CACHE Modules on Energy in the Curriculum

Hydrogen as a Fuel
Module Title: Flame Temperature Analysis and NOx Emissions for Different Fuels
Author Affiliation: Michigan Technological University
Course: Combustion and Air Pollution
Text Reference: S ! Turns" An Introduction to Combustion: Concepts and Application
Concepts# Adia$atic flame temperature" theoretical air" E%! percent
Problem Motiation
For a com$ustion process that ta&es place 'ith no heat loss to the surrounding" the
temperature of the products is referred to as the adia$atic flame temperature (t is found
that 'ith an increase in the adia$atic flame temperature" there is increase in NOx
emissions from internal com$ustion engines As 'e &no'" vehicles are a ma)or source of
air pollutants such as nitric oxides" hydrocar$ons" car$on dioxide" etc" there is a gro'ing
shift in the fuels from the petroleum*$ased fuels such as gasoline and diesel fuel to the
alternative fuels such as natural gas" ethanol" methanol" li+uefied petroleum gas and
hydrogen So" in order to study NOx emissions" the change in adia$atic flame
temperature values for conventional fuels in comparison to the alternative fuels 'ith
various e+uivalence ratios and various E%! rates is studied in this module Depending on
ho' the process is completed" adia$atic flame temperature can $e of constant volume or
constant pressure type
Theory
Theoretical Air#
The minimum amount of air needed for the complete com$ustion of a fuel is called the
stoichiometric or theoretical or ,-- . theoretical air (f the air is less than theoretical air"
a com$ustion process cannot $e complete
Adia$atic Flame Temperature#
According to first la' of thermodynamics" for any thermodynamic system the change in
internal energy of a system is e+ual to the difference $et'een the heat transfer to the
system and the 'or& done $y the system
/et 0 represent the heat added to the system 'ith 1 as the amount of 'or& done $y the
system Also U" 2" 3" T" 4 are internal energy" enthalpy" pressure" temperature and
volume of the system
At state ," 05 -" 15 -" U5 U
,
" 252
,
" 353
,
" T5T
,
" 454
,

2eat is added to the system 607 from 'hich there is 'or& done $y the system 617
Thus" at state 8" 0" 1" U5 U
8
" 252
8
" 353
8
" T5T
8
" 454
8
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Draft N S :orate August ,;" 8-,-
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According to first la' of thermodynamics"
<U 5 U
8
* U
,
5 0 * 1
Furthermore" according to the definition of internal energy" U5 2* 34
ie U
,
5 2
,
* 3
,
4
,
and U
8
5 2
8
* 3
8
4
8
For constant pressure adiabatic process:
As 'e &no'"
U
8
* U
,
5 0 * 1
As the process is adia$atic" 05 - and 'or& done $y the system"
8
8 8 , ,
,
1 3d4 5 3 4 * 34

Su$stituting these values in the a$ove e+uation"

U
8
* U
,
5 - = 63
8
4
8
* 3
,
4
,
7
:ut U5 2 = 34
%iving"
62
8
* 3
8
4
8
7 = 62
,
* 3
,
4
,
7 5 = 3
8
4
8
> 3
,
4
,
ie 2
8
= 2
,
5 -
ie 2
8
5 2
,
For a com$ustion process" reactants and products represent state , and state 8
respectively
So" for a constant pressure adia$atic com$ustion process"
3 !
2 2
For constant olume adiabatic process:
As 'e &no'"
U
8
* U
,
5 0 * 1
As the process is adia$atic" 05 - and 'or& done $y the system"
8
,
1 3d4 5 -

$ecause
there is no change in volume of the system 6 d4 5 - 7
Su$stituting these values in the a$ove e+uation"
U
8
* U
,
5 -
:ut U5 2 = 34
%iving"
62
8
* 3
8
4
8
7 = 62
,
* 3
,
4
,
7 5 -
According ideal gas la'"
34 5 N !
u
T
9
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1here"
!
u
= Universal %as ?onstant
n = Num$er of moles of a gas
For state ," 3
,
4
,
5 N
,
!
u
T
,
and for state 8 3
8
4
8
5 N
8
!
u
T
8
Su$stituting these values in the a$ove e+uation 62
8
* 3
8
4
8
7 = 62
,
* 3
,
4
,
7 5 -"
62
8
* N
8
!
u
T
8
7 = 62
,
* N
,
!
u
T
,
7 5 -
So" for a constant pressure adia$atic com$ustion process"
3 ! 3 3 u a ! ! u i
U U ie 2 N ! T 2 N ! T
1here" T
i
is the temperature at 'hich products enter into the com$ustion cham$er and T
a
is the adia$atic flame temperature of products as sho'n in figure ,
No'" enthalpy of a component on a unit mole $asis is given as enthalpy"
f
- -
2 h 6h h 7 + 'here
f
-
h is the enthalpy of formation at the standard reference state
68@? temperature and , atm pressure7"
-
h
is the sensi$le enthalpy at standard reference
state and
h
is the sensi$le enthalpy at the specified state The enthalpy of a component is
the product of the specific enthalpy ie the enthalpy per unit mole of a component and the
num$er of moles of a component So" total enthalpy of products 6or reactants7 is the
summation of enthalpies of all the product 6or reactant7 components ie
f
- -
3 3
3
2 N h 6h h 7 "
1
+
]

