ME 103: Engineering Thermodynamics

Jan-Apr 2024
(2023-24 Even semester)
Dr. R Santhosh
Department of Mechanical Engineering
IIT (BHU) Varanasi
rsanthosh.mec@iitbhu.ac.in
 January February
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Classes before mid-semester exam: 18

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n d n u
1 2 3 1 2 3 4 5 6 7
4 5 6 7 8 9 10 8 9 10 11 12 13 14
11 12 13 14 15 16 17 15 16 17 18 19 20 21
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Classes after mid-semester exam: 21

Unit-wise Course overview
Unit
1. Basic Concepts, pressure measurements, Zeroth Law & Temperature
measurements, Work and Heat Transfer. (5-6 classes)

2. First law of thermodynamics for cycle and processes ( mainly for closed system,
steady and unsteady processes for open system) (4-5 classes)

3. Second law analysis, Kelvin Planck and Clausius theorem, heat engine &
refrigeration, reversible process, Carnot cycle & theorem (4-5 classes)

4. Entropy, Clausius inequality; entropy increase principle; entropy generation,

entropy balance for closed and open system; entropy and disorder (5-6 classes)
•
5. Thermodynamic Properties of pure
•Chemical substances
Reactions andAnalysis
and Exergy property relations (6-7
classes)
6. Gas power cycles, Vapor power cycle and Refrigeration Cycle (12-15 classes)
 Course outline
Unit 1
• Basic concepts: systems, property, path, process, cycle, Thermodynamic
equilibrium (Mechanical, Thermal and Chemical); Quasi-static process
• Thermodynamics Properties: Pressure (brief discussion about instruments),
volume, Temperature, zeroth law of thermodynamics, temperature
• Work and Heat

Unit 2
• First law of Thermodynamics: Closed system and Flow process (open system)

Unit 3
• Second law: Qualitative analysis of heat and work transfer; heat engine and
refrigerator; Kelvin Planck and Clasius statement; efficiency and cop;
reversible and irreversible process; causes of irreversibility; Carnot cycle;
Carnot theorem; absolute thermodynamic temperature scale, Carnot
efficiency and Carnot cop
 Unit 4
• Entropy: Clausius theorem; inequality of Clausius; entropy increase principle; •
entropy generation; entropy balance equation for closed and open system

• Definition of exergy, Irreversibility, dead state, calculation for irreversibility for

closed and open system;

Unit 5
• Properties of mixtures: Helmholtz and Gibbs function, Review of partial
derivatives and associated relations, Maxwell relations, Clausius-Clayperon
equation, Joule Thomson coefficient
• Pure substances, phases of a pure substance, phase change processes of pure
substances, property diagrams and tables, The ideal-gas equation of state,
compressibility factor, other equations of state
Unit 6
Gas power cycles: Air standard assumptions, Carnot cycle, Otto cycle, Diesel
cycle, dual cycle, Stirling and Ericsson cycle, Brayton cycle (ideal and actual),
Ideal jet propulsion cycle
Vapour power cycles: Rankine cycle (ideal and actual), Ideal reheat Rankine
cycle, Ideal regenerative Rankine cycle, Cogeneration (combined cycle)
Refrigeration cycles: Reversed Carnot cycle, ideal vapor-compression
refrigeration cycle, Absorption refrigeration cycle
Entropy

vFirst Law was stated in terms of cycles

vFirst law was applied for processes :

• defined a property Internal Energy

vSimilarly 2nd law was first stated for cycles

vWhen applied to processes , 2nd law will also leads

to definition:
• A new property known as Entropy
 Quantification of a reversible cycle

𝑄! 𝑇!
TH 𝑄"
=
𝑇"

QH ⇒
𝑄! 𝑄"
=
rev Wnet 𝑇! 𝑇#

HE ⇒
$! $
− "=0
%! %#
QL $ $
⇒ !+ − " =0
%! %#
TL $
⇒ ∑ = 0 [for the system]
%

𝛿𝑄 [T: temperature at system

⇒) =0 boundary across which
𝑇
heat transfer is taking
place]
 Quantification of an irreversible cycle

𝛿𝑄
TH !
𝑇
= 0 [𝑓𝑜𝑟 𝑎 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒]

QH !
𝛿𝑄
=? ?
irrev Wnet,ir 𝑇

HE 𝛿𝑄 𝑄! 𝑄",$%
! = −
QL,ir 𝑇 𝑇! 𝑇&

TL 𝑄! 𝑄",$% 𝑄! 𝑄"
− < − [𝑄",$% > 𝑄" ]
𝑇! 𝑇& 𝑇! 𝑇&
*
𝑄! 𝑄",$% 𝛿𝑄
⇒ − < !
𝑇! 𝑇& 𝑇
'() *
𝑄! 𝑄",$% 𝛿𝑄
⇒ − <0 ! <0
𝑇! 𝑇& 𝑇
$%%()
 Clausius Inequality
𝛿𝑄
! ≤ 0 … … . [𝐶𝑙𝑎𝑢𝑠𝑖𝑢𝑠 𝐼𝑛𝑒𝑞𝑢𝑎𝑙𝑖𝑡𝑦]
𝑇

