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Thermochemistry
Review of Property Relations
Review of Property Relations
Extensive Properties
V(m
3
), U(J), H(J)(=U+PV)
Intensive Properties
v(m
3
/kg), u(J/kg),h=(J/kg)(=u+Pv)
P,T
V=mv;U=mu;H=mh
Equation of State
Equation of State
For Ideal-gas Behavior:
PV=NR
u
T
PV=mRT
Pv=RT
P=RT
where, R=R
u
/MW
R
u
=8315J/kmol-K; MW is the gas
molecular weight
Calorific Equations of State
Calorific Equations of State
u=u(T,v)
h=h(T,P)
du=
dh=
dv
v
u
dT
T
u
T v
) ( ) (
dP
P
h
dT
T
h
T P
) ( ) (
T
T
p ref
T
T
v ref
T
T
ref
ref
dT c h T h
dT c u T u
P
h
v
u
) (
) (
0 ) (
0 ) (
Translation
(a)Monatomic species
Translation Rotation
Vibration
(b)Diatomic Species
Fig.2.2
Ideal-Gas Mixtures
Constituent mole fraction and mass fraction
Mole fraction of species i,x
i
tot
i
i
i
i
N
N
N N N
N
x
+ + +
0 0
Mass fraction of species i, Y
i
tot
i
i
i
i
m
m
m m m
m
Y
+ + +
0 0
By definition
By definition
0
0
i
i
i
i
y
x
Relation of x
Relation of x
i
i
and Y
and Y
i
i
i mix i i
mix i i i
MW MW Y x
MW MW x Y
/
/
i
i i
mix
i
i i mix
MW Y
MW
MW x MW
) / (
0
Partial pressure of ith species,P
i
For ideal gas:
P x P
P P
i i
i
i
E W Q
Heat added to
system in going
fgom state1 to
state 2
Work done by system
on surroundings in
going from state 1 to
state 2
Change in total
system energy in
going from state 1
to state 2
E
1-2
( E
2
-E
1
)
)
0
0
(
0
gz v u m E + +
Mass-specific
system internal
energy
Mass-specific
kinetic energy
Mass-specific
system potential
energy
0 0 0 0 0 0 0 0
e e e w q
dt dE W Q /
Instantaneous rate
of heat transferred
into system
Instantaneous rate
of work done by
system, or power
Instantaneous
time rate of
change of
system energy
dt de w q /
e E/m
First Law-Control Volume-SSSF
) (
0 0 0 i i i cv cv
v P v P m e m e m W Q +
Rate of
heat
transferred
across the
control
surface
from the
surroundin
gs, to the
control
volume
Rate of
all work
done by
the
control
volume,in
cluding
shaft
work, but
excluding
flow
work
Rate of
energy
flowing
out of
the
control
volume
Rate of
energy
flowing
into the
control
volume
Net rate of
workj
associated
with
pressure
forces
where fluid
crosses the
control
surface,
flow work
The principal assumptions
+ +
i i i cv cv
z z g v v h h m W Q
0
0 0
0 0
0
0
( ) ( ) ( )
i i i cv cv
z z g v v h h w q + +
0
0 0
0 0
0
0
Reactant and Product Mixtures
Stoichiometry
3.76=79/21( by volume)
,
_
h
R
h
R
(O/F)
stoic
T
ad,eq
(kJ/kg
fuel
)(kJ/kg
mix
) (kg/kg) (K)
CH
0
+air - , 00000- , 0000 . 0000 0000
H
0
+O
0
- , 111 111 - , 00000. 00 0000
C(s)+air - , 00000- , 0000 . 000 0000
The equivalence ratio
stoic
stoic
A F
A F
F A
F A
) / (
) / (
) / (
) / (
% 000
% tric stoichiome
Percent excess air
Percent excess air
% 000
) - (0
%
excess
Example 2.1
Example 2.1
A small, low-emission, stationary gas-
turbine engine operates at full
load(3950kW) at an equivalence ratio of
0.286 with an air flowrate of 15.9kg/s.
The equivalent composition of the
fuel(natural gas) is C
1.16
H
4.32
. Determine
the fuel mass flowrate and the operating
air-fuel ratio for the engine.
Solution
Given: =0.286, MW
air
=28.85,
m
air
=15.9 kg/s,
MW
fuel
=1.16(12.01)+4.32(1.008)=18.286
Find: m
fuel
and (A/F)
We will proceed by first finding (A/F) and
then m
fuel
.The solution requires only the
application of definitions expressed in
Equs above
where a=x+y/4=1.16+4.32/4=2.24. Thus,
and, from Equ. above
, 00 . 0 ) / (
fuel
air
stoic
MW
MW
a F A
, 00 . 00
000 . 00
11 . 00
) 11 . 0 ( 00 . 0 ) / (
stoic
F A
[ ] [ ] 0 . 00
000 . 0
00 . 00 ) / (
stoic
F A
(A/F)
Since (A/F) is the ratio of the air flowrate to
the fuel flowrate,
Comment
Note that even at full power, a large quantity
of excess air is supplied to the engine.
