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Chapter 7
The classical Second Law of
Thermodynamics
Instructor: Assoc. Prof. Dr. Sinan Eyi
The Second Law of Thermodynamics
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The Second Law of Thermodynamics
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The Second Law of Thermodynamics
►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
HEAT ENGINES
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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
sink.
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A steam power plant
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Steam Power Plant
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Thermal efficiency
Schematic of a
heat engine.
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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
atmosphere.
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.
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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.
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REFRIGERATORS AND HEAT PUMPS
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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.
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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
indoors.
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Equivalence of the Two Statements
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.
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PERPETUAL-MOTION MACHINES
Two familiar reversible Reversible processes deliver the most and consume the
processes. least work.
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• 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.
process
• The presence of any of these effects renders a
irreversible.
process irreversible.
Irreversibilities
(a) Heat
transfer
through a
temperature
difference is
irreversible, Irreversible
and (b) the compression
reverse and
process is expansion
impossible. processes. 26
FRICTION
weight
State 1 State 2
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UNRESTRAINED EXPANSION
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
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UNRESTRAINED EXPANSION
In the reverse process, we compress the air adiabatically (no heat transfer).
P2V2k=P3V3k
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
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UNRESTRAINED EXPANSION
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
0=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
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MIXING OF TWO FLUIDS
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HEAT TRANSFER ACROSS A FINITE
TEMPERATURE DIFFERENCE
Execution of
the Carnot
cycle in a
closed
system.
QL
= f (TL , TH )
QH
Q1 Q2 Q1
= f (T1 , T2 ), = f (T2 , T3 ), = f (T1 , T3 )
Q2 Q3 Q3
Q1 Q1 Q2
=
Q3 Q2 Q3
The left hand side is only function of T1 and T3. The right hand side should be
function of T1 and T3.
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THE THERMODYNAMIC TEMPERATURE SCALE
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 )
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 )
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This temperature scale is
called the Kelvin scale, and
the temperatures on this
scale are called absolute
temperatures.
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THE CARNOT HEAT ENGINE
The Carnot
heat engine
is the most
efficient of
all heat
engines
operating
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
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The Quality of Energy
Can we use °C
unit for
temperature
The higher the temperature
here?
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?
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THE CARNOT REFRIGERATOR
AND HEAT PUMP Any refrigerator or heat pump
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