𝛿𝑄
C ? ? [𝑓𝑜𝑟 𝑎 𝑝𝑟𝑜𝑐𝑒𝑠𝑠]
𝑇

𝛿𝑄 i
! = 0 [𝑓𝑜𝑟 𝑎 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒]
𝑇 A

, $ B
𝛿𝑄 𝛿𝑄 C f
C + C =0
𝑇 𝑇 $ $
$,+ ,,- 𝛿𝑄 𝛿𝑄
, $
C = C
𝑇 𝑇
𝛿𝑄 𝛿𝑄 ,,- ,,.
C + C =0
𝑇 𝑇 (is independent of the path
$,+ ,,.
connecting i and f)
There exists a property whose value at the final state minus its value at the initial state
/0
equals the integral ∫ . This state function as named the entropy by Rudolf Clausius in 1865
1
and is denoted by S 𝛿𝑄
= 𝑑𝑆 [𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠]
𝑇
So we can write, change of entropy from initial state to final state

For infinitesimal change

ædQ ö Unit: S kJ/K and specific s is kJ/kg K
dS = ç ÷
è T ø rev
Reversible adiabatic process,d Q = 0
dS =0; S=Const., Isentropic Process
 Heat transfer in a reversible process

Area under a reversible path on Carnot cycle

T-s diagram represents amount
/0
of heat transfer d𝑆=
1
,

⇒ 𝑄 = C 𝛿𝑄 = C 𝑇𝑑𝑆
$
f
Reversible isothermal process, Qrev = ò Tds = T ( s f - si )
i
 𝛿𝑄JKKLM
! <0 irreversible
𝑇 process 1-2

2
dQ ædQ ö
1

ò T + ò ç T ÷ <£00
1 2è ørev
2
dQ
ò T + ( S1 - S2 ) £< 00 reversible
1

2
dQ
( S2 - S1 ) ³> ò dQ Applicable for
1 T ds ³
T any process
• In these equations the equality holds for a reversible process
• the inequality for an irreversible process.
 Clausius Inequality

• For an irreversible cycle:

𝛿𝑄$%%() 𝛿𝑄%() 𝛿𝑄$%%() 𝛿𝑄%()

! <! ⇒! <0 𝑆𝑖𝑛𝑐𝑒, ! =0
𝑇 𝑇 𝑇 𝑇

,
𝛿𝑄
• For any irreversible process: C 𝑖𝑠 𝑛𝑜𝑡 𝑎 𝑝𝑜𝑖𝑛𝑡 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛
𝑇
$
, , , ,
𝛿𝑄$%%() 𝛿𝑄%() 𝛿𝑄$%%() 𝛿𝑄
C <C ⇒C < ∆𝑆 𝑆𝑖𝑛𝑐𝑒, ∆𝑆 = C (𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒)
𝑇 𝑇 𝑇 𝑇
$ $ $ $

f
Inequality of Clausius Theorem:

𝛿𝑄
! ≤ ∆𝑆
𝑇
+,
• ∫ = 0 ∶ 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒
-
+,
• ∫ < 0 ∶ 𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒
-

+,
• ∫ = ∆𝑆: reversible process
-
+,
• ∫ < ∆S ∶ irreversible process
-

reversible adiabatic process S=??

 𝛿𝑄
C < ∆S ∶ irreversible process
𝑇
𝛿𝑄
C < ∆S
𝑇
𝛿𝑄
⇒C +? ? = ∆S
𝑇
⇒ ∆𝑆( + ∆𝑆$ = ∆S

∆𝐒𝐞 : 𝐂𝐡𝐚𝐧𝐠𝐞 𝐨𝐟 𝐞𝐧𝐭𝐫𝐨𝐩𝐲 𝐝𝐮𝐞 𝐭𝐨 𝐞𝐱𝐭𝐞𝐫𝐧𝐚𝐥 𝐢𝐫𝐫𝐞𝐯𝐞𝐫𝐬𝐢𝐛𝐢𝐥𝐢𝐭𝐲

∆𝐒𝐢 : 𝐂𝐡𝐚𝐧𝐠𝐞 𝐨𝐟 𝐞𝐧𝐭𝐫𝐨𝐩𝐲 𝐝𝐮𝐞 𝐭𝐨 𝐢𝐧𝐭𝐞𝐫𝐧𝐚𝐥 𝐢𝐫𝐫𝐞𝐯𝐞𝐫𝐬𝐢𝐛𝐢𝐥𝐢𝐭𝐲 (Sgen)
2
dQ
( S2 - S1 ) ³ ò
1 T
Entropy change Entropy transfer due
of a system to heat transfer

2
dQ
DS system = ( S2 - S1 ) = ò + S gen
1 T
q Entropy change of a closed system during an irreversible
process is always greater than the entropy transfer by heat
energy.
qSome entropy is generated or created during an irreversible
process because of the presence of irreversibilities.
qThe entropy generated during a process is called entropy
generation and is denoted by S gen
qDifference between the entropy change of a closed system and
the entropy transfer is equal to entropy generation

2
dQ
DS system = ( S2 - S1 ) = ò + S gen • no entropy is related to work
1 T

Q
 Closed system:
2
dQ
DS system = ( S2 - S1 ) = ò + S gen
1 T
• For a reversible process: 𝐒𝐠𝐞𝐧 =? ?