f
- -
! !
!
2 N h 6h h 7
1
+
]

and
f
- -
3 3 u a
3
U 5 N h > 6h h 7 ! T "
1

]

f
- -
! ! u i
!
U N h 6h h 7 ! T
1
+
]

Figure ,
Exhaust %as !ecirculation 6E%!7#
A Exhaust gas re*circulation ie E%! is E%! decreases the adia$atic flame temperature
and so the NOx emissions (t is the most effective techni+ue used to reduce NOx
emissions in internal com$ustion engines As sho'n in figure 8" a fraction 6x
,
7 of the
exhaust gases is re*circulated 'ith the inta&e air into the engine
9
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Draft N S :orate August ,;" 8-,-
3age A
Air
Fuel
3roducts
T
i
T
a
?om$ustion
?ham$er
05 -


Figure 8# Exhaust %as !e* circulation
Problem !nformation
Example Problem "tatement:
6a7 ?ompute the adia$atic flame temperature of 28* air at constant pressure and at
constant volume using EES for 9-" B-" C-" ,--" ,8-" ,9-" ,B-" ,C-" 8-- and 8@-
percent theoretical air ?onsider that $oth the fuel and the air enter the com$ustion
cham$er at 8@ D? Discuss the difference $et'een the adia$atic flame temperature
values at constant pressure and constant volume case
6$7 ?ompute the adia$atic flame temperature of gasoline* air and ethyl alcohol* air
mixtures at constant pressure using EES for ,--" ,8-" ,9-" ,B-" ,C-" 8-- percent
theoretical air O$tain and compare a com$ined plot of adia$atic flame temperature vs
. theoretical air 6,-- = 8-- .7 for 28* air" gasoline* air and ethyl alcohol* air
mixture
Procedure
, %o to Start E All 3rograms E Other Apps E EES E ees
8 ?opy the program given $elo' in solution and paste it in the EES e+uation 'indo'
A %o to FOptionsG E FUnit SystemG 2ere 'e are calculating adia$atic temperature in
this example Select Unit System# FS(G" Specific 3roperties# FMolar $asisG"
Temperature Units# FHG and Energy Units# F&IG
9 To avoid potential unit pro$lems in the solution" go to FOptionsG E F4aria$le (nfoG
and enter units of the enthalpies as &IJ&mol and temperatures as H Also /o'er %uess
value for adia$atic temperature 6Ta7 can $e set as F@-- HG instead of F=infinityG in
varia$le information 'indo'
@ (n EES e+uation 'indo'" comments can $e included 'herever necessary 'ith the use
of $races K L or +uote mar&s F G To comment entire line" JJ can $e used at the start of
the line
B To provide . theoretical air values" go to FTa$lesG E FNe' 3arametric Ta$leG and
then enter num$er of runs Select F4aria$les in e+uationsG as FTheoMairG and FTaG
and then FAddG and clic& FOHG
; Then in parametric ta$le 'indo'" enter the . theoretical air values for 'hich the
adia$atic flame temperature is to $e found For first case ie for . theoretical air less
than ,-- ." enter values less than ,-- . in the parametric ta$le Also ma&e sure that
for these values of theoretical air you run correct enthalpy of products e+uation 6other
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x
,
6Exhaust gases7
Engine
Air
Exhaust %ases
Fuel
Air >
x
,
6Exhaust

%ases7
e+uation for enthalpy of products can $e enclosed in K L or F G for a 'hile7 For
second case ie for . theoretical air greater than or e+ual to ,-- ." enter .
theoretical air values ,-- . and greater in the parametric ta$le and +uote the
previously used e+uation for enthalpy of products
C Alternatively Fif*elseG statement can $e used to automatically select the case
according to . theoretical air input
N Once the parametric ta$le is prepared" go to F?alculateG E FSolve Ta$leG
,- (f any error occurs" chec& for the definition of parameters" constant values" total
num$er of varia$les" total num$er of e+uations" etc
,, ?opy the values o$tained for adia$atic flame temperature 'ith respect to .
theoretical air and paste them into an excel file in order to o$tain a com$ined plot
later
,8 As explained in the theory part" there are some changes in the e+uations for constant
volume and constant pressure adia$atic flame temperature
Hints:
The com$ustion of hydrogen for t'o cases 6ie for /am$daO5, or for TheoMairJ,--
O5 ,--. and for /am$daP , or for TheoMairJ,--P ,--.7 can $e explained 'ith the
follo'ing com$ustion e+uations
,7 /am$daO5, or for TheoMairJ,-- O5 ,--.

