THE SECOND LAW OF

THERMODYNAMICS
BY CAP.ENG HAZIM MOHAMED TAHA YOUSIF
• It is common experience that a cup of hot
coffee left in a cooler room eventually cools
off This process satisfies the first law of
thermodynamics since the amount of energy
lost by the coffee is equal to the amount gained
by the surrounding air. Now let us consider the
reverse process—the hot coffee getting even
hotter in a cooler room as a result of heat
transfer from the room air. We all know that
this process never takes place. Yet, doing so
would not violate the first law as long as the
amount of energy lost by the air is equal to the
amount gained by the coffee.
• It is clear from these argument that processes
proceed in a certain direction and not in the
reverse direction The first law places no
restriction on the direction of a process, but
satisfying the first law does not ensure that the
process can actually occur.
• The use of the second law of thermodynamics is not limited to identifying the direction of
processes, however. The second law also asserts 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.
• Preserving the quality of energy is a major concern to engineers, and the second law
provides the necessary means to determine the quality as well as the degree of
degradation of energy during a process. As discussed later in this chapter, more of high-
temperature energy can be converted to work, and thus it has a higher quality than the
same amount of energy at a lower temperature.
• 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 the degree of completion of chemical reactions.
• A process cannot occur unless it satisfies both the first and the second laws of
thermodynamics
• it is very convenient to have a
hypothetical body with a relatively large
thermal energy capacity that can supply
or absorb finite amounts of heat without
undergoing any change in temperature.
Such a body is called a thermal energy
reservoir, or just a reservoir.
• A reservoir that supplies energy in the
form of heat is called a source, and one
that absorbs energy in the form of heat is
called a sink
• Thermal energy reservoirs are often
referred to as heat reservoirs since they
supply or absorb energy in the form of
heat.
 HEAT ENGINES
• work can be converted to heat directly and completely, but converting heat to work
requires the use of some special devices. These devices are called heat engines.
• Heat engines differ considerably from one another, but all
can be characterized by the following:
1. They receive heat from a high-temperature source (solar energy, oil
furnace, nuclear reactor, etc.).
2. They convert part of this heat to work (usually in the form of a rotating
shaft).
3. They reject the remaining waste heat to a low-temperature sink (the
atmosphere, rivers, etc.).
4. They operate on a cycle.
• Heat engines and other cyclic devices usually involve a fluid to and from which heat is
transferred while undergoing a cycle. This fluid is called the working fluid.
• The term heat engine is often used in
a broader sense to include work
producing devices that do not
operate in a thermodynamic cycle.
Engines that involve internal
combustion such as gas turbines and
car engines fall into this category.
These devices operate in a
mechanical cycle but not in a
thermodynamic cycle since the
working fluid (the combustion gases)
does not undergo a complete cycle.
Instead of being cooled to the initial
temperature, the exhaust gases are
purged and replaced by fresh air-and-
fuel mixture at the end of the cycle.
• The work-producing device that best
fits into the definition of a heat
engine is the steam power plant,
which is an external-combustion
engine. That is, combustion takes
place outside the engine, and the
• The net work output of this power plant is simply the difference between the total work
output of the plant and the total work input
• for a closed system undergoing a cycle, the change in internal energy U is zero, and
therefore the net work output of the system is also equal to the net heat transfer to the
system

Thermal Efficiency
• represents the magnitude of the energy wasted in order to complete the cycle. But is
never zero; thus, the net work output of a heat engine is always less than the amount of
heat input. That is, only part of the heat transferred to the heat engine is converted to
work. The fraction of the heat input that is converted to net work output is a measure of
the performance of a heat engine and is called the thermal efficiency .
• For heat engines, the desired output is the net work output, and the
required input is the amount of heat supplied to the working fluid. Then
the thermal efficiency of a heat engine can be expressed as
 or

Or
• Cyclic devices of practical interest such as heat engines, refrigerators,
and heat pumps operate between a high-temperature medium (or
reservoir) at temperature and a low-temperature medium (or reservoir)
at temperature . To bring uniformity to the treatment of heat engines,
refrigerators, and heat pumps, we define these two quantities:
• Notice that both and are defined as
magnitudes and therefore are positive
quantities. The direction of and is easily
determined by inspection. Then the net
work output and thermal efficiency
relations for any heat engine can also be
expressed as

