Stoichiometric Calculations

Hsin Chu Professor Dept. of Environmental Engineering National Cheng Kung University

1. Applications of the Combustion Equation

(1 !toi"hiometri" proportions for fin#ing the "orre"t air supply rate for a fuel (2 Composition of the "om$ustion pro#u"ts is useful #uring the #esign% "ommissioning an# routine maintenan"e of a $oiler installation &n'site measurements of flue gas "omposition an# temperature are use# as a $asis for "al"ulating the effi"ien"y of the $oiler at routine maintenan"e intervals.
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2. Combustion Air Requirements: Gaseous Fuels

Cal"ulating the air re)uire# for gaseous fuels "om$ustion is most "onvenient to *or+ on a volumetri" $asis. ,he stoi"hiometri" "om$ustion rea"tion of methane is CH. / 2&2 C&2 / 2H2& *hi"h sho*s that ea"h volume (normally 1 m( of methane re)uires 2 volumes of o0ygen to "omplete its "om$ustion.
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 1f *e ignore the "omponents *hi"h are present in the parts per million range% air "onsists of a$out 2.34 $y volume argon% 56.14 nitrogen an# 22.34 o0ygen (ignoring *ater vapor . Car$on #io0i#e is present at 2.2(64. 7or the purposes of "om$ustion "al"ulations the "omposition of air is appro0imate# as a simple mi0ture of o0ygen an# nitrogeno0ygen 214 nitrogen 534
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 ,he "omplete relationship for stoi"hiometri" "om$ustionCH. / 2&2 / 5.82N2 C&2 / 2H2& /5.82N2 as the volume of nitrogen *ill $e 2953:21;5.82. < very small amount of nitrogen is o0i#i=e# $ut the resulting o0i#es of nitrogen (N&> are not forme# in suffi"ient )uantities to "on"ern us here. Ho*ever% they are highly signifi"ant in terms of air pollution.

 1t "an $e seen that the "omplete "om$ustion of one volume of methane *ill re)uire (2/5.82;3.82 volumes of air% so the stoi"hiometri" air'to'fuel (<@7 ratio for methane is 3.82. 1n pra"ti"e it is impossi$le to o$tain "omplete "om$ustion un#er stoi"hiometri" "on#itions. 1n"omplete "om$ustion is a *aste of energy an# it lea#s to the formation of "ar$on mono0i#e% an e0tremely to0i" gas% in the pro#u"ts.
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 E0"ess air is e0presse# as a per"entage in"rease over the stoi"hiometri" re)uirement an# is #efine# $yactual A / F ratio stoichiometric A / F ratio 100% stoichiometric A / F ratio

E0"ess air *ill al*ays re#u"e the effi"ien"y of a "om$ustion system.

 1t is sometimes "onvenient to use term e0"ess air ratio% #efine# as Ahere su$'stoi"hiometri" (fuel'ri"h air'to' fuel ratios may $e en"ountere#% for instan"e% in the primary "om$ustion =one of a lo*'N&> $urner% the e)uivalen"e ratio is often )uote#. ,his is given $ystoichiometric A / F ratio actual A / F ratio
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actual A / F ratio stoichiometric A / F ratio

3. Flue Gas Composition-Gaseous Fuels

,he "omposition of the stoi"hiometri" "om$ustion pro#u"ts of methane is1 volume C&2 5.82 volumes N2 2 volumes H2& Biven a total pro#u"t volume% per volume of fuel $urne#% of 12.82 if *ater is in the vapor phase% or 6.82 if the *ater is "on#ense# to a li)ui#. ,he t*o "ases are usually a$$reviate# to *et an# #ry.
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 ,he proportion of "ar$on #io0i#e in this mi0ture is therefore 1 100% = 9.51% wet and 10.52 1 100% = 11.74% dry 8.52 ,he instruments use# to measure the "omposition of flue gases remove *ater vapor from the mi0ture an# hen"e give a #ry rea#ing% so the #ry flue gas "omposition is usually of greater usefulness.
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 Consi#ering the "om$ustion of methane *ith 224 e0"ess air% the e0"ess air (2.293.82 of 1.3 volumes *ill appear in the flue gases as (2.2191.3 ;2.. volumes of o0ygen an# (1.3'2.. ;1.8 volumes of nitrogen. ,he "omplete "omposition *ill $e"onstituent vol@vol methane C&2 1 &2 2.. N2 3.22 H2& 2 giving a total pro#u"t volume of 12..2 (*et or 12..2 (#ry .

