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BalancesonReactiveSystems
Materialbalancenolonger g takestheform

INPUT=OUTPUT
Mustaccountforthedisappearanceofreactantsand

appearanceofproductsthroughstoichiometry.

Stoichiometric Equations
Thestoichiometric equation ofachemicalreactionisastatement q

oftherelativeamountsofreactantsandproductsthat participateinthereaction.

2SO2 +O2 2SO3


q yifthenumberofatomsof Astoichiometric equation isvalidonly eachatomicspeciesisbalanced.

2S 2S 4O+2O 6O

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Stoichiometric Equations
Thestoichiometric equation ofachemicalreactionisa q

statementoftherelativeamountsofreactantsand productsthatparticipateinthereaction. 2SO2 +O2 2SO3 Astoichiometric ratio oftwomolecularspecies participatinginareactionistheratiooftheir stoichiometric coefficients: 2molSO3 generated/1molO2 consumed 2molSO3 generated/2molSO2 consumed

Stoichiometric Equations
C4H8 +6O2 4CO2 +4H2O Isthisstoichiometric equationbalanced?

Whatisthestoichiometric coefficientofCO2? Whatisthestoichiometric ratioofH2OtoO2? HowmanylbmolO2 reacttoform400lbmolCO2?


400lbmol CO2 6lbmolO2 = 600 lbmol O2 4 lbmol lb l CO2

100lbmol/minC4H8 isfedand50%reacts.Atwhatrateiswater

formed?
lbmol C 4H8 lbmolH2O 4lbmolH2O 0.50 = 200 100 min 1lbmolC 4H8 min

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LimitingandExcessReactants
Tworeactantsaresaidtobeinstoichiometric p proportion ifthe p

ratio(molesApresent/molesBpresent)equalsthe stoichiometric ratiofromthebalancedreactionequation.

2SO2 +O2 2SO3


thefeedratiothatwouldrepresentstoichiometric proportionis

nSO2/nO2 =2:1
If freactantsarefed f dinstoichometric h proportion,and dthe h reaction

proceedstocompletion,allreactantsareconsumed.

LimitingandExcessReactants
Stoichiometric Proportion Reactantsarep presentinaratio p

equivalenttotheratioofthestoichiometric coefficients.

A +2B 2C

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LimitingandExcessReactants
Limiting greactant Areactantislimiting gifitispresent p

inlessthanstoichiometric proportionrelativetoevery otherreactant. A +2B 2C

Excessreactant Allotherreactantsbesidesthe

limitingreactant.

LimitingandExcessReactants
f fractionalexcess(fXS) ratiooftheexcesstothestoichiometric proportion. (n ) (n A )stoich fXS = A feed (n A )stoich

A +2B 2C

5 4 = 0.25 4

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LimitingandExcessReactants
fractionalconversion(f) ratiooftheamountofa

reactantreacted,totheamountfed. A +2B 2C
f=

(n A )reacted (n A )fed

fA =

0 = 0.0 5

fB =

0 = 0.0 8

LimitingandExcessReactants
f fractionalconversion(f) ratiooftheamountofareactant

reacted,totheamountfed.
f=

A +2B 2C

(n A )reacted (n A )fed

fA =

1 = 0.2 5

fB =

2 = 0.25 8

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LimitingandExcessReactants
f fractionalconversion(f) ratiooftheamountofareactant

reacted,totheamountfed.
f=

A +2B 2C

(n A )reacted (n A )fed

fA =

2 = 0.4 5

fB =

4 = 0.5 8

LimitingandExcessReactants
f fractionalconversion(f) ratiooftheamountofareactant

reacted,totheamountfed.

A +2B 2C

f=

(n A )reacted (n A )fed

3 fA = = 0.6 5

fB =

6 = 0.75 8

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LimitingandExcessReactants
f fractionalconversion(f) ratiooftheamountofareactant

reacted,totheamountfed.

A +2B 2C

f=

(n A )reacted (n A )fed

fA =

4 = 0.8 5

fB =

8 = 1.0 8

ExtentofReaction
extentofreaction() anextensivequantitydescribingthe

progress p g ofachemicalreaction. stoichiometric coefficients:A =1,B =2,C =2 n i = n i0 + i A +2B 2C