( ) ( )
8 8 8 8 8
8
TheoMair TheoMair
8 2 O A;B N 8 2 O > A;B N
,-- ,--
TheoMair
, O
,--
_ _
+ +

, ,
_
+

,
87 /am$daP , or for TheoMairJ,-- P ,--.

( ) ( )
8 8 8 8 8
8
TheoMair TheoMair TheoMair
8 2 O A;B N 8 2 O > A;B N
,-- ,-- ,--
TheoMair
8 2
,--
_ _ _
+ +

, , ,
_ _
+ 2

, ,
To get specific enthalpy of each component
f
- -
h 6h h 7
1
+
]
" go to FOptionsG E
FFunction (nfoG and then select FFluid propertiesG There are num$er of fluids and
fluid property values provided in EES Select FEnthalpyG from FFunction (nfoG
column and fuel type from FFluid (nfoG column
"olution #part a$:
EES program for calculation of adia$atic flame temperature of 28* air vs theoretical air
at constant pressure and constant volume#
?onstant 3ressure#
9
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// Initial temperature at which fuel and air enter into the combustion
chamber
Ti=298 [K]
// Molar enthalpies of reactants at initial temperature (Ti
!"!2"Ti=enthalp# ($!2$% T=Ti
!"&2"Ti=enthalp# ($&2$% T=Ti
!"'2"Ti=enthalp# ($'2$% T=Ti
// Molar enthalpies of products at adiabatic temperature (Ta
!"!2'"Ta=enthalp# ($!2'$% T=Ta
!"&2"Ta=enthalp# ($&2$% T=Ta
!"'2"Ta=enthalp# ($'2$% T=Ta
!"!2"Ta=enthalp# ($!2$% T=Ta
// (or constant pressure adiabatic combustion process as deri)ed abo)e
!*=!+
// ,nthalp# of reactants
!*=2-!"!2"Ti. (Theo"air//00-!"'2"Ti. (Theo"air//00-1234-!"&2"Ti
// ,nthalp# of products
56ase /7 (Theo"air//008=/ i2e2 9ambda 8= /5
:!+=2-!"!2'"Ta. (Theo"air//00-1234-!"&2"Ta. ((Theo"air//00;/-!"'2"Ta<
56ase 27 (Theo"air//00 =/ i2e2 9ambda = />
!+=(Theo"air//00-2-!"!2'"Ta.(Theo"air//00-1234-!"&2"Ta.(2;
(Theo"air//00-2-!"!2"Ta
?onstant 4olume#
// Initial temperature at which fuel and air enter into the combustion
chamber
Ti=298 [K]
// ?ni)ersal @as constant
*"u = 821/A [BC/Bmol;K]
// Molar enthalpies of reactants at initial temperature (Ti
!"!2"Ti=enthalp# ($!2$% T=Ti
!"&2"Ti=enthalp# ($&2$% T=Ti
!"'2"Ti=enthalp# ($'2$% T=Ti
// Molar enthalpies of products at adiabatic temperature (Ta
!"!2'"Ta=enthalp# ($!2'$% T=Ta
!"&2"Ta=enthalp# ($&2$% T=Ta
!"'2"Ta=enthalp# ($'2$% T=Ta
!"!2"Ta=enthalp# ($!2$% T=Ta
// (or constant )olume adiabatic combustion process as deri)ed abo)e
?+ = ?*
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Draft N S :orate August ,;" 8-,-
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// ,nthalp# of reactants
