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AE 231 Thermodynamics

Chapter 7
The classical Second Law of
Instructor: Assoc. Prof. Dr. Sinan Eyi
The Second Law of Thermodynamics

►From conservation of mass and energy

principles, mass and energy cannot be created or
►Conservation of mass and energy principles do
not show whether the process can actually occur.
►The second law of thermodynamics provides
information for whether a process can occur.
The Second Law of Thermodynamics

A system that undergoes a cycle involving work and heat.

The Second Law of Thermodynamics

An example showing the impossibility of completing a cycle by transferring

heat from a low-temperature body to a high-temperature body

The Second Law of Thermodynamics

By using the second law of thermodynamics, we can:

►predict the direction of processes.
►establish conditions for equilibrium.
►determine the best theoretical performance of cycles,
engines, and other devices.
►evaluate quantitatively the factors that degrade attainment
of the best theoretical performance level.
►define a temperature scale independent of the properties
of substance.
The second law of thermodynamics can also be used in
philosophy, economics, and other disciplines.
Second Law of Thermodynamics
Alternative Statements

There is no simple statement that captures all

aspects of the second law. Several alternative
formulations of the second law are found in the
technical literature. Three prominent ones are:

►Clausius Statement
►Kelvin-Planck Statement
Second Law of Thermodynamics
Alternative Statements
►Like every physical law, the basis of the second law of
thermodynamics is experimental evidence. While the
three forms given are not directly demonstrable in the
laboratory, deductions from them can be verified
experimentally, and this infers the validity of the
second law statements.
Clausius Statement
of the Second Law

It is impossible for any system to operate in such a way

that the sole result would be an energy transfer by heat
from a cooler to a hotter body.
Thermal Reservoir
► A thermal reservoir is a system that always remains at constant
temperature even though energy is added or removed by heat
► Such a system is approximated by the earth’s atmosphere, lakes
and oceans, and a large block of a solid such as copper.
Kelvin-Planck Statement
of the Second Law
It is impossible for any system to operate in a
thermodynamic cycle and deliver a net amount of
energy by work to its surroundings while receiving
energy by heat transfer from a single thermal
Heat Engines


The devices that convert heat to work.
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.)
Work can always be 3. They reject the remaining waste
converted to heat heat to a low-temperature sink (the
directly and atmosphere, rivers, etc.).
completely, but the
4. They operate on a cycle.
reverse is not true.
Heat engines and other cyclic devices
usually involve a fluid to and from
Part of the heat which heat is transferred while
received by a heat undergoing a cycle. This fluid is
engine is converted called the working fluid.
to work, while the
rest is rejected to a
A steam power plant

A portion of the work output of

a heat engine is consumed
internally to maintain
continuous operation.

Steam Power Plant

Thermal efficiency

Schematic of a
heat engine.

Some heat engines perform better

Even the most
than others (convert more of the
efficient heat
heat they receive to work).
engines reject
almost one-half
of the energy
they receive as
waste heat.

Can we save Qout? In a steam power plant, the
condenser is the device
where large quantities
of waste heat is rejected
to rivers, lakes, or the
Can we not just take the
condenser out of the
plant and save all that
waste energy?
The answer is,
unfortunately, a firm no
A heat-engine cycle cannot be completed without for the simple reason
rejecting some heat to a low-temperature sink. that without a heat
rejection process in a
Every heat engine must waste some condenser, the cycle
energy by transferring it to a low- cannot be completed.
temperature reservoir in order to
complete the cycle, even under
idealized conditions.
The Second Law of
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 percent, or as for a power
plant to operate, the working fluid must A heat engine that violates the Kelvin–
exchange heat with the environment as well Planck statement of the second law.
as the furnace.
The impossibility of having a 100% efficient
heat engine is not due to friction or other
dissipative effects. It is a limitation that
applies to both the idealized and the actual
heat engines.

• 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
• The most frequently used
Basic components of a refrigeration cycle is the vapor-
refrigeration system and compression refrigeration cycle.
typical operating conditions.


In a household refrigerator, the freezer

compartment where heat is absorbed by
the refrigerant serves as the evaporator,
and the coils usually behind the refrigerator
where heat is dissipated to the kitchen air
serve as the condenser.

Coefficient of Performance
The efficiency of a refrigerator is expressed in
terms of the coefficient of performance (COP).
The objective of a refrigerator is to remove heat
(QL) from the refrigerated space.

The objective of a refrigerator is to Can the value of COPR be

remove QL from the cooled space. greater than unity?