=0

n A = n A0

n B = n B0 2

nC = nC0 + 2

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ExtentofReaction
extentofreaction() anextensivequantitydescribingthe

progressofachemicalreaction. stoichiometric coefficients:A =1,B =2,C =2

n i = n i0 + i

A +2B 2C

=0

nA = 5 = 5

n B = 8 2 = 8

nC = 0 + 2 = 0

ExtentofReaction
extentofreaction() anextensivequantitydescribingthe

progressofachemicalreaction. stoichiometric coefficients:A =1,B =2,C =2

n i = n i0 + i

A +2B 2C

=1

nA = 5 = 4

n B = 8 2 = 6

nC = 0 + 2 = 2

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ExtentofReaction
extentofreaction() anextensivequantitydescribingthe

progressofachemicalreaction. stoichiometric coefficients:A =1,B =2,C =2

n i = n i0 + i

A +2B 2C

=2

nA = 5 = 3

n B = 8 2 = 4

nC = 0 + 2 = 4

ExtentofReaction
extentofreaction() anextensivequantitydescribingthe

progress ofachemicalreaction. p g stoichiometric coefficients:A =1,B =2,C =2 n i = n i0 + i =4 A +2B 2C

nA = 5 = 1

n B = 8 2 = 0

nC = 0 + 2 = 8

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2C2 H 4 + O2 2C2 H 4O
Assumeanequimolar reactantfeedof100kmol:
Whatisthelimiting greactant?
Areactantislimitingifitispresentinlessthanstoichiometric proportionrelativetoeveryotherreactant.

n C2H4 nO 2 nC2H4 nO 2

2 = 1 stoich =1 feed 1

ethylene

2C2 H 4 + O2 2C2 H 4O
Assumeanequimolar reactantfeedof100kmol: q
Whatisthepercentageexcessofeachreactant?

fXS ,O2 = =

(n ) (n ) (n )
O2 feed O2 stoich

O2 stoich

100 50 = 1.00 = 100% 50

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2C2 H 4 + O2 2C2 H 4O
Assumeanequimolar reactantfeedof100kmol:
Ifthereactionproceedstocompletion: (a)howmuchoftheexcess
o n O2 = n O + O2 2

reactantwillbeleft?

o n C 2H 4 = n C + C 2H 4 2H 4

0 = 100 + ( 2)

n O2 = 100 + ( 1)50 n O2 = 50

(b)How H much hC2H4O

willbeformed?

n C2H4O = 0 + (2)50 n C2H4O = 100

= 50 o n C 2H 4O = n C + C2H4O 2H 4O

(c)Whatistheextentofreaction?

2C2 H 4 + O2 2C2 H 4O
Assumeanequimolar reactantfeedof100kmol:
Ifthereactionp proceedstoap pointwherethefractional

(n ) f= (n )
f= n
o C 2H 4

conversionofthelimitingreactantis50%,howmuchofeach reactantandproductispresentattheend?Whatis?
C2H 4 reacted C2H 4 fed

= 0.5
= 0.5

100 50 = 100 + ( 2) = 25
o n O2 = n O + O2 2

o n C 2H 4 = n C + C 2H 4 2H 4

n C 2H 4
o C 2H 4

o n C 2H 4O = n C + C2H4O 2H 4O

n C2H4O = 0 + (2)25 n C2H4O = 50

100 n C2H4

n O2 = 100 + ( 1)25

= 0.5 100 n C2H4 = 50

n O2 = 75

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2C2 H 4 + O2 2C2 H 4O
Assumeanequimolar reactantfeedof100kmol: Ifthereactionproceedstoapointwhere60molofO2 is left,whatisthefractionalconversionofC2H4?Whatis?
n O2 = n + O2
o O2

o n C 2H 4 = n C + C 2H 4 2H 4

60 = 100 + ( 1) = 40

n C2H4 = 100 + ( 2)40 n C2H4 = 20

f=

(n ) (n )

C2H 4 reacted C2H 4 fed

100 20 = 0.8 100

ReactionStoichiometry
Acrylonitrile producedbyreactionofammonia,propylene,andO2 at

30%conversionoflimitingreactant:
determinelimitingreactant
limiting

C3 H6 + NH3 + 3 O3 C3 H3 N + 3H 2O
2

(nNH (nNH (nO (nO


2 2

)0 = (0.120 100 0.100 100)= 1.20 nC H ) =( 1 1)= 1 stoich nC H ) = ( 0.780 0.21 100 0.100 100)= 1.64 0 nC H ) =( 1.5 1)= 1.5 stoich
nC 3 H 6
3 6 3 6 3 6

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Acrylonitrile producedbyreactionofammonia,propylene,andO2 at

30%conversionoflimitingreactant:
determinefractionalexcesses
limiting

f XS = 0.20 0 20

C3 H6 + NH3 + 3 O C3 H3 N + 3H2O 2 3
f XS = 0.093

1 mol NH = 10.0 mol NH3 (n NH )stoich = 10.0 mol C3 H6 1 mol C H NH NH ( ) = 12.0 10.0 = 0.20 (f XS )NH = ( () 10.0 NH ) 1.5 mol O = 15.0 mol O2 (nO )stoich = 10.0 mol C3 H6 1 mol C H (O ) (O ) = 16.4 15.0 = 0.093 (f XS )O = (O ) 15.0
3 3 3 6 3 0 3 stoich 3 3 stoich 2 2 3 6 2 0 2 stoich 2 2 stoich

