CHAPTER 6
SECOND LAW OF THERMODYNAMICS
5.1 Introduction
Transferring heat to a
paddle wheel will not
cause it to rotate.
A cup of hot coffee does not
get hotter in a cooler room. Processes occur in a certain
direction, and not in the reverse
direction.
Transferring heat to
a wire will not
generate electricity. A process must satisfy both the first and second laws
of thermodynamics to proceed.
Major Uses of the Second Law the degree of completion of chemical
1. The second law may be used to identify the reactions
direction of processes.
2. The second law assets that energy has
quality as well as quantity. The first law is
concerned with the quantity of energy and
the transformations of energy from one
form to another with no regard to its
quality. The second law provides the
necessary means to determine the quality
as well as the degree of degradation of
energy during a process.
3. The second law of thermodynamics is also
used in determining the theoretical limits for
the performance of commonly used
engineering systems, such as heat engines
and refrigerators, as well as predicting
5. 2. Thermal Energy Reservoirs
A hypothetical body with a relatively large
thermal energy capacity (Mass × Specific
heat) that can supply or absorb finite amounts
of heat without undergoing any change in
temperature is called thermal energy
reservoir, or just a reservoir.
• In practice, large bodies of water such as
oceans, lakes, and riveters as well as
atmospheric air can be modelled as
thermal energy reservoirs.
• A two-phase system can also be modelled Bodies with relatively large thermal
as a reservoir since it can absorb and masses can be modelled as thermal
release large quantities of heat while energy reservoirs.
remaining at constant temperature.
• Another familiar example of a thermal
energy reservoir is the industrial furnace.
A reservoir that supplies energy in the form 5.3. Heat Engines
of heat is called a source, and one that Heat Engines: The devices that convert
absorbs energy in the form heat is called heat to work.
sink.
Thermal energy reservoirs are often referred
to as heat reservoirs since they supply or
absorb energy in the form of heat.
Work can always be converted to heat
directly and completely, but the reverse is not
true.
1. They receive heat from a high-temperature
source (solar energy, oil furnace, nuclear
A source supplies energy in the form of heat, reactor, etc.).
and a sink absorbs it.
2. They convert part of this heat to work Heat engines and other cyclic devices usually
(usually in the form of rotating shaft.) involve a fluid from which heat is transferred
3. They reject the remaining waste heat to a while undergoing a cycle.
low temperature sink (the atmosphere, Part of heat received by heat engine is
rivers, etc.). converted to work, while the rest is rejected
4. They operate on a cycle. to a sink.
This fluid is called the working fluid.
Part of the heat
received by a
heat engine is
converted to Schematic of
work, while the
rest is rejected to
a steam
a sink. power plant.
The work-producing device that best fits into
the definition of a heat engine is the steam The net work output of this power plant is
power plant, which is an external-combustion simply the difference between the total work
engine. output of the plant and the total work input
The various quantities shown on this figure are Wnet,out = Wout − Win (kJ)
as follows: Or
Qin = amount of heat supplied to steam in
boiler from a high-temperature Wnet,out = Qin − Qout (kJ)
source (furnace)
Qout = amount of heat rejected from steam in
condenser to a low-temperature sink (the
atmosphere, a river, etc.)
Wout = amount of work delivered by steam as
it expands in turbine
Win = amount of work required to compress
water to boiler pressure A portion of the work output of a heat engine
is consumed internally to maintain continuous
operation.
Thermal Efficiency Can we not just take the condenser out of
The fraction of the heat input that is the plant and save all that waste energy?
converted to net work output is a measure The answer is, unfortunately a firm no for
of the performance of a heat engine and is the simple reason that without a heat
called the thermal efficiency ηth rejection process in a condenser, the cycle
Net work output cannot be completed.
Thermal Efficiency =
Total heat input Every heat engine must some energy by
𝑊𝑛𝑒𝑡,𝑜𝑢𝑡
𝜂𝑡ℎ = transferring it to a low-temperature
𝑄𝑖𝑛
It can also be expressed as reservoir in order to complete the cycle,
𝑄 even under idealized conditions
𝜂𝑡ℎ = 1 - 𝑜𝑢𝑡
𝑄𝑖𝑛
Since Wnet, out = Qin – Qout
A heat-engine cycle
Can we save Qout?
cannot be completed
In a stem power plant, the condenser is the
without rejecting some
device where large quantifies of waste
heat to a low-
heat is rejected to riverers, lakes, or
temperature sink.
atmosphere.