• For an adiabatic process: ∆𝐒𝒆 =? ?

• For an adiabatic irreversible process: ∆𝐒𝒆 =? ? , 𝐒𝐠𝐞𝐧 =? ?

• For an adiabatic reversible process: ∆𝐒 =? ?

 Entropy Increase principle
Isolated system: which does not undergo any energy interaction
with surroundings
dsiso ³ 0
dsiso = 0 for reversible process
system dsiso > 0 for irreversible
system A process
system B

surrounding

Isolated systems: (system + surrounding) , all interacting systems

∆𝑆$45678(9 4:48(; ≥ 0
∆𝑆<=$)(%4( ≥ 0 Principle of Increase of Entropy !!

• Entropy may decrease locally at some region within the isolated system, but it
must be compensated by a greater increase of entropy somewhere within the
system so that net effect of an irreversible process is an entropy increase of the
whole system
S gen = DSuniv = ( DS system + DS surr ) ³ 0
Some remarks about entropy

• Processes can occur in a certain direction only, not in

any direction.
• A process must proceed in the direction that complies
with the increase of entropy principle

The performance of engineering systems is degraded by the

presence of irreversibilities, and entropy generation is a
measure of the magnitudes of the irreversibilities present
during that process.
A heat source at 800K loses 2000kJ of heat to a sink at (a) 500K and
(b)750K. Determine which heat transfer process is more irreversible.
source, T1 ∆𝑆<=$)(%4( = ∆𝑆+ + ∆𝑆- + ∆𝑆.
𝑄> −𝑄> 𝑄?
= + +0
𝑇> 𝑇?

HE 𝑄> 𝑄?
=− −
𝑇> 𝑇?
𝑊=(8 = 𝑄> − 𝑄? 𝛿𝑄
𝑄? = −!
𝑇

𝛿𝑄
T2 Clausius Inequality: !
𝑇
≤0

∆𝑆<=$)(%4( ≥ 0 Principle of increase of entropy !

Principle of increase of entropy and Clausius Inequality are synonymous!

Finite systems: ∆𝑆<=$)(%4( ≥ 0

A T1 Tf ∆𝑆<=$)(%4( = ∆𝑆+ + ∆𝑆- + ∆𝑆.

𝒇 𝒇
𝜹𝑸𝟏 𝜹𝑸𝟐
Q1 = −C +C +0
𝟏 𝑻 𝟐 𝑻
𝑇, 𝑇,
C = 𝑚> 𝑐@ 𝑙𝑛 + 𝑚? 𝑐@ 𝑙𝑛
W 𝑇> 𝑇?
Q2
For reversible cycle, ∆𝑆<=$)(%4( = 0
B T2 Tf 1! "
Therefore 𝑙𝑛 1 1 =0 , 𝑇, = 𝑇> 𝑇?
# "

𝑑𝑄 = 𝑚𝑐@ 𝑑𝑇

∆𝑆 = C 𝑑𝑄/𝑇 = C(𝑚𝑐@ /𝑇)𝑑𝑇

𝑇,
= 𝑚𝑐@ 𝑙𝑛
𝑇$
ENTROPY CHANGE OF PURE SUBSTANCES

d Q = dU + d W [Closed system] H = U + PV
d Q = TdS ; d W = PdV [Reversible process] dH = dU + PdV + VdP
TdS = dU + PdV TdS = dH - VdP

Tds = du + Pdv Tds = dh - vdP

dT Rdv dT dP
ds = cv + ds = c p -R
T v T P
T2 v2 T2 P2
s2 - s1 = cv ln + R ln s2 - s1 = c p ln - R ln
T1 v1 T1 P1
Oxygen gas is compressed in a piston-cylinder
arrangement from 298K, 0.8m3 to 560K, 0.1m3. Find the
entropy change of oxygen gas during the compression
process.[cv=0.690kJ/kg K, R=0.2598kJ/kgK]
d Q = dU + d W
d Q = TdS ; d W = PdV
TdS = dU + PdV
Tds = du + Pdv
dT Rdv
ds = cv +
T v
T2 v2
s2 - s1 = cv ln + R ln
T1 v1
560 0.1
s2 - s1 = 0.690ln + 0.2598ln
298 0.8
= 0.4353 - 0.5402
= -0.1049 kJ / kgK
A spring loaded piston-cylinder setup contains 1.5kg of air at 270C and 160kPa. It is
now heated in a process where pressure is linear with volume, P=a+bV, to twice the
initial volume where it reaches 900K. Find the work, heat transfer, and total entropy
generation assuming a source at 900K. [161.44kJ, 806.74kJ, 0.584kJ/K].
 ?
𝑊𝑜𝑟𝑘 𝑇𝑟𝑎𝑛𝑠𝑓𝑒𝑟: 𝑊>D? = 𝑚 C 𝑃𝑑𝑣
>