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 ,he resulting "omposition of the flue gases% e0presse# as per"entage $y volume% isConstituent 4 vol (#ry 4 vol (*et C&2 3.? 6.1 &2 (.6 (.2 N2 6?.? 52.? H2& 1?.1
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 E0ample 1< gas "onsists of 524 propane (C(H6 an# (24 $utane (C.H12 $y volume. 7in#(a ,he stoi"hiometri" air'to'fuel ratio an# ($ ,he per"entage e0"ess air present if a #ry analysis of the "om$ustion pro#u"ts sho*s 34 C&2 (assume "omplete "om$ustion . !olution,he "om$ustion rea"tions for propane an# $utane are- C3 H 8 + 5 O2 + 18.8 N 2 3 CO2 + 4 H 2O + 18.8 N 2
C4 H10 + 6.5 O2 + 24.5 N 2 4 CO2 + 5 H 2O + 24.5 N 2
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 (a !toi"hiometri" <ir Ce)uirement &n the $asis of 1 volume of the fuel gas% the propane "ontent re)uires 2.5 9 (8 / 16.6 ; 1?.5 vols air an# the $utane re)uires 2.( 9 (?.8 / 2..8 ; ?.( vols air Hen"e the stoi"hiometri" air'to'fuel ratio is 2(-1.
1.

($ E0"ess <ir ,he "om$ustion pro#u"ts (#ry *ill "ontain (2.5 9 ( / (2.( 9 . ; (.( vols C&2 (2.5 9 16.6 / (2.( 9 2..8 ; 22.8 vols N 2 plus D volumes e0"ess air% giving a total volume of pro#u"ts of (2(.6 / D . Biven that the measure# C&2 in the pro#u"ts is 34% *e "an *rite9 3.3 = 100 (23.8 + ) hen"e D ; 12.65 vols ,he stoi"hiometri" air re)uirement is 2( vols so the per"entage e0"ess 12.87 air is-

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100% = 55.9%

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. Combustion Air Requirements-Soli! an! "iqui! Fuels

,he *ay in *hi"h the "om$ustion e)uation is use# refle"ts the availa$le information on the analysis of the soli# or li)ui# fuels. ,his ta+es the form of an element'$y'element analysis (referre# to as an ultimate analysis *hi"h gives the per"entage $y mass of ea"h element present in the fuel. <n e0ample of an ultimate analysis of a li)ui# fuel (oil might $e Component 4 $y mass Car$on (C 6? Hy#rogen(H2 1.

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 Ea"h "onstituent is "onsi#ere# separately via its o*n "om$ustion e)uation. 7or the "ar$onC / &2 C&2 or for 1 +g of fuel 32 44 0.86 + 0.86 0.86 (kg) 12 12 !o ea"h +g of oil re)uires 2.23 +g o0ygen for "om$ustion of its "ar$on an# pro#u"es (.18 +g C& 2 as pro#u"t.
12+g (2+g ..+g

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 !imilarly H2 / &2 H2&

2+g 1?+g

or per +g of fuel

16+g

1n or#er to $urn the hy#rogen "ontent of the oil 1.12 +g o0ygen are nee#e# an# 1.2? +g *ater is forme#.
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16 18 0.14 + 0.14 0.14 (kg) 2 2

 ,he total o0ygen re)uirement is thus (2.23 / 1.12 or (..1 +g. < given )uantity of air "onsists of 214 $y volume of o0ygen. Ae "an simply transform to a mass $asis thusComponent &0ygen Nitrogen vol fra"tion(vf 2.21 2.53 vf 9 EA ?.52
22.12 28.84

