CHAPTER 8
SECOND LAW OF
THERMODYNAMICS
ENTROPY
Entropy (YAC- Ch. 6)
In this Chapter, we will:
• Introduce the thermodynamic property called Entropy (S)
• Entropy is defined using the Clausius inequality
• Introduce the Increase of Entropy Principle which states that
– the entropy for an isolated system (or a system plus its surroundings)
is always increases or, at best, remains the same.
– Second Law in terms of Entropy
• Learn to use the Entropy balance equation: entropy change = entropy
transfer + entropy change.
• Analyze entropy changes in thermodynamic process and learn how to
use thermodynamic tables
Entropy – A Property
• Entropy, S is a thermodynamic property; it
can be viewed as a measure of disorder.
• More disorganized a system the higher its
entropy.
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Entropy – A Property
• Entropy is a thermodynamic property; it can be viewed as a measure of disorder.
i.e. More disorganized a system the higher its entropy. the integration is
• Defined using Clausius inequality Q
0 entire cycle
performed over
T rev
where Q is the differential heat transfer & T is the absolute The cyclic integral of dq/dt
is always less or equal to 0.
temperature at the boundary where the heat transfer occurs
• Clausius inequality is valid for all cycles, reversible and irreversible.
• Consider a reversible Carnot cycle:
Q QH QL QL TL QL TL
T TH TL
, from Carnot efficiceny th 1
QH
1 ,
TH QH TH
Q Q
Therefore, T
0 for a reversible Carnot cycle T rev 0
Q
• Since 0, i.e. it does not change if you return to the same state,
T rev
it must be a property, by defintion:
• Let’s define a thermodynamic property entropy (S), such that
Q 2 2
Q
dS , for any reversible process dS S2 S1
True for a Reversible
T rev T rev
Process only
1 1
The change of entropy can be defined based on a reversible process
To demonstrate the validity, consider a system connected to TR
ENTROPY
The cyclic devices dWc= dWrev+dWsys, dEc – the change in total energy
receives heat, dQR of combined system
from the reservoir
and supplies heat
dQ to the system
which T (temp) and
produce work,
dWrev. Clasius
inequality
To develop a relation for entropy:
Formal
definition
of
System produces entropy
work dWsys as a
result of heat
transfer.
The system considered in The equality in the Clausius inequality holds
the development of the for totally or just internally reversible cycles
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Clausius inequality. and the inequality for the irreversible ones.
Entropy (cont’d)
Since entropy is a thermodynamic property, it has fixed values at a fixed thermodynamic
states. Hence, the change, S, is determined by the initial and final state. BUT..
The change is = Q only for a Reversible Process
T Q 2 1
Q Q
T T T rev 0
Consider a cycle, where 1 2
Process 2-1 is reversible and 1- From entropy definition
2 may or may not be reversible
Q Q Q Q
2 1
dS=
T
,
rev
dS 0 T rev 1 T 2 T rev
rev
T any 2
Q Q
2 2 2
process Therefore, dS S2 S1 S
1
T 1 T rev 1
Q
2
S S 2 S1 , This is valid for all processes
1
1 reversible T
process Q Q Q
dS , since dS = , dS
T T rev T irrev
S
Equality Inequality
The entropy change between two
specified states is the same whether the
process is reversible or irreversible.
A Special Case: Internally Reversible Isothermal Heat Transfer Processes
Constant T
This equation is particularly useful for determining
the entropy changes of thermal energy reservoirs. 9
EXAMPLE : Entropy change
during an Isothermal Process
A piston cylinder device contains a liquid-vapor mixture of
water at 300 K. During a constant pressure process, 750 kJ of
heat is transferred to the water. As a result, part of the liquid
in the cylinder vaporizes. Determine the entropy change of
the water during this process.
Assumption : no irreversibility occur during the process.
Analysis: the system undergoes internally reversible,
isothermal process.
Increase of Entropy Principle
Q
2
S S 2 S1 , define entropy generation Sgen
1
T
Q Q
2 2
S system S 2 S1 gen
S Increase of Entropy Principle
1 1
T T
gen 0. If the system is isolated and "no" heat transfer
where Schange
Entropy
Entropy Transfer Entropy Generation – entropy generated during a process
The entropy will still increase
(due to or stay the same but never decrease
heat transfer)
S system S gen 0, entropy increase principle
The principle states that for an isolated Or a closed adiabatic Or System + Surroundings
A process can only take place such that Sgen 0 where Sgen = 0 for a reversible process only
And Sgen can never be les than zero.
