THE SECOND LAW OF

THERMODYNAMICS
 Examples
• 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. What you think ???

• Consider the heating of a room by the passage of

electric current through a resistor. Again, the first
law dictates that the amount of electric energy
supplied to the resistance wires be equal to the
amount of energy transferred to the room air as
heat. Now let us attempt to reverse this process.
What you think ???
• Finally, consider a paddle-wheel mechanism
that is operated by the fall of a mass. The
paddle wheel rotates as the mass falls and
stirs a fluid within an insulated container. As a
result, the potential energy of the mass
decreases, and the internal energy of the fluid
increases in accordance with the conservation
of energy principle. Think about reverse???

• It is clear from these arguments 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. A
process cannot occur unless it satisfies both
the first and the second laws of
thermodynamics.
 Thermal Reservoir
• Any physical body whose thermal energy capacity is large relative to
the amount of energy it supplies or absorbs can be modeled as
thermal energy reservoir.
• Example:The air in a room, for example, can be treated as a
reservoir in the analysis of the heat dissipation from a TV set in the
room, since the amount of heat transfer from the TV set to the
room air is not large enough to have a noticeable effect on the
room air temperature.
• 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.
 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 of 100%, or as for a
power plant to operate, the working fluid must exchange heat with
the environment as well as the furnace.
• Related to the Heat Engines.
 Heat Engines
• Work can easily be converted to other forms of energy, but converting other
forms of energy to work is not that easy.

• 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 thermal energy released during this
process is transferred to the steam as heat. The schematic of a basic steam power
plant
• Qin = amount of heat supplied to steam in boiler from a high-temperature
• 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
• Wnet, out = Wout – Win (kJ)
 Thermal Efficiency
• 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 ηth
• Only part of the heat transferred to the heat engine is converted to
work.
• 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
• The thermal efficiencies of work-producing devices are relatively
low. Ordinary spark-ignition automobile engines have a thermal
efficiency of about 25 percent. 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.
 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.
• Related to refrigerators or heat pumps.
 Refrigerators
• The transfer of heat from a low-temperature medium to a high-
temperature one requires special devices called refrigerators. The transfer
of heat from a low-temperature medium to a high-temperature one
requires special devices called refrigerators. Refrigerators, like heat
engines, are cyclic devices. 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 (throttling),
and an evaporator.
 Working
• 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.
 Coefficient of Performance

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. To accomplish
this objective, it requires a work input of Wnet,in.
Then the COP of a refrigerator can be expressed as
 Heat Pumps
• 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.
 Coefficient of Performance
• Measure of performance of a heat pump is also expressed in terms
of the coefficient of performance COPHP
 Interesting Information
• Air conditioners are basically refrigerators whose refrigerated space
is a room or a building instead of the food compartment. A window
air-conditioning unit cools a room by absorbing heat from the room
air and discharging it to the outside. The same air-conditioning unit
can be used as a heat pump in winter by installing it backwards. In
this mode, the unit absorbs heat from the cold outside and delivers
it to the room. Air-conditioning systems that are equipped with
proper controls and a reversing valve operate as air conditioners in
summer and as heat pumps in winter.
 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.
• Processes that are not reversible are called irreversible processes.
• Example: Once a cup of hot coffee cools, it will not heat up by retrieving the
heat it lost from the surroundings. If it could, the surroundings, as well as
the system (coffee), would be restored to their original condition, and this
would be a reversible process.
• Reversible processes actually do not occur in nature. They are merely
idealizations of actual processes.
• The more closely we approximate a reversible process, the more work
delivered by a work-producing device(car engines and gas or steam
turbines) or the less work required by a work-consuming
device(compressors, fans, and pumps).
• The better the design, the lower the irreversibilities and the higher the
second-law efficiency.
 Irreversibilities

• 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. A reversible process involves none of these.
 Internally and Externally Reversible
Processes
• A reversible process involves no irreversibilities associated with
either of them.
• A process is called internally reversible if no irreversibilities occur
within the boundaries of the system during the process. The quasi-
equilibrium process is an example of an internally reversible
process.
• A process is called externally reversible if no irreversibilities occur
outside the system boundaries during the process.
 THE CARNOT CYCLE
• The net work, thus the cycle efficiency, can be maximized by using
processes that require the least amount of work and deliver the most,
that is, by using reversible processes.
• Reversible cycles cannot be achieved in practice because the
irreversibilities associated with each process cannot be eliminated. Heat
engines and refrigerators that work on reversible cycles serve as models
to which actual heat engines and refrigerators can be compared.
• 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.
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)
Reversible Adiabatic Compression (process 4-1, temperature rises from TL to TH)
 THE CARNOT HEAT ENGINE
• 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

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,

This relation is often referred to as the Carnot efficiency, since the Carnot
heat engine is the best known reversible engine. This is the highest efficiency
a heat engine operating between the two thermal energy reservoirs at
Temperatures TL and TH can have.
Thermodynamic temperature scale related to
heat transfer, Temp is in K
• All irreversible (i.e., actual) heat engines operating between these
temperature limits (TL and TH) have lower efficiencies. An actual heat engine
cannot reach this maximum theoretical efficiency value because it is
impossible to completely eliminate all the irreversibilities associated with
the actual cycle.
• The thermal efficiencies of actual and reversible heat engines operating
between the same temperature limits compare as follows
• Most work-producing devices (heat engines) in operation today
have efficiencies under 40 percent.
• The thermal efficiency of actual heat engines can be maximized by
supplying heat to the engine at the highest possible temperature
(limited by material strength) and rejecting heat from the engine at
the lowest possible temperature
 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, reversible or irreversible, is
given by

• 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 above relations by
the ratios of the absolute temperatures of the high- and low-temperature
reservoirs.
• These are the highest coefficients of performance that a refrigerator or a
heat pump operating between the temperature limits of TL and TH can have.
All actual refrigerators or heat pumps operating between these
temperature limits (TL and TH) have lower coefficients of performance .
• The coefficients of performance of actual and reversible refrigerators
operating between the same temperature limits can be compared as
follows:
 Assignment # 6
• Q-23,43,44,45,49,55,75,76,80,90,
92,95,101,103,108,124,126,142