𝐸𝑛𝑒𝑟𝑔𝑦 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛: 𝑄>D? = 𝑊>D? + 𝑚 𝑢? − 𝑢>

Tds = du + Pdv
T2 v2
s2 - s1 = cv ln + R ln
T1 v1
560 0.1
s2 - s1 = 0.690ln + 0.2598ln
298 0.8
= 0.4353 - 0.5402
= -0.1049 kJ / kgK
Open system analysis

W! cv
inlet i

m! i , Pi , Ti ,vi , si
dmcv dScv dE cv
hi ,ui ,Vi , Zi dt dt dt exit
e
m! e , Pe , Te ,ve , se
he ,ue ,Ve , Ze
Q! cv
dSc.v. Q!
= å + å m! i si - å m! e se + S!gen
dt T
Summarize
1. Energy Balance 1st law
Change in Energy of the system=Total Energy In−Total Energy Out

a. Closed system
• ∆𝐸4:4 = 𝐸$= − 𝐸5<8

= • 𝑄$= − 𝑄5<8 + • 𝑊$= − 𝑊5<8

b. Open System

• ∆𝐸.E = ∑ 𝑄$= − 𝑄5<8 + ∑ 𝑊$= − 𝑊5<8 + ∑ 𝑚𝑒$= − 𝑚𝑒5<8

E"
𝐸 =𝑈+ + 𝑔𝑧
?
E"
e = u + p𝑣 + + 𝑔𝑧
?

In terms of Rates: dmcv

= åm
! i -å m
!e
dt
9F$%
• 98
= ∑ 𝑄̇ $= − 𝑄̇ 5<8 + ∑ 𝑊̇ $= − 𝑊̇ 5<8 + ∑ 𝑚𝑒
̇ $= − 𝑚𝑒
̇ 5<8
2. Entropy Balance
Change in Entropy of the system=Total Entropy In−Total Entropy Out+ Total Entropy generated

Closed system
• ∆𝑆*+* = 𝑆,- − 𝑆./0 + 𝑆12-234025
dSc.m. Q! !
𝑄 = å + S gen
=3 + 𝑆12- dt T
𝑇!

Open System
$
• ∆𝑆67 = ∑ + ∑ 𝑚𝑠,- − 𝑚𝑠./0 + 𝑆12-
%!

58$% $̇
• =∑ + ∑ 𝑚𝑠
̇ ,- − 𝑚𝑠 ̇
̇ ./0 + 𝑆12-
50 %!
 9F$%
• = ∑ 𝑄̇ $= − 𝑄̇ 5<8 + ∑ 𝑊̇ $= − 𝑊̇ 5<8 + ∑ 𝑚𝑒
̇ $= − 𝑚𝑒
̇ 5<8
98
E"
𝐸=𝐻+ + 𝑔𝑧
? ⇒ 0 = 𝑄̇ =(8 + 𝑊̇ $= + 𝑚̇ ℎ$= − ℎ5<8
E"
e=h+ + 𝑔𝑧
?

𝑄̇ =(8 = .98 𝑘𝑊
 𝑻𝒇 𝑷𝒇
𝒔𝒇 − 𝒔𝒊 = 𝒄𝒑 𝒍𝒏 − 𝑹𝒍𝒏
𝑻𝒊 𝑷𝒊
𝑻𝟏 𝑷𝟏
𝒔𝟏 − 𝒔𝟎 = 𝒄𝒑 𝒍𝒏 − 𝑹𝒍𝒏
𝑻𝟎 𝑷𝟎
𝑻𝟐 𝑷𝟐
𝒔𝟐 − 𝒔𝟎 = 𝒄𝒑 𝒍𝒏 − 𝑹𝒍𝒏
𝑻𝟎 𝑷𝟎
 Availability/Available Energy/Exergy
Second law of thermodynamics gives the concept of:

• LOW GRADE ENERGY Heat Work (W<Q; Q=W + Qreject)

• HIGH GRADE ENERGY Work Heat (Q=W)

Low grade energy

Low grade energy

[Anergy/non-availability]

High grade energy surrounding

[Availability/Exergy]: work potential of energy
 𝑊 = η 𝑄>
T1 𝑇?
𝑊;7J = η;7J 𝑄> = 1 − 𝑄
𝑇> >
Q1
For a fixed 𝑸𝟏 at 𝑻𝟏 , maximum work is obtained at
minimum temperature ,i.e, 𝑻𝟎 (surrounding
temperature),that is, the system comes to a dead
W
state (equilibrium )
Q2
𝑇K
𝑊;7J = 1− 𝑄
T2 𝑇> >