Acrylonitrile producedbyreactionofammonia,propylene,andO2 at

30%conversionoflimitingreactant:
limiting

f XS = 0.20

C3 H 6 + NH3 + 3 O3 C3 H 3 N + 3H2O
usefractional conversiontodetermine amountofpropylene thatleavesthereactor
f XS = 0.093

nC 3 H 6 = 1 f nC 3 H 6

( )(

)0 = (1 0.30)(10.0 mol C3H6 )= 7.0 mol C3H6

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Acrylonitrile producedbyreactionofammonia,propylene,andO2 at

30%conversionoflimitingreactant:

C3 H6 + NH3 + 3 O C3 H3 N + 3H2O 2 3
determine extent of reaction by applying mole balance to propylene

limiting

f XS = 0.20

f XS = 0.093

= 3 mol

n i = n i0 + i

nC 3 H 6 = 7.0 mol C3 H6

nC3 H 6 = nC 3 H 6

7.0 mol = 10.0 mol = 3 mol

)0 + (1)

Acrylonitrile producedbyreactionofammonia,propylene,

andO2 at30%conversionoflimitingreactant:
f XS = 0.20
f XS = 0.093

applymolebalanceto allremainingspecies

C3 H 6 + NH 3 + 3 2 O2 C3 H 3 N + 3 H 2 O
= 3 mol n i = n i0 + i

nC 3 H 6 = 7.0 mol C3 H 6
nNH 3 = (0.12)(100 ) + ( 1)(3) = 9 nC3 H 3 N = (0) + (+ 1)(3.0) = 3 nH 2O = (0) + (3)(3.0) = 9

)(3) = 11.9 nO2 = (0.21)(0.78)(100) + ( 3 2


nN 2 = (0.79)(0.78)(100 ) + (0 )(3) = 61.6

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Fuel for motor vehicles other than gasoline are being eyed because they generate lower levels of pollutants than does gasoline. gasoline Compressed propane has been suggested as a source of economic power for vehicles. Suppose that in a test 22 kg of C3H8 is burned with 400 kg of air to produce 44 kg of CO2 and 12 kg of CO. a. What was the percent excess air? b. The components in the product stream.

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C3H8 +5O2
Component C3H8 Air O2 N2 CO2 CO H2O. Total 44 12 Amount (kg) 22 400

3CO2 +4H2O
Molecular weight 44 29 Input (kg-mol) 0 50 0.50 13.80 0.21*13.80 =2.90 0.79*13.80 =10.9 44 28 18 29.87 Output (kg-mol) ? ? ? ? 1 0.43 ? ?

Percentexcessair=(O2 in O2 used)/(O2 theory) =(2.90 5*0.5)/(5*0.5)=16%


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C3H8 +5O2 C3H8 +7/2O2


Component Input (kg-mol) 0.50 Consumed [1] [ ] (kg-mol) 0.33

3CO2 +4H2O 3CO+4H2O


Consumed [2] [ ] (kg-mol) 0.43/3=0.14 3.5*0.14= 0.49 Generated [1] [ ] (kg-mol) 1 4*0.33= 1.32

[1] [2]
Total Output (kg-mol) 0.03 0.76 10.9 1 0.43 1.88 15

Generated [2] [ ] (kg-mol) 0.43 4*0.14= 0.56

C3H8 O2 N2 CO2 CO H2O. Total

0.21*13.80 5*0.33= 1.65 =2.90 0.79*13.80 =10.9 29.87 -

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Example
A gas stream containing 80 mol% C2H6 and 20 mol% O2 is burned in an engine with 200% excess air. If 80% of the ethane goes to CO2, 10% goes to CO and the remaining unburned, determine the amount of the excess air per 100 moles of the feed gas.

C2H6 +7/2O2 C2H6 +5/2O2

2CO2 +3H2O[1] 2CO+3H2O[2]

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Basis=100molefeedgas

C2H6 +7/2O2

2CO2 +3H2O
Component Input Gas Stream 80 20 + 0.21*Gair= 799.7 Gair= 4.76*780 = 3,712.8 0.79*Gair= 2,933.1

[1]
Output (kg-mol)

Percentexcessair(basedonair): (O2 in O2 used)/(O2 theory)=2 O2 theory (Eq 1) = 3.5*80=280 O2 used (air) =O2 theory (Eq 1)-20=260 moles (O2 in (air)-260)/(260)=2 O2in (air)=260+(2*260)=780moles N 780 ,93 .8 N2 in = 3.76 3.76*780=2,932.8 Air stream=2,932.8 + 780=4.76*780=3,712.8
C2H6 O2 Air N2 CO2 CO H2O. Total