Implications:
•Entropy, unlike energy, is non-conservative since it is always increasing.
•The entropy of the universe is continuously increasing, in other words, it is becoming
disorganized and is approaching chaotic.
• The entropy generation is due to the presence of irreversibilities. Therefore, the higher the
entropy generation the higher the irreversibilities and, accordingly, the lower the efficiency
of a device since a reversible system is the most efficient system.
• The above is another statement of the second law
The entropy for an isolated system (or a system plus its
surroundings) is always increases or, at best, remains the same.
EXAMPLE – entropy generation during heat
transfer processes
A heat source at 800 K loses 2000 kJ of heat to a sink at (a)
500 K and (b) 750 K. Determine which heat transfer process
is more irreversible.
Analysis: Both cases involve heat transfer through a finite
temperature difference – both a irreversible.
Because heat is naturally transferred from a higher temperature body to a
lower temperature body, we can rightly assume that heat (in both cases) is
being transferred from the source to the sink. Heat transferred out of a body
is a negative term (energy is leaving the system), while heat transferred
into a body is a positive term.
Second Law & Entropy Balance (YAC- Ch. 6-4)
• Increase of Entropy Principle is another way of stating the Second Law of Thermodynamics:
Second Law : Entropy can be created but NOT destroyed
(In contrast, the first law states: Energy is always conserved)
•Note that this does not mean that the entropy of a system cannot be reduced, it can.
• However, total entropy of a system + surroundings cannot be reduced
• Entropy Balance is used to determine the Change in entropy of a system as follows:
Entropy change = Entropy Transfer + Entropy Generation where,
Entropy change = S = S2 - S1
Entropy Transfer = Transfer due to Heat (Q/T) + Entropy flow due to mass flow (misi – mese)
Entropy Generation = Sgen 0
For a Closed System: S2 - S1 = Qk /Tk + Sgen
In Rate Form: dS/dt = Qk /Tk + Sgen
dS cv Q
For an Open System (Control Volume): k m i s i m e s e S gen ,CV
dt Tk
Similar to energy and mass conservation, the entropy balance equations can be simplified
Under appropriate conditions, e.g. steady state, adiabatic….
ENTROPY CHANGE OF PURE SUBSTANCES
Entropy is a property, and thus the
value of entropy of a system is fixed
once the state of the system is fixed.
Schematic of the T-s diagram for water.
Value of S in the compressed liquid Entropy change of a specified mass, m
and superheated vapor – obtained for a closed system
directly from property tables.
For mix region – using formula 17
ENTROPY BALANCE
Entropy Change of a
System, ∆Ssystem
When the properties of the
system are not uniform
Energy and entropy
balances for a system.
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Mechanisms of Entropy Transfer, Sin and Sout
1 Heat Transfer
Entropy transfer by heat transfer:
Entropy transfer by
work:
Heat transfer is always accompanied by
entropy transfer in the amount of Q/T,
where T is the boundary temperature.
No entropy accompanies work as it crosses
the system boundary. But entropy may be
generated within the system as work is 19
dissipated into a less useful form of energy.
2 Mass Flow
Entropy transfer by mass:
When the properties of the mass
change during the process
Mass contains entropy as well as
energy, and thus mass flow into or out
of system is always accompanied by
energy and entropy transfer.
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Entropy Generation, Sgen Entropy generation
outside system
boundaries can be
accounted for by
writing an entropy
balance on an
extended system that
includes the system
and its immediate
surroundings.
Mechanisms of entropy transfer for a
general system. 21
Closed Systems
The entropy change of a closed system during a process is equal to the
sum of the net entropy transferred through the system boundary by heat
transfer and the entropy generated within the system boundaries.
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EXAMPLE: Entropy change of a
substance in a Tank
A rigid tank contains 5 kg or refrigerant-134 a initially at
20°C and 140 kPa. The refrigerant is now cooled while
being stirred until its pressure drops to 100 kPa.
Determine the entropy change during this process.
Analysis: It is a closed system. Change of entropy is the
difference between entropy values at final and initial
states.
FINAL EXAM – DEC 2016