𝑨𝒗𝒂𝒊𝒍𝒂𝒃𝒊𝒍𝒊𝒕𝒚 𝒐𝒇 𝑸𝟏 𝒂𝒕 𝑻𝟏
𝑻𝟎
= 𝟏− 𝑸 𝒘𝒊𝒕𝒉 𝒓𝒆𝒔𝒑𝒆𝒄𝒕 𝒕𝒐 𝒂 𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈 𝒂𝒕 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆 𝑻𝟎
𝑻𝟏 𝟏

1&
𝑄> : non-availability
1#
• Reversible cycle
• System is reduced to a dead state with respect to its surrounding
• Availability/Exergy: work potential of energy and not the actual work
 Loss of Availability/Exergy
𝑨𝒗𝒂𝒊𝒍𝒂𝒃𝒊𝒍𝒊𝒕𝒚 𝒐𝒇 𝑸𝟏 𝒂𝒕 𝑻𝟏
𝑻𝟎
= 𝟏− 𝑸 𝒘𝒊𝒕𝒉 𝒓𝒆𝒔𝒑𝒆𝒄𝒕 𝒕𝒐 𝒂 𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈 𝒂𝒕 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆 𝑻𝟎
𝑻𝟏 𝟏

𝑻𝟎
T1 𝑵𝒐𝒏 − 𝒂𝒗𝒂𝒊𝒍𝒂𝒃𝒊𝒍𝒊𝒕𝒚 𝒐𝒇 𝑸𝟏 𝒂𝒕 𝑻𝟏 = 𝑸
𝑻𝟏 𝟏

Q1 𝑻𝟎
𝑨𝒗𝒂𝒊𝒍𝒂𝒃𝒊𝒍𝒊𝒕𝒚 𝒐𝒇 𝑸𝟏 𝒂𝒕 𝑻𝟏 = 𝟏 − 𝑸 = 𝑨𝟏
𝑻𝟏 𝟏
T2 <T1 𝑻𝟎
𝑨𝒗𝒂𝒊𝒍𝒂𝒃𝒊𝒍𝒊𝒕𝒚 𝒐𝒇 𝑸𝟏 𝒂𝒕 𝑻𝟐 = 𝟏 − 𝑸 = 𝑨𝟐
𝑻𝟐 𝟏
Q1

W
Q3 • Availability is reduced at lower temperature
of the source (A2<A1)
T3
• Loss of availability: A2-A1=??
 Loss of availability?

𝑻𝟎
T1 𝑨𝒗𝒂𝒊𝒍𝒂𝒃𝒊𝒍𝒊𝒕𝒚 𝒐𝒇 𝑸𝟏 𝒂𝒕 𝑻𝟏 = 𝟏 − 𝑸 = 𝑨𝟏
𝑻𝟏 𝟏
𝑻𝟎
𝑨𝒗𝒂𝒊𝒍𝒂𝒃𝒊𝒍𝒊𝒕𝒚 𝒐𝒇 𝑸𝟏 𝒂𝒕 𝑻𝟐 = 𝟏 − 𝑸 = 𝑨𝟐
Q1 𝑻𝟐 𝟏

T2 <T1
𝑨𝟏 − 𝑨𝟐 =
𝑻𝟎 𝑻𝟎
− 𝑸
Irreversibility
𝑻𝟐 𝑻𝟏 𝟏

−𝑄> 𝑄> 𝟏 𝟏
∆𝑆<=$) = + = − 𝑸
𝑇> 𝑇? 𝑻𝟐 𝑻𝟏 𝟏
Irreversibilities defined with respect to a reference temperature
[𝒊𝒓𝒓𝒆𝒗𝒆𝒓𝒔𝒊𝒃𝒊𝒍𝒊𝒕𝒚 𝒊𝒏 𝒕𝒆𝒓𝒎𝒔 𝒐𝒇 𝒆𝒏𝒆𝒓𝒈𝒚]

Irreversibility, 𝑰 = 𝑻𝟎 ∆𝑺𝒖𝒏𝒊𝒗
𝟏 𝟏
𝑰 = 𝑻𝟎 − 𝑸
𝑻𝟐 𝑻𝟏 𝟏
 Concept of Useful Work

W 𝑷𝒂𝒕𝒎
𝑽𝒊 = 𝑽
P
system
system
𝑽𝒇 = 𝑽 + 𝒅𝑽
𝑷𝒂𝒕𝒎
surrounding

𝑾 = 𝑷(𝑽𝒇 − 𝑽𝒊 )

𝑾𝒖𝒔𝒆𝒇𝒖𝒍 = (𝑷 − 𝑷𝒂𝒕𝒎 )(𝑽𝒇 − 𝑽𝒊 )