The objective of Heat
a heat pump is
to Pumps
supply heat QH
into the
warmer space.
The work
supplied to a
heat pump is
used to extract
energy from the
cold outdoors
and carry it into
the warm

Can the value of COPHP be

lower than unity?
What does COPHP=1
for fixed values of QL and QH
The Second Law of Thermodynamics:
Clasius 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

It states that a refrigerator cannot operate unless its

compressor is driven by an external power source,
such as an electric motor.
This way, the net effect on the surroundings involves
the consumption of some energy in the form of work,
in addition to the transfer of heat from a colder body
to a warmer one. A refrigerator that violates
To date, no experiment has been conducted that the Clausius statement of
contradicts the second law, and this should be taken the second law.
as sufficient proof of its validity.

Equivalence of the Two Statements

Proof that the

violation of the
statement leads
to the violation
of the Clausius

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
Any device that violates the Kelvin–Planck statement also violates the Clausius
statement, and vice versa.

A perpetual-motion machine that

violates the second law of
A perpetual-motion machine that
thermodynamics (PMM2).
violates the first law (PMM1).
Perpetual-motion machine: Any device that violates the first or the second law.
A device that violates the first law (by creating energy) is called a PMM1.
A device that violates the second law is called a PMM2.
Despite numerous attempts, no perpetual-motion machine is known to have
worked. If something sounds too good to be true, it probably is.
Reversible process: A process that can be reversed without leaving any trace on the
Irreversible process: A process that is not reversible.
• All the processes occurring in nature are irreversible.
• Why are we interested in reversible processes?
• (1) they are easy to analyze and (2) they serve as idealized
models (theoretical limits) to which actual processes can be
• Some processes are more irreversible than others.
• We try to approximate reversible processes. Why?

Two familiar reversible Reversible processes deliver the most and consume the
processes. least work.
• 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
Friction temperature difference, electric resistance, inelastic
renders a deformation of solids, and chemical reactions.
• The presence of any of these effects renders a
process irreversible.

(a) Heat
through a
difference is
irreversible, Irreversible
and (b) the compression
reverse and
process is expansion
impossible. processes. 26


block İnclined plane

Friction makes a process irreversible.

System: block and inclined plane
Surrounding: weight and air.
The block is pulled up the inclined plane by lowering the weight.
In the process a →b
(potential enery change of the sytem) + (heat transfer to surrounding by friction) =
(potential enery change in surrounding)
In the process b →c
(potential enery change of the sytem) + (heat transfer to surrounding by friction) =
(potential enery change in surrounding)
When the system returns to its initial state , the surrounding gains heat but loses
potential energy.

State 1 State 2

Process 2→3 Process 3→1

Example: Assume that we have air (ideal gas) inside the cylinder. Initially, the
cylinder is insulated. (for air: R=0.287kJ/kgK, Cp= 1.004kJ/kgK,
Cv= 0.717kJ/kgK, k=1.4)
At State 1: P1 = 200kPa, T1 = 50oC, V1 = 1m3
From the equation of state for ideal gas (PV = mRT) :
m= (P1V1)/(RT1) = (200*1)/[0.287*(273.15+50)] = 2.156kg
After the expansion the volume doubles , V2 = 2*V1 = 2m3
From the first law of thermodynamics for closed system: Q12-W12=U2-U1
Q12 = 0, W12 = 0 → U2 = U1
From the Joule’s experiment , we know that the internal energy of ideal gas
depends only the temperature. Hence, T2 = T1 = 50oC.
Since the mass of air inside the cylinder is constant, from the equation of state
(P2V2)/RT2 = (P1V1)/RT1 → P2V2 = P1V1 → P2*2 = 200*1 → P2 = 100kPa
At State 2 : P2 = 100kPa, T2 = 50oC, V2 = 2m3
In the reverse process, we compress the air adiabatically (no heat transfer).
V3 = V1 = 1m3
P3 = P2(V2/V3)k = 100*(2/1)1.4 = 263.9 kPa
From the equation of state T3= P3V3/(mR) = 263.9*1/(2.156*0.287) = 426.49 K
T3= 431.14 – 273.15 = 153.34oC
At State 3 : P3 = 263.9 kPa, T3 = 153.14 oC, V3 = 1m3
During the adiabatic compression the boundary work: W23 = (P3V3 – P2V2)/(1-k)
W23 = (263.9*1- 100*2)/(1-1.4) = -159.75 kJ
To reach the initial state we need to have heat transfer to surrounding at
constant volume.
At State 1 : P1= 200 kPa, T1 = 50oC, V1 = 1m3
Q31= m*Cv*(T1-T3) = 2.156*0.717*(50-153.34) = -159.75 kJ

When we reach the initial state, we go through the states 1 → 2 → 3 → 1
Qnet- Wnet= U1 - U1 = 0
Since the initial and the final states are the same,
Qnet = Q31 = -159.75 kJ
Wnet= W23 = -159.75 kJ
Substituting above values into the conservation of energy equation.
(-159.75 ) - (-159.75) = 0
Hence, we satisfy the conservation of energy.
We can show that unrestrained expansion is an irreversible process. The reason
is that after the we reach the initial state, we have trace in the system and
surrounding. Even though we satisfy the conservation of energy the type of
energies are different
•The system receives energy in the form of work
•The system gives energy in the form of heat

A certain amount of work is necessary to sperate O2 ad N2.

