Lecture 7.

5
Chemical Exergy
CONCEPT OF CHEMICAL
EXERGY
Exergy : Max. work that can be
obtained from any form of
energy( e.g. in a flowing
stream)
Environment can interact with systems
in three ways:
Thermal interaction
Mechanical Interaction
Chemical interaction
CONCEPT OF CHEMICAL
EXERGY
Environmental State & Dead State
Mech & Thermal
eqlbm. With
environment
{Thermo-
mechanical exergy}
M+T+Chemical
eqlbm.
{Total exergy}
Ex : CO
2
flowing in a pipe at T
o
, P
0
.
CONCEPT OF CHEMICAL
EXERGY
Chemical Exergy :
Max amount of work obtainable when
the substance under consideration
is brought from environmental state
to Dead State by processes involving
heat transfer & exchange of matter
only with the environment.
or work obtainable due to diff. in
the chemical potential
3 kinds of
ref.
substances
(i) Gaseous
components of
atmosphere
(ii)Solid substances
from the Earths crust
(iii)Ionic-Nonionic
substances from
oceans
Reference Substances for e
x
ch.

for ref. substances
=
ch
x
e
Diff in chem. Potentials of the
substance in stream & that in
the environment
e.g. for gaseous phase, say CO
2
, at
T
o
, P
o
we would visualise a
system for extracting ch
x
e
Reference Substances for e
x
ch.

Chemical Exergy
W
sh

S.P.M.
T
o
, P
o
1
2
Environ-
ment
TER
Chemical Exergy

=
ch
x
e
Work output in isothermal exp.
2 1 2 1
= = g g
2
1
f
f
n RT =
Making ideal gas assumption
Chemical Exergy

( )
e
co
o
co
o
ch
x
y n RT
P
P
n RT e
2
2
=
|
|
.
|

\
|
=
Ideal gas Mixture
? =
ch
x
e
mol. fraction of
CO
2
in
environment

=
i
i
e
i i
ch
y y y RT e )} / {ln(
0
Total Exergy
ch
x x
e gz
V
s T h s T h e + + + =
2
) ( ) (
2
0 0 0 0
Flow Process
Non-flow Process
ch
x
e gz
V
s T v P u s T v P u + + + + + =
2
) ( ) (
2
0 0 0 0 0 0 0

Chemical Exergy of fuels

For substances not present in
environment consider an
idealised reaction of the
substance with other substances
(usually ref. substances for
which exergies are known) so
that the final products also are
reference substances

Chemical Exergy of fuels
ex. Hydrocarbon fuel.
O
2

C
a
H
b

Q
W
sh

H
2
O (liq)
CO
2

(T
0
, P
0
)
T
0
P
0

Chemical Exergy of fuels
Assuming no irreversibility
ch
x
ch
x sh
ch
x
ch
fuel x
O H co o
e
b
e a W e
b
a e
2 2
max
2
2 4
,
+ + =
|
.
|

\
|
+ +
O H
b
aCO O
b
a H C
b a 2 2 2
2 4
+
|
.
|

\
|
+ +
As already proved
r sh
G W A =
max ,
&
e
i
ch
x
y n RT e
i
=

|
|
.
|

\
|
+ A =
+
2
4 /
2 2
2
b e
o H
a e
co
b a e
o
r
ch
x
y y
y
n RT G e
fuel

Chemical Exergy of fuels
Standard Environment for Calculating the
Chemical Exergy of Hydrocarbon Fuels
0.7567
0.2035
0.0303
0.0003
0.0092
N
2
0
2
H
2
0
C0
2
Other
101.325 kPa 298.15 K
Mole
Fraction
x
i
Substance
(All in Gas
Phase)
Pressure,P
0

Temperature
T
0
Composition
Example
Solution : The reaction equation is
( ) u 0 2 0 20
2 2 2 4
H C CH + +
( )
( )( )
2
0 0
2
0
0
2 2
2
H C
T R
e e
e
y y
y
ln +
( )
( ) ( ) | |
2 4 2 2
0 0 0
2 2 g g g g e
CH H C
Ch
x
+ + =
u
Calculate the chemical exergy in methane gas at
25
0
C and 101.325 kPa.
SOLUTION
2035 . 0
2
0
=
e
y
0003 . 0
2
0
=
C
e
y
0303 . 0
0
2
=
H
e
y
At 25
0
C and 101.325 kPa
mol kg kJ g
C
/ 630 , 394
2
0
=
mol kg kJ g
H
/ 730 , 228
0
2
=
mol kg kJ g
CH
/ 844 , 50
4
=
0
2
0
= g
SOLUTION
( ) ( ) | 730 , 228 2 630 , 394 + =
Ch
x
e
( )| 0 844 , 50 +
( )
( )( )
2
2
0303 . 0 0003 . 0
2035 . 0
ln 15 . 298 3143 . 8 +
mol kg kJ 550 , 29 250 , 801 + =
mol kg kJ 800 , 830 =
End of Lecture