THE SECOND LAW
OF THERMODYNAMICS
BITS Pilani
Pilani Campus
Reviewed
•Heat Reservoirs
•Heat Engine
•Efficiency
•Refrigerator and Heat pump
•Coefficient of Performance
•Second law of thermodynamics
•Kelvin-Plank Statement
•Clausius Statement
•Equivalence of Statements
•Factors that Render Processes irreversible
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
The combination of the heat engine and refrigerator in the left figure
acts like a heat pump that transfers heat QL from the low-
temperature reservoir without any external energy input. This is a
violation of the Clausius statement of the second law.
BITS Pilani, Pilani Campus
Factors that Render
Processes irreversible
Friction
Heat Transfer through finite
temperature difference
Unrestrained expansion
Mixing of two different substances
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
Reversible Processes
A reversible process is a quasi-equilibrium, or quasi-static, process
with a more restrictive requirement.
Internally reversible process
The internally reversible process is a quasi-equilibrium process,
which, once having taken place, can be reversed and in so doing
leave no change in the system.
This says nothing about what happens
to the surroundings about the system.
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
Totally or externally reversible process
The externally reversible process is a quasi-equilibrium process,
which, once having taken place, can be reversed and in so doing
leave no change in the system or surroundings.
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
The Carnot Cycle
Carnot was the first to introduce
the concept of cyclic operation
and devised a reversible cycle
that is composed of four
reversible processes, two
isothermal and two adiabatic
processes.
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
Process 1-2: Reversible isothermal heat addition at high
temperature, TH >TL, to the working fluid in a piston/cylinder
device that does boundary work.
Process 2-3:Reversible adiabatic expansion during which the
system does work as the working fluid temperature decreases
from TH to TL.
Process 3-4:The system is brought in contact with a heat
reservoir at TL < TH and a reversible isothermal heat exchange
takes place while work of compression is done on the system.
Process 4-1:A reversible adiabatic compression process
increases the working fluid temperature from TL to TH
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
You may have observed that
power cycles operate in the
clockwise direction when plotted
on a process diagram. The
HEAT ENGINE
Carnot cycle may be reversed, in
which it operates as a refrigerator.
The refrigeration cycle operates in
the counterclockwise direction.
REFRIGERATION (REVERSE CARNOT
CYCLE)
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
Two propositions regarding the efficiency of a Carnot Cycle:
The second law of thermodynamics puts limits on the operation of
cyclic devices as expressed by the Kelvin-Planck and Clausius
statements. A heat engine cannot operate by exchanging heat
with a single heat reservoir, and a refrigerator cannot operate
without net work input from an external source.
Consider heat engines operating between two fixed temperature
reservoirs at TH > TL. We draw two conclusions about the thermal
efficiency of reversible and irreversible heat engines, known as the
Propositions
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
First proposition
The efficiency of an irreversible heat engine is always less than
the efficiency of a reversible one operating between the same
two reservoirs.
h < h
th th, Carnot
BITS Pilani, Pilani Campus
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
Second Proposition:
The efficiencies of all reversible heat engines operating between
the same two constant-temperature heat reservoirs have the same
efficiency.
As the result of the above, Lord Kelvin in 1848 used energy as a
thermodynamic property to define temperature and devised a
temperature scale that is independent of the thermodynamic
substance.
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
The Thermodynamic Temperature
Scale
The following is Lord Kelvin's
Carnot heat engine arrangement.
Since the thermal efficiency in general is
QL
hth = 1-
QH
hth = 1- ψ(TL , TH )
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
Considering engines A, B, and C
Q1
=y (T1,T2 )
Q2
Q2
=y (T2,T3)
Q3
Q1
=y (T1,T3 )
Q3
Since
Q1 Q1 Q2
=
Q3 Q2 Q3
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
This looks like
y T1 , T3 = y T1 , T2 y T2 , T3
The left side is the function of T1 and T3 and therefore the right side
of this equation must be a function of T1 and T3. From this fact we
can conclude that the form of the function ψ must be such that
y (T1,T2 ) = f (T1 ) y (T2,T3 ) = f (T2)
f (T2 ) f (T3 )
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
in this way f(T2) will cancel from the product of ψ(T1,T2) X ψ(T2,
T3). Therefore we conclude that
Q1
=y (T1,T3 ) = f (T1 )
Q3 f (T3 )
In general terms
QH = f (TH )
QL f (TL )
QH (TH )
QL = (TL )
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
The Carnot thermal efficiency becomes
TL
hth, rev = 1 -
TH
This means that if the thermal efficiency of a Carnot cycle
operating between two given constant temperature reservoirs is
known, the ratio of the two absolute temperatures is also known.
BITS Pilani, Pilani Campus
• The temperature scale is called the Kelvin
scale.
• The temperature on this scale is called absolute
temperature.
• A temperature scale that is independent of the
properties of the substances that are used to
measure temperature is called a
thermodynamic temperature scale.
BITS Pilani, Pilani Campus
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
The Carnot thermal efficiency becomes
TL
hth, rev = 1 -
TH
This means that if the thermal efficiency of a Carnot cycle
operating between two given constant temperature reservoirs is
known, the ratio of the two absolute temperatures is also known.
BITS Pilani, Pilani Campus
Constant volume gas
thermometer
P
T = 273.16
Pt . p.
BITS Pilani, Pilani Campus
Ideal vs Real machines
QL TL
Heat Engine hreal thermal = 1- 1-
QH TH
QL TL
Re frigerator real =
QH - QL TH - TL
QH TH
Heat Pump real
'
=
QH - QL TH - TL
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
Example
A Carnot heat engine receives 500 kJ of heat per cycle from a
high-temperature heat reservoir at 652oC and rejects heat
to a low-temperature heat reservoir at 30oC. Determine
(a) The thermal efficiency of this Carnot engine.
(b) The amount of heat rejected to the low-temperature
heat reservoir.
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
Example
An inventor claims to have invented a heat engine that
develops a thermal efficiency of 80 percent when operating
between two heat reservoirs at 1000 K and 300 K.
Evaluate his claim.
BITS Pilani, Pilani Campus
Example:
A dwelling requires 633 MJ per day to maintain its
temperature at 21°C when the outside temperature is
0°C. A) if an electric heat pump is used to supply this
energy, determined the minimum theoretical work input
for one day operation in kJ/day. B) Evaluating electricity
at Rs. 8/kW.h, determine the minimum theoretical cost
to operate the heat pump, in Rs/day
BITS Pilani, Pilani Campus
Example:
A coal fired power plant has an efficiency of 35% and
produces net 500 MW of electricity. Coal releases
25 000 kJ/kg as it burns so how much coal is used
per hour?
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Example:
A water cooler for drinking water should cool 25 L/h
water from 18°C to 10°C using a small refrigeration
unit with a COP of 2.5. Find the rate of cooling
required and the power input to the unit.
BITS Pilani, Pilani Campus
Example:
A farmer runs a heat pump with a 2 kW motor. It
should keep a chicken hatchery at 30°C, which
loses energy at a rate of 10 kW to the colder
ambient Tamb. What is the minimum coefficient of
performance that will be acceptable for the heat
pump?
BITS Pilani, Pilani Campus
THE SECOND LAW OF
THERMODYNAMICS
Example
A Carnot heat engine receives 500 kJ of heat per cycle from a
high-temperature heat reservoir at 652oC and rejects heat
to a low-temperature heat reservoir at 30oC. Determine
(a) The thermal efficiency of this Carnot engine.
(b) The amount of heat rejected to the low-temperature
heat reservoir.
BITS Pilani, Pilani Campus