This work should be supplied by surrounding.


We need a refrigerator to return

the system (soda) to İts initial state.

. the process, although the system

returns its initial state, we create a trace
in surrounding.

Surrounding gives energy in the form of work.

But receives energy in the form heat.
Internally and Externally Reversible Processes
• Internally reversible process: If no irreversibilities occur within the boundaries of the system
during the process.
• Externally reversible: If no irreversibilities occur outside the system boundaries.
• Totally reversible process: It involves no irreversibilities within the system or its
• A totally reversible process involves no heat transfer through a finite temperature difference,
no nonquasi-equilibrium changes, and no friction or other dissipative effects.

A reversible process involves

no internal and external Totally and internally reversible heat transfer
irreversibilities. processes.
Example: Internally Reversible Process
Water contained within a piston-cylinder evaporates
from saturated liquid to saturated vapor at 100oC. As the
water evaporates, it passes through a sequence of
equilibrium states while there is heat transfer to the water
from hot gases at 500oC.
►For a system enclosing the water there are no
internal irreversibilities, but
►Such spontaneous heat
transfer is an irreversibility
in its surroundings: an
external irreversibility.

Execution of
the Carnot
cycle in a

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)
P-V diagram of the Carnot cycle. P-V diagram of the reversed
Carnot cycle.

The Reversed Carnot Cycle

The Carnot heat-engine cycle is a totally reversible cycle.
Therefore, all the processes that comprise it can be reversed, in
which case it becomes the Carnot refrigeration cycle.
Carnot Power Cycles

The p-v diagram and schematic of water executing a Carnot cycle

through four interconnected components are shown below:

Proof of the first Carnot principle.

The Carnot principles.

1. The efficiency of an irreversible heat engine is always less than the

efficiency of a reversible one operating between the same two reservoirs.
2. The efficiencies of all reversible heat engines operating between the same
two reservoirs are the same.
A temperature scale that is
independent of the
properties of the substances
that are used to measure
temperature is called a
temperature scale.
Such a temperature scale
offers great conveniences in
thermodynamic calculations.

All reversible heat

engines operating
between the same two
reservoirs have the The arrangement of heat
same efficiency.
engines used to develop
the thermodynamic
temperature scale.
η th = 1 −
QH The functional form of f(TH, TL) can be
developed with the help of reversible heat
η th = g ( TL , TH ) = 1 − f ( TL , TH ) engines.

= f (TL , TH )

Q1 Q2 Q1
= f (T1 , T2 ), = f (T2 , T3 ), = f (T1 , T3 )
Q2 Q3 Q3

Q1 Q1 Q2
Q3 Q2 Q3

f (T1 , T3 ) = f (T1 , T2 )i f (T2 , T3 )

The left hand side is only function of T1 and T3. The right hand side should be
function of T1 and T3.

This condition is satisfied if the function f has the following form
φ (T1 ) φ (T2 )
f (T1 , T2 ) = , f (T2 , T3 ) = ,
φ (T2 ) φ (T3 )

Q1 φ (T1 )
= f (T1 , T3 ) =
Q3 φ (T3 )

For a reversible heat engine operating between TH and TL

QH φ (TH )
QL φ (TL )
If we choose
φ (T ) = T
the thermodynamic temperature scale can be defined as

 QH  φ (TH )
  =
 QL  rev φ (TL )
This temperature scale is
called the Kelvin scale, and
the temperatures on this
scale are called absolute

For reversible cycles, the heat A conceptual experimental setup to

transfer ratio QH /QL can be determine thermodynamic
replaced by the absolute temperatures on the Kelvin scale by
temperature ratio TH /TL. measuring heat transfers QH and


The Carnot
heat engine
is the most
efficient of
all heat
between the
same high-
and low- No heat engine can have a higher efficiency
temperature than a reversible heat engine operating
reservoirs. between the same high- and low-
temperature reservoirs.
Any heat Carnot heat
engine engine

The Quality of Energy

Can we use °C
unit for
The higher the temperature
of the thermal energy, the
higher its quality.

The fraction of heat that can How do you increase the thermal
be converted to work as a efficiency of a Carnot heat
function of source engine? How about for actual
temperature. heat engines?
AND HEAT PUMP Any refrigerator or heat pump

Carnot refrigerator or heat pump

How do you increase the COP

No refrigerator can have a higher COP of a Carnot refrigerator or
than a reversible refrigerator operating heat pump? How about for
between the same temperature limits. actual ones?