Eass fra"tion
6.72 = 0.233 28.84

22.12 = 0.767 28.84

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 Ae "an no* esta$lish that (..1 +g o0ygen% *hi"h is the stoi"hiometri" re)uirement% *ill $e asso"iate# *ith3.41 0.767 = 11.23 kg nitrogen 0.233

,he stoi"hiometri" air'to'fuel ratio is thus (..1 / 11.2( ; 1..? - 1

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#. Combustion $ro!ucts-Soli! an! "iqui! Fuels ,he stoi"hiometri" "om$ustion pro#u"ts from "om$ustion of the oil areC&2 (.18 +g H2& 1.2? +g N2 11.2( +g ,he "om$ustion pro#u"ts *oul# normally $e nee#e# as a volume per"entage% so the reverse operation to that *hi"h *as performe# for air a$ove is re)uire#.
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 Hen"e if *e re)uire a #ry volume per"entage of the a$ove pro#u"ts the follo*ing ta$ular pro"e#ure is "onvenientComponent C&2 N2 Eass@+g fuel (.18 11.2( +moles@+g fuel
3.15 = 0.0716 44 11.23 = 0.4011 28 0.4727

mole fra"tion 2.181 2.6.3

,he stoi"hiometri" "om$ustion pro#u"ts are thus 18.14 C&2 an# 6..34 N2.
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 !oli# fuels% an# many li)ui# fuels% "ontain "ompoun#s of sulfur. 7or the purposes of stoi"hiometri" "al"ulations this is assume# to $urn to sulfur #io0i#e! / &2 !&2 1n reality a mi0ture of sulfur #io0i#e an# sulfur trio0i#e (!&( is pro#u"e#% $ut it is "onventional to assume "om$ustion to !&2 *hen "al"ulating air re)uirements.
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 !oli# fuels an# some oils pro#u"e ash *hen they $urn. ,he per"entage of ash in the fuel is part of the ultimate analysis an#% as far as *e are "on"erne# at the moment% ash is simply treate# as a totally inert su$stan"e. Eany soli# fuels "ontain small amounts of o0ygen an# nitrogen. ,he o0ygen present in the fuel is "onsi#ere# to $e availa$le for $urning the "ar$on% hy#rogen an# sulfur present. ,he nitrogen in the fuel is ta+en to appear as gaseous nitrogen in the "om$ustion pro#u"ts.

2.

 E0ample 2- Com$ustion Cal"ulation for a Coal < "oal has the follo*ing ultimate analysis4 $y mass Car$on 32 Hy#rogen ( &0ygen 2.8 Nitrogen 1 !ulfur 2.8 <sh ( Cal"ulate(a the volumetri" air supply rate re)uire# if 822 +g@h of "oal is to $e $urne# at 224 e0"ess air an# ($ the resulting 4C&2 (#ry $y volume in the "om$ustion pro#u"ts.

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 !olutionFay out the "al"ulation on a ta$ular $asis using 1 +g "oalEass (per +g Car$on Hy#rogen !ulfur &0ygen Nitrogen <sh 2.3 2.2( 2.228 2.228 2.21 2.2( &2 Ce)uire#
0.9

Pro#u"ts
0.9

32 = 2.4 12 16 0.03 = 0.24 2 32 0.005 = 0.005 32

44 = 3.3 12 18 0.03 = 0.27 2 64 = 0.01 32

0.005

'2.228 ' '

' 2.21 '