[ ] [ ] s kg
s kg
F A
m
m
air
/ 000 . 0
0 . 00
/ 0 . 00
) / (
Example 2.2
Example 2.2
A natural gas-fired industrial boiler
operates with an oxygen
concentration of 3 mole percent in
the flue gases. Determine the
operating air-fuel ratio and the
equivalence ratio. Treat the natural
gas as methane.
Solution
Solution
Given: x
O
2
=0.03, MW
fuel
=16.04
MW
air
=28.85.
Find : (A/F)and .
We can use the given O
2
mole fraction to
find the air-fuel ratio by writing an
overall combustion equation assuming
complete combustion, i.e., no
dissociation (all fuel C is found in CO
2
and all fuel H is found in H
2
O):
CH
4
+a(O
2
+3.76N
2
)CO
2
+
2
H
2
O+bO
2
+3.76aN
2
where a and b are related from conservation
of O atoms.
2a=2+2+2b
From the definition of a mole fraction
.
00 . 0 0
0
00 . 0 0 0
0
0
a
a
a b
b
N
N
x
mix
O
O
+
+ + +
Substituting the known value of x
O
2
(=0.03)
and then solving for a yields
or a=2.368
The mass air-fuel ratio, in general, is
expressed as
a
a
00 . 0 0
0
00 . 0
+
0 . 00
11 . 00
) 00 . 00 )( 000 . 0 ( 00 . 0
) / (
0
00 . 0
) / (
, ) / (
F A
MW
MW a
F A
so
MW
MW
N
N
F A
fuel
air
fuel
air
fuel
air
To find , we need to determine(A/F)
stoic.
For a=2,hence,
0000 . 0
111 . 00
000 . 00
00 . 0
0000 . 0
000 . 00
00 . 00
00 . 0
1111 . 0
000 . 00
00 . 00
00 . 0
0
0
N
CO
CO
Y
Y
Y
Enthalpy of Combustion and
Heating Values
For the steady-flow reactor, complete
combustion:
All C CO
2
All H H
2
O
Fig.2.7
reac prod i cv
h h h h q
0
reac prod cv R
h h q h
reac prod R
H H H
where,
mix
fuel
fuel
R
mix
R
m
m
kg
kJ
h
kg
kJ
h ) ( ) (
0 ) / (
0
+
F A m m
m
m
m
fuel air
fuel
mix
fuel
The stoichiometric air-fuel ratio for CH
4
is
17.11; thus,
mix
kg
kJ
h
The heat of combustion-heating
value h
c
h
c
= h
R
We obtain
Or on a per-mass-of-mixture basis
) , ( ) , ( P T H P T H
ad prod i reac
) , ( ) , ( P T h P T h
ad prod i reac
T
ad
is defined from this first-law
statement, which is called the
constant-pressure adiabatic flame
temperature.
T
ad
is simple and this quantity
requires knowledge of the
composition of the combustion
products.
The flame temperature
are typically several
thousand kelvins.
Calculating the complex
composition by invoking
chemical equilibrium is the
subject of the next section.
Example 2.5
Example 2.5
Mixture composition:
Properties(Appendices A and B)
00 . 0 , 0 , 0
00 . 0 0 0 ) 11 . 0 ( 0
0 0 0
0 0 0 0 0 0
+ + + +
N O H CO
N N N
N O H CO N O CH
Species Enthalpy of
Formation @ K 000
h
0
f,i
(kJ/kmol)
Specific Heat
@ K 0000
c
P,i
(kJ/kmol-K)
CH
0
- , 00000 -----
CO
0
- , 111 111 . 0000
H
0
O - , 000 000 . 0000
N
0
0 . 0000
O
0
0 ----
From First Law
From First Law
)] 000 - . ( 0000 ( . )[ 1111
)] 000 ( 00 . 00 000 , 000 )[ 0 (
) 000 ( 00 . 11 000 , 000 )[ 0 (
)] 000 ( [
000 , 00 ) 0 ( 00 . 0 ) 0 ( 0 ) 000 , 00 )( 0 (
,
0
,
ad
ad
ad
ad i p i f i prod
react
i
prod
i prod
react
i i react
T
T
T
T c h N H
kJ H
h N H h N H
+ +
+ +
+
+
+ +
Equating H
react
to H
prod
and
solving for T
ad
yields
T
ad
=2318K
Constant-volume adiabatic
Constant-volume adiabatic
flame temperature
flame temperature
Ideal Otto-cycle analysis:
where U is the absolute(or standardized)
internal energy of the mixture.
