Introduction to the

Exergy Concept

2.83/2.813
T. G. Gutowski
2
 Readings
1. Ch.2 Thermodynamics Revisited (p 7-13), and
2. Ch 6 Exergy, a Convenient Concept (p
59-62), Jakob de Swaan Arons, 2004
3. Ch 6 Thermodynamic Analysis of Resources
Used in Mfg Processes, Gutowski & Sekulic,
in TDR 2011
4. Appendix, Tables of Standard Chemical
Exergy, Szargut, Morris & Steward, 1988
3
 Exergy Accounting
Exergy Units: Joules J, rate in Watts, W
Exergy symbols: B, Ex, X, and b, ex, x
Also called Availability by Keenan, 1941
and Available Energy , R, by
Gyftopoulos and Beretta, 1991

4
 Definition of Exergy
Exergy is the amount of work obtainable
when some matter is brought to a state of
thermodynamic equilibrium with the
common components of the natural
surroundings by means of reversible
processes, involving interaction only with
the above mentioned components of
nature [Szargut et al 1988].

5
 Exergy
System State

Maximum work obtainable

between System and Reference
States.

Reference State

6
 Exergy
System State

The minimum work needed

to raise System from the reference
state to the System State

Reference State

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 Aggregate Exergy
Accounting

Exout
Exin
Exlost

Exin ! Exout = Exlost

8
 Thermodynamics Overview
Systems
Heat Interactions
Exergy of heat interaction
Entropy and Enthapy
Physical and Chemical Exergy

9
 Open System
Work interaction

W
massin

Mass
massout

Heat interaction

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Closed System

X
W
massin

X
Mass
massout

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Isolated System

X
massin
X
W

X
Mass
massout

X
Q

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 The 1st Law

#U = Qin " Wout

dU = !Qin " !Wout

! dQ " ! dW = 0

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Heat Interaction Q
TH
Q

Wout = Q ! Qo

Qo Wout Qo
!= = 1"
Q Q
To
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Carnots Reversible Heat
Engine
Qout TL
!reversible = f (TH ,TL ) =
Qin TH

TL
" = 1!
TH

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 Maximum Work Output
max TL
W out = Qin (1 ! )
TH
Qin is at TH, let TL be Tref or To
This gives the available energy of a heat
interaction at TH in reference To.
Work and Heat are no longer equivalent!

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 Exergy Ex of Heat
Interaction
Q To
E = Q(1 ! )
X
T
Exergy, Ex is the available energy w.r.t.
a reference environment, T0, and P0
Ex(work) = W; Ex (heat) = Q(1-T0/T)

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 Availability
The First Law states that in every cyclic
process either work is converted into heat
or heat is converted into work. In this
sense it makes no distinction between
work and heat except to indicate a means
of measuring each in terms of equivalent
units. Once this technique of
measurement is established, work and
heat become entirely equivalent for all
applications of the First Law.
Keenan, 1941 18
 Availability
The Second Law, on the other hand,
marks the distinction between these two
quantities by stating that heat from a
single source whose temperature is
uniform cannot be completely converted
into work in any cyclic process, whereas
work from a single source can always be
completely converted into heat.

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Keenan, 1941
 Availability
The efforts of the engineer are very largely
directed toward the control of processes
so as to produce the maximum amount of
work, or so as to consume the minimum
amount of it. The success of these efforts
can be measured by comparing the
amount of work produced in a given
process with the maximum possible
amount of work that could be produced in
the course of a change of state identical
with that which occurs in the process. 20
Keenan, 1941
 Energy, E and Exergy, B = Ex
E2, B2

E1, B1 Properties for two different states

of the system shown by the boxes.
This change may come about due to
spontaneous changes or due to heat
or work interaction, or mass transfer.

B1- B2 = E1- E2 reversible process

B1- B2 > E1- E2 irreversible process
Ref: Gyftopoulos and Beretta
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 Define Entropy
1
S1 = So + "#( E1 ! Eo ) ! (B1 ! Bo ) $%
CR

They show CR = TR = T0
Entropy is a Property
Entropy is a measure of something lost

Ref: Gyftopoulos and Beretta

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 Entropy Difference
1
S2 ! S1 = "#( E2 ! E1 ) ! (B2 ! B1 ) $%
CR

S = 0, reversible process
S > 0, irreversible process

Ref: Gyftopoulos and Beretta

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 Example, Heat Interaction
Q, T

T T0

E2 = E1 +Q
B2 = B1 + Q(1-T0/T)
S = (1/T0)(Q Q + Q(T0/T)) = Q/T

S = Q/T
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Example, Work Interaction
W

E2 = E1 +W
B2 = B1 + W
S = (W - W) = 0

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Homeworks 1 & 2
TH
Qin 1. Calculate the entropy change
for a reversible heat engine,and
2. Calculate the entropy loss for a
reversible heat engine.