?*=2-(!"!2"Ti;*"u- Ti .(Theo"air//00-(!"'2"Ti; *"u- Ti .
(Theo"air//00-1234-(!"&2"Ti;*"u- Ti
// ,nthalp# of products
56ase /7 (Theo"air//008=/ i2e2 9ambda 8= />
?+=2-(!"!2'"Ta;*"u- Ta . (Theo"air//00-1234-(!"&2"Ta;*"u- Ta .
((Theo"air//00;/-(!"'2"Ta;*"u- Ta
56ase 27 (Theo"air//00 =/ i2e2 9ambda = />
5?+= (Theo"air//00-2-(!"!2'"Ta;*"u-Ta . (Theo"air//00-1234-(!"&2"Ta;
*"u- Ta . (2;(Theo"air//00-2-(!"!2"Ta;*"u- Ta5
Results:
Theo%air
#&$
T
adiabatic' CP
#($
T
adiabatic' C)
#($
*+ ,N-; 8AA,
,+ 8,NN 8B;-
-+ 8AN, 8CN-
.++ 8@8; A-9@
./+ 88B; 8;99
.*+ 8-BA 8@-@
.,+ ,CN; 8A,-
.-+ ,;B, 8,9C
/++ ,B9B 8-,,
/0+ ,98; ,;9@
9
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Draft N S :orate August ,;" 8-,-
3age ;
The adia$atic flame temperature at constant volume is greater than that at constant
pressure $ecause there is no 'or& done 6due to no volume change7
$7 ?ompute the adia$atic flame temperature of gasoline* air and ethyl alcohol* air
mixtures at constant pressure using EES for ,--" ,8-" ,9-" ,B-" ,C-" 8-- percent
theoretical air O$tain and compare a com$ined plot of adia$atic flame temperature vs .
theoretical air 6,-- = 8-- .7 for 28* air" gasoline* air and ethyl alcohol* air mixture
Procedure
, As explained in procedure of example pro$lem part 6a7" follo' steps from , to B
8 Then in parametric ta$le 'indo'" enter the . theoretical air values for 'hich the
adia$atic flame temperature is to $e found 2ere 'e are considering only one case in
'hich . theoretical air is greater than or e+ual to ,-- . So" here in program there is
only one e+uation for enthalpy of products
A Once the parametric ta$le is prepared" go to F?alculateG E FSolve Ta$leG
9 (f any error occurs" chec& for the definition of parameters" constant values" total
num$er of varia$les" total num$er of e+uations" etc
@ ?opy the values o$tained for adia$atic flame temperature 'ith respect to .
theoretical air and paste them into an excel file in order to o$tain a com$ined plot
later
Hints:
The com$ustion of gasoline and ethyl alcohol for /am$daO5, or for TheoMairJ,-- O5
,--. can $e explained 'ith the follo'ing com$ustion e+uations
9
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Draft N S :orate August ,;" 8-,-
3age C
%asoline
( ) ( )
C ,C 8 8 8 8 8
8
TheoMair TheoMair
? 2 ,8@ O A;B N ? N 2 O >,8@ A;B N
,-- ,--
TheoMair
,8@ , O
,--
_ _
+ + 8 +

