Second law of Thermodynamics

• The first law of thermodynamics is a statement of conservation of energy,

generalized to include internal energy.
• This law states that a change in internal energy in a system can occur as a result
of energy transfer by heat or by work, or by both.
• The law makes no distinction between the results of heat and the results of
work—either heat or work can cause a change in internal energy. However, an
important distinction between the two is not evident from the first law.
• One manifestation of this distinction is that it is impossible to convert internal
energy completely to mechanical energy by taking a substance through a
thermodynamic cycle such as in a heat engine
• Although the first law of thermodynamics is very important, it makes no
distinction between processes that occur spontaneously and those that do not.
• The second law of thermodynamics establishes which processes do and which
do not occur in nature.
• The following are examples of processes that proceed in only one direction, governed by the second
law:
– A rubber ball dropped to the ground bounces several times and eventually comes to rest, but a
ball lying on the ground never begins bouncing on its own.
– When two objects at different temperatures are placed in thermal contact with each other,
energy always flows by heat from the warmer to the cooler, never from the cooler to the
warmer.
– An oscillating pendulum eventually comes to rest because of collisions with air molecules and
friction at the point of suspension. The mechanical energy of the system is converted to internal
energy in the air, the pendulum, and the suspension; the reverse conversion of energy never
occurs.
• All these processes are irreversible—that is, they are processes that occur naturally in one direction
only. No irreversible process has ever been observed to run backward—if it were to do so, it would
violate the second law of thermodynamics.
• From an engineering standpoint, perhaps the most important implication of the second law is the
limited efficiency of heat engines. The second law states that a machine capable of continuously
converting internal energycompletely to other forms of energy in a cyclic process cannot be
constructed.
 Heat engines
• A heat engine is a device that converts internal energy to
mechanical energy.
• For instance, in a typical process by which a power plant
produces electricity, coal or some other fuel is burned, and
the high-temperature gases produced are used to convert
liquid water to steam. This steam is directed at the blades of a
turbine, setting it into rotation. The mechanical energy
associated with this rotation is used to drive an electric
generator.
• Another heat engine—the internal combustion engine in an
automobile—uses energy from a burning fuel to perform
work that results in the motion of the automobile.
• A heat engine carries some working substance through a
cyclic process during which (1) the working substance
absorbs energy from a high-temperature energy reservoir,
(2) work is done by the engine, and (3) energy is expelled by
the engine to a lower-temperature reservoir.
• Consider the operation of a steam engine in which the
working substance is water. The water in a boiler absorbs
energy from burning fuel and evaporates to steam, which
then does work by expanding against a piston. After the
steam cools and condenses, the liquid water produced
returns to the boiler and the cycle repeats.
• It is useful to represent a heat engine schematically as in the
Figure. The engine absorbs a quantity of energy Q h from the hot
reservoir, does work W, and then gives up a quantity of energy Q c
to the cold reservoir.
Because the working substance goes through a cycle, its initial and
final internal energies are equal, and so Hence, from the first law of
thermodynamics, and with no change in internal energy, the net work
W done by a heat engine is equal to the net energy Q net flowing
through it. As we can see from Figure therefore
• In this expression, to be consistent with
traditional treatments of heat engines, we take
both Q h and Q c to be positive quantities, even
though Q c represents energy leaving the engine.
• In discussions of heat engines, we shall describe
energy leaving a system with an explicit minus.
Also note that we model the energy input and
output for the heat engine as heat, as it often is;
however, the energy transfer could occur by
another mechanism
The net work done in a cyclic process is the area
enclosed by the curve representing the process
on a PV diagram. This is shown for an arbitrary
cyclic process in the Figure
 Thermal efficiency
The thermal efficiency e of a heat engine is
defined as the ratio of the net work done by the
engine during one cycle to the energy absorbed
at the higher temperature during the cycle:
• We can think of the efficiency as the ratio of what
you get (mechanical work) to what you give (energy
transfer at the higher temperature).
• In practice, we find that all heat engines expel only a
fraction of the absorbed energy as mechanical work
and that consequently the efficiency is less than
100%.
• For example, a good automobile engine has an