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 (a &0ygen re)uire# to $urn 1 +g "oal ; 2.. / 2.2. / 2.228 ' 2.228 ; 2.?2 +g. 2.62 <ir re)uire# ; 0.233 = 11.25 kg <"tual air supplie# ; 11.28 9 1.2 ; 1(.8 +g <ssuming a #ensity for air of 1.2 +g@m(% the flo* rate *ill $e500 3 13.5 = 1.56 m /s 1.2 3600
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 ($ ,o get the 4C&2 in the "om$ustion pro#u"ts *e nee# to +no* the amounts of o0ygen an# nitrogen in the flue gases. <ir supplie# ; 1(.8 +g per +g "oal% of *hi"h o0ygen is 1(.8 9 2.2(( ; (.1. +g% an# nitrogen 1(.8 (.1. ; 12.(? +g. ,he "om$ustion pro#u"ts *ill thus "ontain(.1. 2.?2 ; 2.82 +g &2 an# 12.(? / 2.21 ; 12.(5 +g N2.

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 < se"on# ta$ular pro"e#ure "an no* $e use# for the volumetri" "omposition of the flue gasesPro#u"t Eass@+g "oal Eol. At. +moles@+g "oal 4volume
C&2 !&2 &2 N2 (.( 2.21 2.82 12.(5 .. ?. (2 26 2.258;((.(@.. 2.22218? 2.2( (.81 62.22 1?.28;(2.258@2..?1.

0.37 2.21?2 0.4614

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%. $ractical Si&nificance of the Flue Gas Composition 1t is "omparatively easy to ma+e on'site measurements of the #ry volumetri" "on"entration of either "ar$on #io0i#e or o0ygen in the flue gases. Either of these measurements "an $e use# to "al"ulate the air'to'fuel ratio (or e0"ess air if the "omposition of the fuel is +no*n an# the "om$ustion of the fuel is "omplete. ,he volume per"entage of o0ygen or "ar$on #io0i#e in the flue gas *ill $e influen"e# $y the level of e0"ess air an# also $y the "ar$on-hy#rogen ratio present in the fuel.

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 1f pure "ar$on is $urnt% the only "om$ustion pro#u"t is "ar$on #io0i#e% so ea"h mole"ule of o0ygen in the "om$ustion air $e"omes a mole"ule of "ar$on #io0i#e in the flue gas. ,his means that the stoi"hiometri" "om$ustion of "ar$on *ill pro#u"e 214 $y volume C&2. 1f *e "onsi#er for the moment that hy#ro"ar$on fuels "onsist only of "ar$on an# hy#rogen% as the "ar$on-hy#rogen ratio of the fuel #e"reases the stoi"hiometri" air'to'fuel ratio *ill in"rease. ,his is $e"ause 1 +g "ar$on re)uires (2@12;2.?5 +g of o0ygen for "omplete "om$ustion $ut 1 +g hy#rogen re)uires 6 +g o0ygen.
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 ,he per"entage C&2 in the flue gases *ill fall as the "ar$on-hy#rogen ratio in the fuel #e"reases as (1 less "ar$on #io0i#e *ill $e pro#u"e# per +ilogram of fuel an# (2 the in"rease# air re)uirement means that the "ar$on #io0i#e pro#u"e# *ill $e #ilute# $y the e0tra nitrogen in the flue gas. ,his effe"t is illustrate# in ,a$le 2.1 (ne0t sli#e . ,he "ar$on-hy#rogen ratio in fuels lie $et*een the limits of 58-28 (methane to aroun# 38-8 (high "ar$on "oals .
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'able 2.1 Carbon !io(i!e concentraton in flue &ases

C - H ($y mass 122 2 38 32 68 62 58 52 ?8 8 12 18 22 28 (2 (8 !atoi"hiometri" 4C&2 21.22 16.?5 1?.?2 1..61 1(.13 11.5( 12..2 3.2(
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 Ne0t sli#e (7ig. 2.1 ,here is a uni)ue relationship $et*een the "omposition of the flue gas an# the e0"ess air for any given fuel.

(.

Constituent

% by vol.