Use the results given in this

Presentation.
Qout

TL
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 Answers for 1 & 2
Consider the process in two stages; 1) you transfer heat in, and
2) You transfer heat and work out. Use the result from Carnot to
Show that the change in entropy is zero. This leads to the result that
The exergy lost is also zero.

1 QL QH
!S = S2 " S1 = #$( E2 " E1 ) " (B2 " B1 ) %& = "
To TL TH
Blost = QH " QL + To !S " W

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 Properties or State Variables
T = temperature
P = pressure intensive variables
V = volume
U = internal energy
E = energy
extensive
B = exergy and
H = enthalpy (H = U + PV) intensive
variables
S = entropy

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 State Variables
2

! dU = 0 # d ! = ! 2 " !1
1

dQ
!T = 0 ! d (U + PV ) = 0

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 Enthalpy H=U+PV

1 2

Here the Work done is W = P(V2 V1)

The First Law can be written as Q = (U+PV)2 (U + PV)1

The quantity in parenthesis is Enthalpy H = U + PV

The First Law can be written as Qin = H

Constant Pressure Equilibrium Process 30

For Flow System Energy
1 1
U + P! + mV + mgz = H + mV 2 + mgz
2

2 2

Control Volume
F

d
Wboundary = Fd = P

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 Open System with H, S
W
H, S
po, To

H, S
p, T
Q, To

Consider the Work to bring the system from the

reference environment at standard conditions,
To, po to the state at T, p

See Ch 6 de Swaan Arons

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From EQ 1 & 2(Ch 6), de Swaan Arons

H! in ! H! out ! Q! out + W!in = 0

Q!
S!in ! S!out ! out + S! generated = 0
To

! = !H! " T !S! + T S!

W o o generated

Steady State Work to bring system from Po, To to P, T

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Minimum Work = Exergy
W! rev
Wmin = = "H ! To "S
m!
= ( H p ,T ! H po ,To ) ! To ( S p ,T ! S po ,To )

B = ( H ! To S ) ! ( H ! To S ) o
W! rev
Wmin = = Bout ! Bin
m!

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Lost Work & Lost Exergy

Recall:
! = B! out ! B! in + To S!generated
W

Let: ! =W
W ! min + Wlost then

! lost = B
W ! lost = To S!generated

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 Exergy also is W

p, T

W! max
b! = wmax po, To
m!
Q

B = ( H ! To S ) ! ( H ! To S ) o
the maximum amount of work that can be
obtained from a system in reference to the
environment at standard conditions, To, Po
Standard ref. values T0 = 298.2! K , Po = 101.3kPa
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Open flow system

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First Law for a Flow System

' dU $ ' ui2 $

% " = )m ! i %% hi + + gzi ""
& dt # cv in & 2 #
' ui2 $
!)m ! j %% h j + + gz j ""
out & 2 #

+ ) Q! in ! ) Q! out + ) W! sh ,in ! ) W! sh ,out

' (u 2 $ !
! %% (H +
m + g(z "" + Q in ! W!out = 0 EQ 1
& 2 #
38
one stream steady state
Second Law for a Flow System
' dS $
% " = (m ! i Si ! ( m ! jSj
& dt # cv in out

*Q! k *Q!1 !
+() !() + Sgenerated
in T out T

Q! surr !
! !S +
m + Sgenerated = 0 EQ 2

T
one stream steady state 39
 From EQ 1 & 2
' (u 2 $ !
! %% (H +
m + g(z "" + Q ! W!out = 0
& 2 #

Q!
! !S +
m + S! generated = 0
T0

2
! ( !u %
W rev
! && !H +
=m ! To !S
+ g!z ## " m
' 2 $
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 Physical and Chemical
Exergy
B = Bph + Bch
Bph(T=To, p=po , = * ) =0
this is the restricted dead state

Bch(* = ) = 0
when B = Bph + Bch = 0
this is the dead state

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Thank you Jan Szargut

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Chemical Reaction, at To, po
n1R1 + n2 R2 n33

R1
3
R2

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 Chemical Reactions
stoichiometric mass balance
va Ra + vb Rb + .... # v j " j + vk " k + ...