Or
• Thermal efficiency is a measure of how efficiently a heat engine
converts the heat that it receives to work. Heat engines are built for the
purpose of converting heat to work, and engineers are constantly trying
to improve the efficiencies of these devices since increased efficiency
means less fuel consumption and thus lower fuel bills and less
pollution.
• The thermal efficiencies of work-producing devices are relatively low.
Ordinary spark-ignition automobile engines have a thermal efficiency of
about 25 percent. That is, an automobile engine converts about 25
percent of the chemical energy of the gasoline to mechanical work.
This number is as high as 40 percent for diesel engines and large gas-
turbine plants and as high as 60 percent for large combined gas-steam
power plants. Thus, even with the most efficient heat engines available
today, almost one-half of the energy supplied ends up in the rivers,
lakes, or the atmosphere as waste or useless energy.
 Example 1
• Heat is transferred to a heat engine from a furnace at a rate of 80 MW. If the rate of waste
heat rejection to a nearby river is 50 MW, determine the net power output and the thermal
efficiency for this heat engine.
 The Second Law of Thermodynamics:
Kelvin–Planck Statement
• even under ideal conditions, a heat engine
must reject some heat to a low-temperature
reservoir in order to complete the cycle.
That is, no heat engine can convert all the
heat it receives to useful work. This
limitation on the thermal efficiency of heat
engines forms the basis for the Kelvin–
Planck statement of the second law of
thermodynamics, which is expressed as
follows:
• 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.
 REFRIGERATORS AND HEAT PUMPS
• We all know from experience that heat is transferred in
the direction of decreasing temperature, that is, from
high-temperature mediums to low temperature ones.
This heat transfer process occurs in nature without
requiring any devices. The reverse process, however,
cannot occur by itself. The transfer of heat from a low-
temperature medium to a high-temperature one
requires special devices called refrigerators.
• The working fluid used in the refrigeration cycle is
called a refrigerant. The most frequently used
refrigeration cycle is the vapor-compression
refrigeration cycle, which involves four main
components: a compressor, a condenser, an expansion
valve, and an evaporator,
• The refrigerant enters the compressor as a vapor and is compressed to
the condenser pressure. It leaves the compressor at a relatively high
temperature and cools down and condenses as it flows through the
coils of the condenser by rejecting heat to the surrounding medium. It
then enters a capillary tube where its pressure and temperature drop
drastically due to the throttling effect. The low-temperature refrigerant
then enters the evaporator, where it evaporates by absorbing heat
from the refrigerated space. The cycle is completed as the refrigerant
leaves the evaporator and reenters the compressor. In a household
refrigerator, the freezer compartment where heat.

Coefficient of Performance
• The efficiency of a refrigerator is expressed in terms of the coefficient
of performance (COP), denoted by . The objective of a refrigerator is
to remove heat () from the refrigerated space. To accomplish this
objective, it requires a work input of . Then the COP of a refrigerator
can be expressed as
 Heat pump
• Another device that transfers heat from a low-temperature medium to
a high-temperature one is the heat pump.
• Refrigerators and heat pumps operate on the same cycle but differ in
their objectives. The objective of a refrigerator is to maintain the
refrigerated space at a low temperature by removing heat from it.
Discharging this heat to a higher-temperature medium is merely a
necessary part of the operation, not the purpose. The objective of a
heat pump, however, is to maintain a heated space at a high
temperature. This is accomplished by absorbing heat from a low-
temperature source, such as well water or cold outside air in winter,
and supplying this heat to the high-temperature medium such as a
house
 The Second Law of Thermodynamics:
Clausius Statement
• It is impossible to construct a device
that operates in a cycle and produces
no effect other than the transfer of
heat from a lower-temperature body
to a higher-temperature body.
• The Kelvin–Planck and the
Clausius statements are
equivalent in their
consequences, and either
statement can be used as the
expression of the second law
of thermodynamics. Any
device that violates the
Kelvin–Planck statement also
violates the Clausius
statement, and vice versa.
This can be demonstrated as
follows.
 REVERSIBLE AND IRREVERSIBLE PROCESSES
• A reversible process is defined as a process that can be reversed without leaving any trace on
the surroundings That is, both the system and the surroundings are returned to their initial
states at the end of the reverse process. This is possible only if the net heat and net work
exchange between the system and the surroundings is zero for the combined (original and
reverse) process. Processes that are not reversible are called irreversible processes.
• It should be pointed out that a system can be restored to its initial state
following a process, regardless of whether the process is reversible or
irreversible. But for reversible processes, this restoration is made without
leaving any net change on the surroundings.
• A totally reversible process involves no heat transfer (adiabatic) through a
finite temperature difference, no non quasi-equilibrium changes, and no
friction or other dissipative effects.
• 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.
 THE CARNOT heat engine