) , ( ) , (
f ad prod init init reac
P T U P T U
0 ) (
f init prod reac
P P V H H
For the ideal-gas law
0 ) (
,
prod
ad
reac
init
u prod reac
prod prod mix
reac reac mix
MW
T
MW
T
R h h
MW N m
or
MW N m
Example 2.6
Example 2.6
Estimate the constant-volume
adiabatic flame temperature for
a stoichiometric CH
4
-air
mixture using the same
assumtions as in Example 2.5.
Initial conditions are T
i
=298K,
P=1 atm(101,325Pa).
Solution
Solution
The same composition and properties used in
Example 2.5 apply here. We note,
however, that the c
p,i
values should be
evaluated at a temperature somewhat
greater than 1200K, since the constant-
volume T
ad
will be higher than the
constant-pressure T
ad
. Nevertheless, we
will use the same values as before.
First Law:
0 ) (
0 ) (
ad prod init reac u
prod
i i
reac
i i
ad prod init reac u prod reac
T N T N R h N h N
or
T N T N R H H
Substitute numerical values, we
have
kJ T
T
T
T H
kJ H
ad
ad
ad
ad prod
reac
) 000 ( 0 . 000 111 , 000
)] 000 . ( 1111 ( . )[ 1111
)] 000 ( 00 . 00 000 , 000 )[ 0 (
)] 000 ( 00 . 00 000 , 000 )[ 0 (
000 , 00 ) 0 ( 00 . 0 ) 0 ( 0 ) 000 , 00 )( 0 (
+
+ +
+ +
+
+ +
And
where N
reac
=N
prod
=10.52kmol.
Reassembling and solving for T
ad
yields
T
T
ad ad
=2889K
=2889K
) 000 )( 00 . 00 ( 000 . 0 ) (
ad ad prod init reac u
T T N T N R
Chemical Equilibrium
In high temperature combustion
processes, the products of
combustion are not a simple mixture
of ideal products, as may be
suggested by the simple atombalance
used to determine stoichiometry.
Rather, the major species dissociate,
producing a minor species.
For example
For example
+ +
1
]
1
+
0 0
tan
0
0
) 0 (
0
0
is the fraction of the CO
2
dissociated.
T
ad
is the function of the dissociation fraction
: =1, no heat released and unchanged.
=0, the maximum amount of heat release
occurs and the temperature and pressure
would be the highest possible allowed by
the first law.
Where N
i
is the number of moles of species
i in the mixture. The individual species
entropies are obtained from
0
,
0
ln ) (
P
P
R
T
dT
c T s s
i
u
T
T
i p ref i i
f
ref
+
=1/2 and v
C
=1 for forming a
mole of CO from O2 and C, respectively. As with
enthalpies, the Gibbs functions of formation of
the naturally occurring elements are assigned
values of zero at the reference state.
The Gibbs function for a mixture
of ideal gases
where N
i
is the number of moles of the ith
species.
or
+ )] / ln( [
0 0
, ,
P P T R g N g N G
i u T i i T i mix
0
mix
dG
The second term can be shown to be zero by
reconizing that d(lnP
i
)=dP
i
/P
i
and that
dP
i
=0, since all changes in the partial
pressures must sum to zero because the
total pressure the total pressure is constant.
Thus,
0 ] / ln( [ )] / ln( [
0 0
,
0 0
,
+ + +
P P T R g d N P P T R g dN
i u T i i i u T i i
+ )] / ln( [ 0
0 0
,
P P T R g dN dG
i u T i i mix
For the general system, where
the change in the number of moles of
each species is directly proportional
to its stoichiometric coefficient, i.e.,
+ + + + fF eE bB aA
kf dN
ke dN
kb dN
ka dN
F
E
B
A
+
+
Substituting and canceling the
proportionality constant k, we obtain
Equation can be rearranged and the log terms
grouped together to yield:
0 )] / ln( [ )] / ln( [
)] / ln( [ )] / ( [
0 0
,
0 0
,
0 0
,
0 0
,
+ + + + +
+ +
P P T R g f P P T R g e
P P T R g b P P T R g a
F u T F E u T E
B u T B A u T A
. ) / ( ) / (
. ) / ( ) / (
ln
...) ... (
0 0
0 0
0
,
0
,
0
,
0
,
etc P P P P
etc P P P P
T R
g b g a g f g e
b
B
a
A
f
F
e
E
u
T B T A T F T E
+ +
The term in parentheses on the left-hand-side
is called the standard-state Gibbs function
change G
T
0
,i.e.,
T B f A f F f E f
T B T A T F T E T
g b g a g f g e
g b g a g f g e G
...) ... ( g
y, alternatel or
...) ... (
0
,
0
,
0
,
0
,
0
T
0
,
0
,
0
,
0
,
0
+ +
+ +
The equilibrium constant K
P
. ) / ( ) / (
. ) / ( ) / (
0 0
0 0
etc P P P P
etc P P P P
K
b
B
a
A
f
F
e
E
p