, ,
_
+

,
Ethyl Alcohol
( ) ( )
8 @ 8 8 8 8 8
8
TheoMair TheoMair
? 2 O2 A O A;B N ? A 2 O >A A;B N
,-- ,--
TheoMair
A , O
,--
_ _
+ + 2 +

, ,
_
+

,
"olution #part b$:
EES program for calculation of adia$atic flame temperature of gasoline* air and ethyl
alcohol* air vs theoretical air at constant pressure#
%asoline#
// Initial temperature at which fuel and air enter into the combustion
chamber
Ti=298 [K]
// Molar enthalpies of reactants at initial temperature (Ti
!"68!/8"Ti=enthalp# ($68!/8$% T=Ti
!"&2"Ti=enthalp# ($&2$% T=Ti
!"'2"Ti=enthalp# ($'2$% T=Ti
// Molar enthalpies of products at adiabatic temperature (Ta
!"6'2"Ta=enthalp# ($6'2$% T=Ta
!"6'"Ta=enthalp# ($6'$% T=Ta
!"!2'"Ta=enthalp# ($!2'$% T=Ta
!"&2"Ta=enthalp# ($&2$% T=Ta
!"'2"Ta=enthalp# ($'2$% T=Ta
// Dt adiabatic flame temperature constant pressure% the enthalp# of
the reactants is eEual to the enthalp# of the products
!*=!+
// ,nthalp# of products
56ase7 (Theo"air//008=/5
!+=8-!"6'2"Ta.9-!"!2'"Ta./22F-(Theo"air//00-1234-!"&2"Ta./22F-((Theo"a
ir//00;/-!"'2"Ta
// ,nthalp# of reactants
!*=/-!"68!/8"Ti./22F-(Theo"air//00-!"'2"Ti./22F-(Theo"air//00-1234-!"
&2"Ti
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Ethyl alcohol#
// Initial temperature at which fuel and air enter into the combustion
chamber
Ti=298 [K]
// ,nthalpies of reactants at initial temperature (Ti
!"62!F'!"Ti=enthalp# ($62!F'!$% T=Ti
!"&2"Ti=enthalp# ($&2$% T=Ti
!"'2"Ti=enthalp# ($'2$% T=Ti
// ,nthalpies of products at adiabatic temperature (Ta
!"6'2"Ta=enthalp# ($6'2$% T=Ta
!"6'"Ta=enthalp# ($6'$% T=Ta
!"!2'"Ta=enthalp# ($!2'$% T=Ta
!"&2"Ta=enthalp# ($&2$% T=Ta
!"'2"Ta=enthalp# ($'2$% T=Ta
// Dt adiabatic flame temperature% the enthalp# of the reactants is
eEual to the enthalp# of the products
!*=!+
// ,nthalp# of products
56ase7 (Theo"air//008=/5
!+=2-!"6'2"Ta.1-!"!2'"Ta.1-(Theo"air//00-1234-!"&2"Ta.1-((Theo"air//00
;/-!"'2"Ta
// ,nthalp# of reactants
!*=/-!"62!F'!"Ti.1-(Theo"air//00-!"'2"Ti.1-(Theo"air//00-1234-!"&2"Ti
9
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Draft N S :orate August ,;" 8-,-
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Results
Theo%air
#&$
T
a' hydrogen
#($ T
a' gasoline
#($ T
a' ethyl alcohol
#($
.++ 8@8; 89,, 8A@@
./+ 88B; 8,AB 8,-9
.*+ 8-BA ,N8B ,N-N
.,+ ,CN; ,;B- ,;@A
.-+ ,;B, ,B8B ,B8@
/++
,B9B ,@,@ ,@,C
From the nature of the graph of the adia$atic temperature vs the theoretical air percent for
different fuels" it is clear that hydrogen has higher adia$atic flame tempearture values
compared to other fuels Also since NOx emissions increase 'ith increasing flame
temperature values" NOx emissions are expected to $e higher for hydrogen fuel For the
fuels gasoline and ethyl alcohol" the trends for the adia$atic flame tempeature are similar
For these fuels" the adia$atic flame temperature reaches a maximum approximately at
,-- . theoretical air and then starts decreasing 'ith increasing excess air
9
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Draft N S :orate August ,;" 8-,-
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Home Problem "tatement:
?ompute the adia$atic flame temperature of the stoichiometric mixture of 28* air"
gasoline* air" and ethyl alcohol* air at constant pressure using EES for -" @" ,-" ,@" 8-" 8@"
A-. E%! percent Assume that each fuel is $urned 'ith the stoichiometric amount of air
in the com$ustion cham$er O$tain and compare a com$ined plot of adia$atic flame
temperature vs E%! percent for 28* air" gasoline* air and ethyl alcohol* air mixture
Assume that the recirculation does not change the air feed temperature to the exhaust

Procedure:
, As explained in procedure of example pro$lem part 6a7" follo' steps from , to 9
8 To provide E%! percent values" go to FTa$lesG E FNe' 3arametric Ta$leG and then
enter num$er of runs Select F4aria$les in e+uationsG as FE%!MpercentG and FTaG"
clic& FAddG and then clic& FOHG
A Then in parametric ta$le 'indo'" enter the E%! percent values for 'hich the
adia$atic flame temperature is to $e found 2ere 'e are considering stoichiometric
mixtures of fuel and air
9 Once the parametric ta$le is prepared" go to F?alculateG E FSolve Ta$leG
@ (f any error occurs" chec& for the definition of parameters" constant values" total
num$er of varia$les" total num$er of e+uations" etc
B ?opy the values o$tained for adia$atic flame temperature 'ith respect to E%!
percent and paste them into an excel file in order to o$tain a com$ined plot for all the
fuels later
Hints:
%eneraliQed e+uation for com$ustion of fuel Q x y
? 2 O
including E%! is given $y

Q x y 8 8 8 8 8
8 8 8 8 8 8
y Q y y Q
? 2 O x 6O A;B N 7 x, x ?O 2 O A;B x N
9 8 8 9 8
y y Q y y Q
x ?O 2 O A;B x N x, x ?O 2 O A;B x N
8 9 8 8 9 8
_ _ _
+ + + + + + +

, , ,
_ _ _
+ + + + + + +

, , ,
E%! 6fraction7 and the num$er of moles of the exhaust gas mixture to $e re*
circulated per mole of fuel ?
x
2
y
O
Q
6x,7 are related to each other $y an e+uation"

E%!
x, 5
,* E%!
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Draft N S :orate August ,;" 8-,-
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