Example 1 Given
Heat is transferred to a heat engine from a 𝑄ሶ 𝐻 = 80 MW and 𝑄ሶ 𝐿 = 50 MW
furnace at a rate of 80 MW. If the rate of The net power output of this heat engine is
waste heat rejection to a nearby river is 50
MW, determine the net power output and the 𝑊ሶ 𝑛𝑒𝑡 , 𝑜𝑢𝑡= 𝑄ሶ 𝐻 - 𝑄ሶ 𝐿 = (80 - 50) MW = 30MW
thermal efficiency for this heat engine. Then the thermal efficiency is easily
determined to be
𝑊ሶ 𝑛𝑒𝑡 ,𝑜𝑢𝑡 30 𝑀𝑊
𝜂𝑡ℎ = = = 0.375 (or 37.5
𝑄ሶ 𝐻 80 𝑀𝑊
percent)
The Second Law of Thermodynamics:
Kelvin–Planck Statement
It is impossible for any device that operates on
a cycle to receive heat from a
single reservoir and produce a net amount of
work.
No heat engine can have a thermal efficiency 5.4. Refrigerators and Heat Pumps
of 100 percent or as for a power plant to The transfer heat from low-
operate, the working fluid must exchange heat
temperature medium to a high-
with the environment as well as the furnace.
A heat engine that violets the Kelvin Planck temperature one requires devices
statement of the second law called Refrigerators.
Refrigerators, like heat engines are
cyclic device.
The working fluid used in the
refrigeration cycle is called a
refrigerant.
The most frequently used refrigeration
cycle is the vapour-compression
refrigeration cycle
Basic Components of refrigeration system and Coefficient of Performance
typical operating conditions. The efficiency of a refrigerator is expressed in
terms of the coefficient of performance (COP),
denoted by COPR.
The objective of a refrigerator is to remove
heat (QL) from the refrigerated space.
𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑜𝑢𝑡𝑝𝑢𝑡 𝑄𝐿
COPR = =
𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑖𝑛𝑝𝑢𝑡 𝑊𝑛𝑒𝑡,𝑖𝑛
𝑄𝐿 1
COPR = = 𝑄𝐻
𝑄 𝐻 − 𝑄𝐿 ൗ𝑄 −1
𝐿
Can the value of COPR be greater than unity?
Yes! Efficiency can never be greater than 1,
but COP can.
Heat Pumps
The objective of a heat pump is to move heat
from a cooler environment to a warmer one.
𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑜𝑢𝑡𝑝𝑢𝑡 𝑄𝐻
COPHP = =
𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑖𝑛𝑝𝑢𝑡 𝑊𝑛𝑒𝑡,𝑖𝑛
𝑄𝐻 1
COPHP = =
𝑄𝐻 −𝑄𝐿 1 − 𝑄𝐿ൗ𝑄
𝐻
The objective of a heat
pump is to supply heat
The objective of a refrigerator is to remove QH into the warmer space
QL from the cooled space.
COP HP = COPR + 1
Example COPR =
7.43 𝐾𝑊
= 2.80
2.65 𝐾𝑊
A refrigerator is used to cool water from
Qin = mcp (T1 – T2)
23℃ to 5℃ in a continuous manner. The heat 𝑄𝑖𝑛 7.43 𝐾𝑊
rejected in the condenser is 605 KJ/min and m= 𝐾𝐽
𝑐𝑝 𝑇1 −𝑇2 4.18𝐾𝐺℃ (23 −5)
the power is 2.65 kW. Determine the rate at 𝑚ሶ = 0.0988 kg/s
which water is cooled in L/min and the COP 𝑚ሶ
𝜌= ሶ
of the refrigerator. The specific heat of water 𝑉
𝑘𝑔
is 4.18 kJ/kg.℃and the density is 1 Kg/L 𝑚ሶ 0.0988 𝑠 60 𝑆
𝑉ሶ = = 𝐾𝑔 = 5.928 L/min
Solution 𝜌 1 𝐿 1 𝑚𝑖𝑛
𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝐶𝑜𝑜𝑙𝑖𝑛𝑔
COPR = The Second Law of Thermodynamics:
𝑃𝑜𝑤𝑒𝑟 𝑖𝑛
𝑄ሶ 𝑛𝑒𝑡 = 𝑊ሶ 𝑛𝑒𝑡 in a cycle Clausius Statement
Qin – Qout = Wout – Win It is impossible to construct a device that
It’s a fridge so no work output operates in a cycle and produces no effect
605𝐾𝐽/𝑚𝑖𝑛 other than the transfer of heat from a lower-
ሶ ሶ
𝑄in = Qout – Win = - 2.65 KW =
60 𝑠/𝑚𝑖𝑛 temperature body to a higher-temperature
7.43 KW body
5.5. Reversible and Irreversible
Processes
Reversible Process: A process that can be
reversed without leaving any trace on the
surroundings.