• Reversible Isothermal Expansion (process 1-2,

constant). Initially (state 1), the temperature of the gas
is and the cylinder head is in close contact with a
source at temperature . The gas is allowed to expand
slowly, doing work on the surroundings. As the gas
expands, the temperature of the gas tends to decrease.
But as soon as the temperature drops by an
infinitesimal amount dT, some heat is transferred from
the reservoir into the gas, raising the gas temperature
to . Thus, the gas temperature is kept constant at .
Since the temperature difference between the gas and
the reservoir never exceeds a differential amount dT,
this is a reversible heat transfer process. It continues
until the piston reaches position 2. The amount of total
heat transferred to the gas during this process is .
• Reversible Adiabatic Expansion (process 2-3,
temperature drops from to ). At state 2, the reservoir
that was in contact with the cylinder head is removed
and replaced by insulation so that the system
becomes adiabatic. The gas continues to expand
slowly, doing work on the surroundings until its
temperature drops from to (state 3). The piston is
assumed to be frictionless and the process to be
quasi equilibrium, so the process is reversible as well
as adiabatic.
• Reversible Isothermal Compression (process 3-4,
constant). At state 3, the insulation at the cylinder head is
removed, and the cylinder is brought into contact with a
sink at temperature . Now the piston is pushed inward by
an external force, doing work on the gas. As the gas is
compressed, its temperature tends to rise. But as soon as it
rises by an infinitesimal amount dT, heat is transferred from
the gas to the sink, causing the gas temperature to drop to
. Thus, the gas temperature remains constant at . Since the
temperature difference between the gas and the sink never
exceeds a differential amount dT, this is a reversible heat
transfer process. It continues until the piston reaches state
4. The amount of heat rejected from the gas during this
process is .
• Reversible Adiabatic Compression
(process 4-1, temperature rises from to
). State 4 is such that when the low-
temperature reservoir is removed, the
insulation is put back on the cylinder
head, and the gas is compressed in a
reversible manner, the gas returns to its
initial state (state 1). The temperature
rises from to during this reversible
adiabatic compression process, which
completes the cycle.
• The P-V diagram of this cycle is shown
 The Reversed Carnot Cycle
• The Carnot heat-engine cycle just described is a
totally reversible cycle. Therefore, all the
processes that comprise it can be reversed, in
which case it becomes the Carnot refrigeration
cycle. This time, the cycle remains exactly the
same, except that the directions of any heat and
work interactions are reversed: Heat in the
amount of is absorbed from the low-temperature
reservoir, heat in the amount of is rejected to a
high-temperature reservoir, and a work input of
is required to accomplish all this. The P-V
diagram of the reversed Carnot cycle is the same
as the one given for the Carnot cycle, except that
the directions of the processes are reversed
• The hypothetical heat engine that operates on the reversible Carnot cycle is called the
Carnot heat engine. The thermal efficiency of any heat engine, reversible or irreversible,
is
• where is heat transferred to the heat engine from a high-temperature reservoir at , and is
heat rejected to a low-temperature reservoir at . For reversible heat engines, the heat
transfer ratio in the above relation can be replaced by the ratio of the absolute
temperatures of the two reservoirs, Then the efficiency of a Carnot engine, or any
reversible heat engine, becomes This relation is often referred to as the Carnot efficiency
• The thermal efficiencies of actual and reversible heat engines operating
between the same temperature limits compare as follows
 THE CARNOT REFRIGERATOR AND HEAT PUMP

• A refrigerator or a heat pump that operates on the reversed Carnot cycle is called a
Carnot refrigerator, or a Carnot heat pump. The coefficient of performance of any
refrigerator or heat pump
 Example
• An inventor claims to have developed a refrigerator that maintains the refrigerated space
at 35°F while operating in a room where the temperature is 75°F and that has a COP of
13.5. Is this claim reasonable?
Example
• A heat pump is to be used to heat a house during the
winter, as shown in Fig. The house is to be maintained
at 21°C at all times. The house is estimated to be losing
heat at a rate of 135,000 kJ/h when the outside
temperature drops to -5°C. Determine the minimum
power required to drive this heat pump.