heat from a high-temperature reservoir and it must reject some
amount of heat to a low-temperature reservoir.

Relating to the Refrigerators and heat pump: Clausius Statement

“It is impossible for any device that operates in a cycle and produce
no effect other than the transfer of heat energy from a lower
temperature body to higher temperature body”.
Heat energy cannot flow by itself from a low-temperature body to a high-temperature body
without addition of work.

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 Equivalence of two statements

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 Reversible Process: Ideal Process
A reversible process is defined as a process that once having taken place in a direction,
can be reversed without leaving any trace on either system or surroundings.
Reversible processes do not occur in nature. They are idealization of actual processes.
Engineers are always interested in reversible processes because work-producing devices
such as engines and turbines develop maximum work and work-consuming devices, such
as compressors, blowers and pumps, etc., consume least work when they are operated
reversibly.

Conditions for a reversible process:

1. The process should not involve friction of any kind.
2. Heat transfer should not take place due to finite temperature difference between the
system and surroundings.
3. There should not be a mixing of fluid layers at different temperatures.
4. There should not be free and unrestrained expansion.
5. The process must proceed through a series of equilibria.

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 IRReversible Process: Actual Process
All processes occuring in nature are irreversible. When these processes are reversed, they
cannot return to their initial state of the system without changing the surroundings.

The irreversibility of the processes may be caused due to

(i) Mechanical or thermal irreversibility
(ii) Internal and external irreversibility

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 Carnot Cycle

The Carnot cycle, also called reversible cycle, comprises of

four reversible processes as given:
1. Reversible isothermal expansion,
2. Reversible adiabatic (isentropic) expansion,
3. Reversible isothermal compression, and
4. Reversible adiabatic (isentropic) compression.

Assumptions:
1. The working substance for the Carnot engine is a perfect
gas.
2. The piston movement in the cylinder is frictionless.
3. The walls of the cylinder and piston are considered
perfectly insulated.
4. The cylinder head is so arranged that it is partially a very
good conductor of heat and partially a perfect insulator.
5. The heat supply and heat rejection are at constant
temperatures.

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Example of a real heat engine: Coal-based power plant

Photo courtesy of Progress Energy Carolinas, Inc.

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Example of a real heat engine: Coal-based power plant
A steam power plant produces 50 MW of net work while burning fuel to
produce 150 MW of heat energy at the high temperature. Determine the
cycle thermal efficiency and the heat rejected by the cycle to the
surroundings.

Wnet , out
 th =
QH
50 MW
= = 0.333 or 33.3%
150 MW
Wnet , out = QH − QL
QL = QH − Wnet , out
= 150 MW − 50 MW
= 100 MW
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 Lets solve some problems

A heat pump is to be used to heat a building during the winter. The building is to be
maintained at 21oC at all times. The building is estimated to be losing heat at a rate
of 135,000 kJ/h when the outside temperature drops to -5oC. Determine the
minimum power required to drive the heat pump unit for this outside temperature.

Q Lost

oC
Win
21

Q H
HP Q L
-5 oC

The heat lost by the building has to be supplied by the heat pump.

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 Lets solve some problems

Using the basic definition of the COP

  kJ Q H
QH = QLost = 135000 COPHP =
h Wnet , in
Q H TH Q H
COPHP = = Wnet , in =
 
QH − QL TH − TL COPHP
( 21 + 273) K =
135,000 kJ / h 1h 1 kW
=
( 21 − ( −5)) K 1131
. 3600s kJ / s
= 11.31 = 3.316 kW

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