Irreversible processes: A process that is not
reversible.
All the processes occurring in nature are are
irreversible.
Why are we interested in reversible
processes?
1) They are easy to analyse and
2) They serve as idealized models
(theoretical limits ) to which actual
processes can be compared
Some processes are more irreversible than
others.
The factors that cause a process to be
irreversible are called Irreversibilities.
They include friction, unrestrained
expansion, mixing of two fluids, heat
transfer across a finite temperature
difference, electric resistance, inelastic
deformation of solids, and chemical
reactions.
The presence of any of these effects renders a
process irreversible.
Irreversible compression and expansion
processes.
5.6. Carnot Cycle
Probably the best known reversible cycle is the
Carnot cycle, first proposed in 1824 by
French engineer Sadi Carnot. The theoretical
heat engine that operates on the Carnot cycle
is called the Carnot heat engine.
The Carnot cycle is composed of four
reversible processes—two isothermal and two
adiabatic—and it can be executed either in a
closed or a steady-flow system. P-V Diagram of Carnot
Cycle
Reversible Isothermal Expansion (process 1-
2, TH = constant)
Reversible Adiabatic Expansion (process 2-3,
temperature drops from TH to TL).
Reversible Isothermal Compression (process
3-4, TL = constant)
Execution of the Carnot cycle in
Reversible Adiabatic Compression (process 4-1, temperature
a closed system
rises from TL to T H)
5. 7 Carnot Principles 5.8. The Carnot Heat Engine
Two conclusions pertain to the thermal The Carnot heat engine is the most efficient of
efficiency of reversible and irreversible (i.e., all heat engines operating between the same
actual) heat engines, and they are known as high temperature and low temperature
the Carnot principles (Fig below), expressed reservoir.
as follows: The thermal efficiency of any heat engine,
1. The efficiency of an irreversible heat reversible or irreversible, is given
engine is always less than the efficiency of a
reversible one operating between the same
two reservoirs.
2. The efficiencies of all reversible heat For Carrot Engine
engines operating between the same two
reservoirs are the same
The Carnot
principles.
Example
A Carnot heat engine receives 500 kJ of heat
per cycle from a high temperature source at
652℃ and reject heats to a low temperature
sink at 30℃. Determine the thermal efficiency
and heat rejected from this engine.
A refrigerator or a heat pump that operates on the
5.9 The Carnot Refrigerator and Heat reversed Carnot cycle is called a Carnot
Pump refrigerator, or a Carnot heat pump. The
coefficient of performance
of any refrigerator or heat pump, reversible or
irreversible, is given
where QL is the amount of heat absorbed from the low-
temperature medium and QH is the amount of heat rejected
to the high-temperature medium.
The COPs of all reversible refrigerators or heat
pumps can be determined by replacing the heat
transfer ratios in the preceding relations with the
ratios of the absolute temperatures of the high-
No refrigerator can have a higher COP than and low-temperature reservoirs
a reversible refrigerator operating between
the same temperature limits.
Example
A heat pump is to be used to heat a house
during the winter, as shown in the figure. The
house is to be maintained at 21°C at all times.
The house is estimated to be losing heat at a
The COP of a reversible refrigerator or heat rate of 135,000 kJ/h when the outside
pump is the maximum theoretical value for the temperature drops to –5°C. Determine the
specified temperature limits. minimum power required to drive this heat
Actual refrigerators or heat pumps may pump.
approach these values as their designs are
improved, but they can never reach them.
The COPs of both the refrigerators and the
heat pumps decrease as TL decreases.
Discussion This reversible heat pump can meet the
heating requirements of this house by consuming
electric power at a rate of 3.32 kW only. If this house
were to be heated by electric resistance heaters
instead, the power consumption would jump up 11.3
times to 37.5 kW. This is because in resistance
heaters the electric energy is converted to heat at a
one-to-one ratio. With a heat pump, however,
energy is absorbed from the outside and carried to
the inside using a refrigeration cycle that consumes
only 3.32 kW. Notice that the heat pump does not
create energy. It merely transports it from one
medium (the cold outdoors) to another
(the warm indoors)