𝑾𝒔𝒖𝒓𝒓 = 𝑷𝒂𝒕𝒎 (𝑽𝒇 − 𝑽𝒊 )

𝑾𝒖𝒔𝒆𝒇𝒖𝒍 = 𝑾 − 𝑷𝒂𝒕𝒎 (𝑽𝒇 − 𝑽𝒊 )

Some work is wasted against the surrounding

 Exergy of Closed Systems (Fixed mass of non-flow systems)
W
final state: ∆𝐸4:4 = 𝐸K − 𝐸> = 𝑄 − 𝑊
(𝑷𝟏 , 𝑽𝟏 , 𝑻𝟏 )
𝑷𝟎 𝑄
system 𝑽𝟎 ∆𝑆4:4 = 𝑆K − 𝑆> ≥
𝑇K
𝑻𝟎
𝑄
Q ⇒ 𝑆K −𝑆> − ≥ 0
𝑇K
surrounding (𝐸K − 𝐸> + 𝑊)
𝑷𝟎 , 𝑻 𝟎 ⇒ 𝑆K −𝑆> − ≥0
𝑇K
Maximum useful work ⇒ 𝑊 ≤ 𝑇K 𝑆K − 𝑇K 𝑆> − 𝐸K + 𝐸>
obtained from a closed
system : if the system 𝑾𝒖𝒔𝒆𝒇𝒖𝒍 = 𝑾 − 𝑷𝟎 (𝑽𝟎 − 𝑽𝟏 )
interacts reversibly with
𝑾𝒖𝒔𝒆𝒇𝒖𝒍 ≤ 𝑻𝟎 𝑺𝟎 − 𝑻𝟎 𝑺𝟏 − 𝑬𝟎 + 𝑬𝟏 − 𝑷𝟎 (𝑽𝟎 − 𝑽𝟏 )
the surrounding and
comes to the dead state ⇒ 𝑾𝒖𝒔𝒆𝒇𝒖𝒍 ≤ (𝑬𝟏 + 𝑷𝟎 𝑽𝟏 − 𝑻𝟎 𝑺𝟏 ) − (𝑬𝟎 + 𝑷𝟎 𝑽𝟎 − 𝑻𝟎 𝑺𝟎 )
⇒ 𝑾𝒎𝒂𝒙 = (𝑬𝟏 + 𝑷𝟎 𝑽𝟏 − 𝑻𝟎 𝑺𝟏 ) − (𝑬𝟎 + 𝑷𝟎 𝑽𝟎 − 𝑻𝟎 𝑺𝟎 )
∅ = 𝑬 + 𝑷𝟎 𝑽 − 𝑻 𝟎 𝑺
⇒ 𝑾𝒎𝒂𝒙 = ∅𝟏 − ∅𝟎 availability function or exergy function
Exergy change during a process [property of both the system and
surrounding]
Maximum useful work obtained from a closed system : if the system interacts reversibly with
the surrounding and comes to the dead state

AVAILABILITY 𝑾𝒎𝒂𝒙 = ∅𝟏 − ∅𝟎 ∅ = 𝑬 + 𝑷𝟎 𝑽 − 𝑻 𝟎 𝑺

Maximum useful work obtained if a system changes from state 1 to state 2

𝑾𝒎𝒂𝒙 = ∅𝟏 − ∅𝟐

⇒ 𝑾𝒎𝒂𝒙 = (𝑬𝟏 + 𝑷𝟎 𝑽𝟏 − 𝑻𝟎 𝑺𝟏 ) − (𝑬𝟐 + 𝑷𝟎 𝑽𝟐 − 𝑻𝟎 𝑺𝟐 )

This is max work that you could get if the system expands reversibly (ideally) to the dead
state. In practice, reversible processes are never achieved. Hence, irreversibilities would
kick in. So the work derived would be less than this and thus there is loss in availability
due to irreversibilities.
 Availability/Exergy Balance of Closed Systems- Decrease of exergy principle

W 1. Energy : Q , W
(𝑷𝟏 , 𝑽𝟏 , 𝑻𝟏 ) final state:
2. Availability/Exergy:
𝑻𝟎
system 𝑷𝟐 associated with Q = 𝑸 𝟏 −
𝑻𝑯 𝒂
𝑽𝟐
Q 𝑻𝟐 associated with W = 𝑾 − 𝑷𝟎 ∆𝑽

𝑻𝑯 surrounding
𝑻𝟎 • Energy Balance

𝐸? − 𝐸> = 𝑄 − 𝑊 ………… …… …..(1)

𝑻𝟎
• Availability In: 𝑸 𝟏−
𝑻𝑯

• Availability Out: 𝑾 − 𝑷𝟎 ∆𝑽

• Initial Availability of System : (𝑬𝟏 + 𝑷𝟎 𝑽𝟏 − 𝑻𝟎 𝑺𝟏 ) = ∅𝟏

• Final Availability of System : (𝑬𝟐 + 𝑷𝟎 𝑽𝟐 − 𝑻𝟎 𝑺𝟐 ) = ∅𝟐

• Initial Availability of System : (𝑬𝟏 + 𝑷𝟎 𝑽𝟏 − 𝑻𝟎 𝑺𝟏 ) = ∅𝟏 𝐸? − 𝐸> = 𝑄 − 𝑊
𝑄
• Final Availability of System : (𝑬𝟐 + 𝑷𝟎 𝑽𝟐 − 𝑻𝟎 𝑺𝟐 ) = ∅𝟐 𝑆? − 𝑆> = + 𝑆W(=
𝑇!