efficiency of about 20%, and diesel engines have
efficiencies ranging from 35% to 40%.
 Second law of thermodynamics
• The thermal efficiency equation shows that a heat engine has 100%
efficiency (e =1) only if Q c = 0—that is, if no energy is expelled to
the cold reservoir.
• In other words, a heat engine with perfect efficiency would have to
expel all of the absorbed energy as mechanical work.
• On the basis of the fact that efficiencies of real engines are well
below 100%, the Kelvin–Planck form of the second law of
thermodynamics states the following:
This statement of the second law means that, during
the operation of a heat engine, W can never be equal
to Q h , or, alternatively, that some energy Q c must be
rejected to the environment. The figure is a schematic
diagram of the impossible “perfect” heat engine.
 Summary of first and second laws
• The first and second laws of thermodynamics
can be summarized as follows:
• The first law specifies that we cannot get
more energy out of a cyclic process by work
than the amount of energy we put in
• The second law states that we cannot break
even because we must put more energy in, at
the higher temperature, than the net amount
of energy we get out by work.
 Example
• Find the efficiency of a heat engine that
absorbs 2 000 J of energy from a hot reservoir
and exhausts 1 500 J to a cold reservoir.
 Example
• A heat engine is rated to have an efficiency of
27%. Find the work done if the engine is
measured to exhaust 1800J of heat to a cold
reservoir
 Example
• A heat engine absorbs 24% more energy from
a hot reservoir than it exhausts. Determine its
efficiency . Compare this to an engine that
absorbs 30% more energy than it exhausts.
 Refrigerators and Heat Pumps
• Refrigerators and heat pumps are heat
engines running in reverse. Here, we
introduce them briefly for the purposes of
developing an alternate statement of the
second law
• In a refrigerator or heat pump, the engine
absorbs energy Qc from a cold reservoir and
expels energy Qh to a hot reservoir
• This can be accomplished only if work is done on the
engine.
• From the first law, we know that the energy given up
to the hot reservoir must equal the sum of the work
done and the energy absorbed from the cold reservoir.
• Therefore, the refrigerator or heat pump transfers
energy from a colder body (for example, the contents
of a kitchen refrigerator or the winter air outside a
building) to a hotter body (the air in the kitchen or a
room in the building).
• In practice, it is desirable to carry out this process
with a minimum of work. If it could be
accomplished without doing any work, then the
refrigerator or heat pump would be “perfect”
• Again, the existence of such a device would be in
violation of the second law of thermodynamics,
which in the form of the Clausius statement
• In simpler terms, energy does not flow spontaneously from a
cold object to a hot object.
• For example, we cool homes in summer using heat pumps
called air conditioners. The air conditioner pumps energy
from the cool room in the home to the warm air outside.
• This direction of energy transfer requires an input of energy
to the air conditioner, which is supplied by the electric power
company.
• The Clausius and Kelvin–Planck statements of the second law
of thermodynamics appear, at first sight, to be unrelated, but
in fact they are equivalent in all respects.
 REVERSIBLE AND IRREVERSIBLE
PROCESSES
• In the next section we discuss a theoretical heat
engine that is the most efficient possible.
• To understand its nature, we must first examine the
meaning of reversible and irreversible processes.
• In a reversible process, the system undergoing the
process can be returned to its initial conditions along
the same path shown on a PV diagram, and every
point along this path is an equilibrium state. A process
that does not satisfy these requirements is irreversible.
• All natural processes are known to be irreversible
 THE CARNOT ENGINE
• In 1824 a French engineer named Sadi Carnot
described a theoretical engine, now called a Carnot
engine, that is of great importance from both
practical and theoretical viewpoints.
• He showed that a heat engine operating in an ideal,
reversible cycle—called a Carnot cycle—between
two energy reservoirs is the most efficient engine
possible.
• Such an ideal engine establishes an upper limit on the
efficiencies of all other engines.
• That is, the net work done by a working substance taken
through the Carnot cycle is the greatest amount of work
possible for a given amount of energy supplied to the
substance at the upper temperature.
• Carnot’s theorem can be stated as follows:

• All real engines are less efficient than the Carnot engine
because they do not operate through a reversible cycle.
• The efficiency of a real engine is further reduced by such
practical difficulties as friction and energy losses by
conduction.
 Description of Carnot cycle
• To describe the Carnot cycle taking place
between temperatures Tc and Th , we assume
that the working substance is an ideal gas
contained in a cylinder fitted with a movable
piston at one end. The cylinder’s walls and the
piston are thermally nonconducting.