 Ne0t !li#e (7ig. 2.2 < plot of the per"entage C&2 in the flue gases over a range of values of e0"ess air for C-H ratios ranging from 58-28 to 38-8. ,he "urves for fuels *ith higher C-H ratios lie a$ove those for fuels *ith a lo*er value of this ratio.
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 Ne0t !li#e (7ig. 2.( ,he relationship $et*een the per"entage o0ygen in the flue gas an# the e0"ess air is very similar for a *i#e range of fuels. ,his is #ifferent from the C&2 "urves.

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 ,a+e the "om$ustion of t*o e0treme "ases- one +mole of "ar$on an# one +mole of methane. 1n ea"h "ase *e *ill "onsi#er 1224 e0"ess air. ,he "om$ustion of "ar$on un#er these "on#itions is #es"ri$e# $yC/ 2 &2 / 5.82 N2 C&2 / &2 / 5.82 N2 ,he per"entage of o0ygen in the flue gas is thusG1@(1/1/5.82 H91224;12.84 ,he "orrespon#ing e)uation for methane is CH. / . &2 / 18.28 N2 C&2 /2 H2& /2 &2 /18.28 N2 giving a per"entage o0ygen of G2@(1/2/18.28 H91224;114

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). Sub-stoichiometric Combustion
,here are "ir"umstan"es in *hi"h lo"ali=e# fuel'ri"h "om$ustion "an ta+e pla"e% su"h as *here "om$ustion of the fuel is a t*o' stage pro"ess *ith se"on#ary air a##e# #o*nstream of the primary "om$ustion =one. ,he me"hanism of "om$ustion of a fuel *ith less than the stoi"hiometri" air re)uirement "onsists of the follo*ing se)uen"e of events(1 ,he availa$le o0ygen firstly $urns all the hy#rogen in the fuel to *ater vapor. (2 <ll the "ar$on in the fuel is then $urne# to "ar$on mono0i#e. (( ,he remaining o0ygen is "onsume# $y $urning "ar$on mono0i#e to "ar$on #io0i#e.

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 Ne0t sli#e (7ig. 2.. 1t "an $e seen that as the air supply falls $elo* the stoi"hiometri" re)uirement the per"entage of "ar$on mono0i#e in the flue gas in"reases very )ui"+ly.

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Air fuel ratio Figure 2.4 Sub-stiochiometric combustion of natural gas

 E0ample (- Com$ustion of a 7uel un#er !u$' !toi"hiometri" Con#itions Estimate the *et an# #ry flue gas "omposition if propane is $urne# *ith 384 of the stio"hiometri" air re)uirement. !olutionthe stoi"hiometri" rea"tion for this fuel is C(H6 / 8 &2 ( C&2 / .H2& &n a volumetri" $asis *e have (8 9 2.38 ;..58 volumes of &2 availa$le. ,his means that the a""ompanying nitrogen is 15.65 volumes.
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 7irstly all the hy#rogen in the fuel is $urne# to *ater. ,his *ill pro#u"e . volumes of *ater vapor an# "onsume 2 volumes of o0ygen% leaving 2.58 volumes for further "om$ustion of the "ar$on in the fuel. Ae assume that all the "ar$on initially $urns to "ar$on mono0i#e an# then the remaining o0ygen is use# in $urning the "ar$on mono0i#e to "ar$on #io0i#e.
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 Iurning the "ar$on to C& *ill pro#u"e ( volumes of C& an# use up 1.8 volumes of o0ygen% leaving (2.58' 1.8 ;1.28 volumes of o0ygen for further "om$ustion. Ne0t rea"tion is C& / &2 C&2 !o 1.28 volumes o0ygen "an $urn 2.8 volumes of "ar$on mono0i#e% pro#u"ing 2.8 volumes of "ar$on #io0i#e. ,he remaining "ar$on mono0i#e is therefore (('2.8 ;2.8 volume.
.?

 ,he pro#u"ts of "om$ustion are thusN2 15.65 volumes C& 2.8 C&2 2.8 H2& ..2 ,otal 2..65 Biving the per"entage "ompositionsAet(4 Dry(4 N2 51.3 68.? C& 2.2 2.. C&2 12.2 12.2 H2& 1?.1 '

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