• Change in Availability of System :

∅𝟏 −∅𝟐 = (𝑬𝟏 + 𝑷𝟎 𝑽𝟏 − 𝑻𝟎 𝑺𝟏 ) - (𝑬𝟐 + 𝑷𝟎 𝑽𝟐 − 𝑻𝟎 𝑺𝟐 )

= 𝑬𝟏 − 𝑬𝟐 + 𝑷𝟎 (𝑽𝟏 − 𝑽𝟐 ) − 𝑻𝟎 (𝑺𝟏 − 𝑺𝟐 )
𝑻𝟎
• Availability In: 𝑸 𝟏−
𝑻𝑯

• Availability Out: 𝑾 − 𝑷𝟎 ∆𝑽 = 𝑾 − 𝑷𝟎 (𝑽𝟐 − 𝑽𝟏 )

𝑻𝟎
• Availability Transfer to system : Ain -Aout = 𝑸 𝟏 − − (𝑾 − 𝑷𝟎 ∆𝑽)
𝑻𝑯

Change in Availability of the System - Availability transferred to the system

= (∅𝟏 − ∅𝟐 ) −(Ain -Aout )
𝑻𝟎
= 𝑬𝟏 − 𝑬𝟐 + 𝑷𝟎 (𝑽𝟏 − 𝑽𝟐 ) − 𝑻𝟎 (𝑺𝟏 − 𝑺𝟐 ) − 𝑸 𝟏 − + (𝑾 − 𝑷𝟎 (𝑽𝟐 − 𝑽𝟏 )
𝑻𝑯
𝑇K
= 𝑇K 𝑆? − 𝑆> − 𝑄 = 𝑇K 𝑆W(= > 0 Gouy-Stodola theorem
𝑇!
Change in Availability of the System - Availability transferred to the system= Positive quantity

This implies that some availability is destroyed in the system. This is due to Irreversibility

= (∅𝟏 − ∅𝟐 ) −(Ain -Aout ) = 𝑻𝟎 𝑺𝒈𝒆𝒏 > 𝟎

⇒ (∅𝟏 − ∅𝟐 ) −(Ain -Aout ) =𝑰

⇒ ∅𝟐 − ∅𝟏 = (Aout -Ain ) - I

Change in Availability of the System = Availability transferred to the system –Availability Loss
∆E=Energy transferred to the system [ Energy in−Energy out]
∆S=Entropy transferred + Entropy generated
∆∅=Availability transferred to the system-Availability lost

Quantity of Energy is Conserved

Entropy is Increased
Exergy/Availability is Destroyed
 Open Systems
𝑑𝐸
= 𝑄 − 𝑊 + (𝑚𝑒)&' −(𝑚𝑒)()*
𝑑𝑡
,!" ,#"
(steady flow)⇒ 0 = q − w + ℎ+ + + 𝑔𝑧+ − ℎ. + + 𝑔𝑧.
- -
,!" , "
⇒ 𝑞 = w − ℎ+ + + 𝑔𝑧+ + ℎ. + + # + 𝑔𝑧.
- -
W
dSc.v. Q!
= å + å m! i si - å m! e se + S!gen
dt T For steady state, on mass
min basis and absorbing Sgen in
𝑷𝟎 𝑞 the inequality
⇒ 𝑠K −𝑠> − ≥0
𝒗𝟎 =0 𝑇K
𝑻𝟎 𝑣+- 𝑣.-
w − ℎ+ + 2 + 𝑔𝑧+ + (ℎ. + + 2 + 𝑔𝑧.)
⇒ 𝑠. −𝑠+ − ≥0
mout 𝑇.

Q ,!" ,#"
⇒ 𝑤 ≤ 𝑇.(𝑠. − 𝑠+) − (ℎ. − ℎ+) + + 𝑔𝑧+ + + 𝑔𝑧.
surrounding - -
𝑻𝟎 𝑣+- 𝑣.-
⇒ 𝑤/01 = (ℎ+ − 𝑇.𝑠+) − ℎ. − 𝑇.𝑠. + + 𝑔𝑧+ − ( + 𝑔𝑧.)
2 2
⇒ 𝑤/01 = (𝑎2+ − 𝑎2.)
Flow availability:
𝑣> ?
𝑎, = ℎ> − 𝑇K 𝑠> + + 𝑔𝑧> 𝝍 = 𝒉 − 𝑻𝟎 𝑺
2
• Helmholtz Function: F=U-TS
∅= 𝑈 + 𝑃K 𝑉 − 𝑇K 𝑆

𝑊;7J = ∅> − ∅?