exergy " balance"

va bRa + vbbRb + .... ! v j b" j ! vk b" k = Blost

where exergy b is given in kJ/mole

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 Example: Burning Carbon
C + O2 CO2

BC + BO2 - BCO2 = B
410.3 kJ + 3.97 kJ 19.9 kJ = 394.4kJ
mol mol mol

The maximum work you can get out of one mol of carbon is
394.4 kJ = 32.9 MJ
mol of carbon kg

These exergy values come from Szargut s Appendix Tables

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 Burning Octane
2C8H18(l) + 25 O2(g) 16 CO2(g) + 18H2O(g)

2(5413.1) + 25(3.97) - 16(19.87) - 18(9.5) = B

B = 10,436.53 kJ/2 mols of octane

10,436.53 = 45.8 MJ
(2[(8 x 12) + 18]= 228g) kg

Note: B = -Gf = H - ToS LHV

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 Note that g h
(lower heating value) for fuels

Ref

& Beretta

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Gyftopolous
48
Example: Oxidation of Aluminum

3
2Al + O2 ! Al2O3
2
kJ 3 kJ kJ
2 " 888.4 + " 3.97 # 200.4 = Blost
mol 2 mol mol

kJ
Blost = (1776.8 + 6.0 # 200.4 ) = 1582.4
mol(Al2O3 )

See Appendix of Szargut for exegy values49

Materials can do work?
System State (TH)
QH

Insert reversible
heat engine between
Wrev high and low
temperatures

QL

Reference State (TL)

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 Chemical Properties referenced to
the environment
Crust

Oceans

Atmosphere

T0 = 298.2 K, P0 = 101.3 kPA 51

Exergy Reference System

pure metal, element

chemical
reactions
oxides, sulfides

crustal component
extraction
earth s crust (ground state)

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Exergy Reference System

Aluminum (c=1) 888.4 kJ/mol

Al2O3 (c=1) 200.4 kJ/mol

Al2SiO5 (c=1) 15.4kJ/mol

Al2SiO5 (c = 2 x 10-3) 0 kJ/mol (ground)

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Example; making pure iron from
the crust

Fe (c = 1) 376.4 kJ/mol

reduction

Fe2O3 (c=1) 16.5 kJ/mol

extraction
Fe2O3 (c = 1.3 x 10-3) 0 kJ/mol (ground)

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55
 Extraction from the crust

Extracting Fe 2O 3 from c = 1.3x10 !3 (crust) to c = 1

1
B = To R ln
1.3x10 !3

o J 1 kJ
B = 298.2 K " 8.314 " ln !3
= 16.5
mol K 1.3 " 10 mol

Note: R = k Navo (Boltzmann s constant X Avogadro s number)

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 Reduction of Fe2O3 (Hematite)

2Fe2O3 + 3C 4Fe + 3CO2

2 x 16.5 + 3 x 410.3 4 x 376.4 3 x 19.9 =

Blost = - 301.4 kJ
this is an endothermic reaction
i.e. minimum energy required to reduce 2 mole of hematite

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 Iron Ore Reduction
Recall C + O2 CO2 produces 394.8 kJ/mol C

301.4
We need = 0.76 mols of carbon
394.8

2Fe2O3 + 3.76C + 0.76O2 4Fe + 3.76 CO2

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 Iron Ore Reduction
but the efficiency of the use of carbon
is only 30.3%
therefore the actual reaction is

2Fe2O3 + 12.42C + 9.42O2 4Fe + 12.42CO2

33kJ + 5095.9 + 37.7 - 1505.6 - 247.2kJ =
3,413.8 kJ for 4 mol of Fe
this is 15.2 MJ/kg (Fe)

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 Iron Ore Reduction
12.42 ! 394.8 4.903MJ MJ
Fuel (C) Intensity = = = 22
4 ! 55.85 g .2234kg kg

12.42 ! 44 kg CO2
CO2 Intensity = = 2.5
4 ! 55.85 kg Fe

Exergy value of pure Fe is 376.4 kJ/mole = 6.7 MJ/kg

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 Summary for Iron Ore

fuel used = 22 MJ/kg 15.2(Blost) + 6.7(BFe)

Credit for producing

pure iron from the crust

Lost exergy from making iron

from Fe2O3

See Smil Table A.12, iron from ore 20 - 25 MJ/kg

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Exergy Balance, Open System

B!W ,in
B!W ,out
B!Q,in
B! loss B!Q,out
B! in
B! out

B! in + B!W ,in + B!Q,in = B! out + B!W ,out + B!Q,out + B! loss

Includes: materials flows, heat and work interactions

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