• Four stages of the Carnot cycle are shown in

the Figure
• The PV diagram for the cycle is shown in the Figure. The
Carnot cycle consists of two adiabatic processes and two
isothermal processes, all reversible:
 Carnot Efficiency
• The net work done in this reversible, cyclic process is equal to
the area enclosed by the path ABCDA in the Figure
• Since the change in internal energy is zero, the net work W
done in one cycle equals the net energy transferred into the
system, Qh - Qc .
• The thermal efficiency of the engine is given by
• In this case,
 Example
• The highest theoretical efficiency of a certain
engine is 30%. If this engine uses the
atmosphere, which has a temperature of 300
K, as its cold reservoir, what is the
temperature of its hot reservoir?
 Coefficient of performance
• The effectiveness of a heat pump is described
in terms of a number called the coefficient of
performance (COP).
• In the heating mode, the COP is defined as the
ratio of the energy transferred to the hot
reservoir to the work required to transfer that
energy:
• Note that the COP is similar to the thermal
efficiency for a heat engine in that it is a ratio of
what you get (energy delivered to the interior of
the building) to what you give (work input).
• Because Qh is generally greater than W, typical
values for the COP are greater than unity.
• It is desirable for the COP to be as high as
possible, just as it is desirable for the thermal
efficiency of an engine to be as high as possible.
 Example
• In an electric heater, electrical energy can be
converted to internal energy with an
efficiency of 100%. By what percentage does
the cost of heating your home change when
you replace your electric heating system with
a heat pump that has a COP of 4? Assume that
the motor running the heat pump is 100%
efficient.
• The cost of heating your home decreases to 25%
of the original cost. With electric heating, you
receive the same amount of energy for heating
your home as enters it by electricity.
• The COP of 4 for the heat pump means that you
are receiving four times as much energy as the
energy entering by electricity. With four times as
much energy per unit of energy from electricity,
you need only one-fourth as much electricity.
 Entropy
• The zeroth law of thermodynamics involves the
concept of temperature, and the first law involves
the concept of internal energy.
• Temperature and internal energy are both state
functions—that is, they can be used to describe
the thermodynamic state of a system.
• Another state function—this one related to the
second law of thermodynamics—is entropy S.
 Entropy

A reversible engine has the following relation between the

heat transferred and the reservoir temperatures:

Rewriting,

This quantity, Q/T, is the same for both reservoirs.

This conserved quantity is defined as the change in
entropy.
 Entropy

Like internal energy, entropy is a state function

Unlike energy, entropy is NOT conserved

In a reversible heat engine, the

entropy does not change.
 Entropy
A real engine will operate at a lower efficiency than a
reversible engine; this means that less heat is converted to
work.

for irreversible
processes

Any irreversible process results in an

increase of entropy.
Example: An irreversible engine operating between the temperatures of 550
K and 300 K extracts 1200 J of heat from the hot reservoir and produces 450
J of work. How much entropy is created in the process?

Qc Qh
Stot  
Tc Th
Qh  1200 J
Tc  300 K
Th  550 K
W  Qh  Qc  450 J  Qc  1200  450  J  750 J
750 1200
 Stot    0.318 J
300 550 K
 Entropy

To generalize:
• The total entropy of the universe increases whenever an
irreversible process occurs.
• The total entropy of the universe is unchanged whenever a
reversible process occurs.
Since all real processes are irreversible, the entropy of the
universe continually increases. If entropy decreases in a
system due to work being done on it, a greater increase in
entropy occurs outside the system.
 What you need to remember….
• What is a heat engine
• What is thermal efficiency
• What is coefficient of performance
• What does the second law of thermodynamics
state
• What is carnot efficiency
• Entropy