For a closed system undergoing an isothermal process at the temperature T=T0 (of
the surrounding)
𝑊;7J = (𝑈> +𝑃K 𝑉> − 𝑇K 𝑆> ) − (𝑈? +𝑃K 𝑉? − 𝑇K 𝑆? )

⇒ 𝑊;7J = (𝑈> −𝑇𝑆> ) − (𝑈? − 𝑇𝑆? ) ⇒ 𝑊;7J = 𝐹> −𝐹?

• Gibbs Function: G=H-TS

𝑎, = h − 𝑇K 𝑆
⇒ 𝑊;7J = 𝐺> −𝐺?
𝑊;7J = 𝑎,> − 𝑎,?
 Second law efficiency
Let both engines have same thermal efficiency (First-law
efficiency)

Both engines seem to convert to work the same fraction

of heat that they receive; thus they are performing
equally well.

These engines, at best, can perform as reversible

engines, in which case their efficiencies would be

Second law efficiency

That is, engine A is converting 60 percent of the available work potential to useful work.
This ratio is only 43 percent for engine B.
Summarize
1. Energy Balance: Change in Energy of the system=Total Energy In−Total Energy Out

Closed system
W • ∆𝐸4:4 = 𝐸$= − 𝐸5<8
min

⇒ 𝐸4:4,, −𝐸4:4,$ = • 𝑄$= − 𝑄5<8 + • 𝑊$= − 𝑊5<8

mout
Open system

9F
Q • 98
= ∑ 𝑄̇ $= − 𝑄̇ 5<8 + ∑ 𝑊̇ $= − 𝑊̇ 5<8 + ∑ 𝑚𝑒
̇ $= − 𝑚𝑒
̇ 5<8
surrounding
𝑻𝟎
Steady state ‘Control Volume’:

• 0 = ∑ 𝑞$= − 𝑞5<8 + ∑ 𝑤$= − 𝑤5<8 + ∑ 𝑒$= − 𝑒5<8

E"
𝐸 =𝑈+ ?
+ 𝑔𝑧
E" E"
e = u + p𝑣 + + 𝑔𝑧 = h + + 𝑔𝑧
? ?
 Summarize
1. Entropy Balance:
Change in Entropy of the system=[Total Entropy In−Total Entropy Out ]+Total Entropy generated

W
min
Closed system
𝜹𝑸𝒏𝒆𝒕
• ∆𝑺𝒔𝒚𝒔 = ∑ + 𝑺̇ 𝒈𝒆𝒏
𝑻

Open system
mout 𝒅𝑺 ̇ 𝒏𝒆𝒕
𝜹𝑸
• = + ∑ 𝒎𝒔 ̇ 𝒐𝒖𝒕 + 𝑺̇ 𝒈𝒆𝒏
̇ 𝒊𝒏 − 𝒎𝒔
𝒅𝒕 𝑻
Q
surrounding
𝑻𝟎 Steady state ‘Control Volume’:
𝜹𝒒𝒏𝒆𝒕
• 𝟎= + ∑ 𝒔𝒊𝒏 − 𝒔𝒐𝒖𝒕 + 𝒔𝒈𝒆𝒏
𝑻
 Summarize
1. Exergy Balance:
Change in Exergy of the system=Total Exergy In−Total Exergy Out−Total Exergy Destroyed
W Closed system
min 1
§ ∆∅4:4 = ∑ 𝑄 1 − 1& − ∑ 𝑊 − 𝑃K 𝑉> − 𝑉K −𝐼
,

Open system

𝑑𝑋 𝑇K
= • 𝑄̇ 1 − − • 𝑊̇ + • 𝑚𝑎 ̇ ,,5<8 − 𝐼 ̇
̇ ,,$= − 𝑚𝑎
mout 𝑑𝑡 𝑇!

Q Steady state ‘Control Volume’:

surrounding 1&
𝑻𝟎 § 0 = ∑𝑞 1 − − ∑ 𝑤 + ∑ 𝑎,,$= − 𝑎,,5<8 − (𝑑𝐼/𝑑𝑚)
1,

Rate of loss of available energy (exergy) in a

process is proportional to the rate of entropy
E" ̇
generation
𝑎, = h − 𝑇K 𝑠 + + 𝑔𝑧 𝐼 ̇ = 𝑇K 𝑆W(=
? Gouy-Stodola theorem
∅= 𝑈 + 𝑃K 𝑉 − 𝑇K 𝑆 (𝑛𝑒𝑔𝑙𝑒𝑐𝑡𝑖𝑛𝑔 𝐾𝐸 𝑎𝑛𝑑 𝑃𝐸 𝑐ℎ𝑎𝑛𝑔𝑒𝑠)