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C2H6 +7/2O2 C2H6 +5/2O2


Component Input (mol) 80 799.7 2,933.1 3812.8 Consumed [1] [ ] (mol) 64 224 -

2CO2 +3H2O[1] 2CO+3H2O[2]


Consumed [2] [ ] (mol) 8 20 192 Generated [1] [ ] (mol) 128 Generated [2] [ ] (mol) 16 24 Total Output (mol) 8 204 2933.1 128 16 216 3,505.1

C2H6 O2 N2 CO2 CO H2O. Total

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ChemicalEquilibrium
Given asetofreactivespecies,and reactionconditions Determine 1. thefinal(equilibrium)compositionofthereaction mixture 2. howlongthesystemtakestoreachaspecifiedstate shortofequilibrium

ChemicalEquilibrium
Irreversiblereaction reactionproceedsonlyinasingledirectionA B concentrationofthelimitingreactanteventually approacheszero(timedurationcanvarywidely)

Equilibriumcompositionofanirreversiblereactionis thatwhichcorrespondstocompleteconversion.

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ChemicalEquilibrium
Reversiblereaction reactionproceedsinbothdirectionsA B netrate(forward backward)eventuallyapproaches zero(again,timecanvarywidely)

Equilibriumcompositionofareversiblereactionisthat whichcorrespondstotheequilibriumconversion.

EquilibriumComposition
Anequilibriumreactionproceeds
K(T ) =
yi =

y CO2 y H2 y CO y H2O
ni ntotal

toanextentattemperatureTbased ontheequilibriumconstant,K(T).
whereyi isthemolefractionofspeciesi

ni = ni0 + i

CO(g ) + H2O(g ) CO2 (g ) + H2 (g ) Watergasshiftreaction: Assume1moleCOand2moleH2O K(1105K)=1.00

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EquilibriumComposition
CO = (nCO )0 + ( 1) = (1 ) n

nH2O = nH2O 0 + ( 1) = (2 )
CO2 0

nCO2 nH2

( ) = (n ) + (+ 1) = = (n ) + (+ 1) =
H2 0

K(T ) =

y CO2 y H2 y CO y H2O

yi =

ni = ni0 + i

ni ntotal

ntotal = nCO + nH2O + nCO2 + nH2 = 3

CO(g ) + H2O(g ) CO2 (g ) + H2 (g ) Watergasshiftreaction: Assume1moleCOand2moleH2O K(1105K)=1.00

EquilibriumComposition
nCO = 1 = 0.333 nH2O = 2 = 1.333 nCO2 = = 0.667 nH2 = ntotal = 3

()() =1= (1 )(2 )


= (1 )(2 )
2

K(T ) =

y CO2 y H2 y CO y H2O

yi =

ni ntotal

= 0.667

2 = 2 2 + 2 = 0.667mol

ni = ni 0 + i

CO(g ) + H2O(g ) CO2 (g ) + H2 (g ) Watergasshiftreaction: Assume1moleCOand2moleH2O K(1105K)=1.00

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EquilibriumComposition ( )( ) = 1 (1 )(2 ) y = 0.333 / 3 = 0.111


CO

K(T ) =

y CO2 yH2 y CO y H2O


ni ntotal

y H2O = 1.333 / 3 = 0.444 y CO2 = 0.667 / 3 = 0.222 y H2 = 0.667 / 3 = 0.222 ntotal = 3

2 = (1 )(2 ) 2 = 2 2 + 2 = 0.667mol

yi =

ni = ni0 + i

CO(g ) + H2O(g ) CO2 (g ) + H2 (g ) Watergasshiftreaction: Assume1moleCOand2moleH2O K(1105K)=1.00

y CO = 0.333 / 3 = 0.111 y H2O = 1.333 / 3 = 0.444 y CO2 = 0.667 / 3 = 0.222 y H2 = 0.667 / 3 = 0.222 ntotal = 3

limitingreactantisCO equilibrium atequilibrium,


= 0.667mol

ni = ni0 + i
nCO = 1 + ( 1)(0.667) = 0.333mol

fractionalconversionatequilibrium
0.333 f = 1.001 = 0.667 .00

CO(g ) + H2O(g ) CO2 (g ) + H2 (g ) Watergasshiftreaction: Assume1moleCOand2moleH2O K(1105K)=1.00

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MultipleReactions
C2 H 4 + 1 O2 C2 H 4O C2 H 4 + 3O2 2CO2 + 2H2O
forj reactionsofi species, molebalancebecomes
2

ni = (ni )0 + ij j
j

nC2H4 = nC2H4 nO2 = nO2 nC2H4O


0

( ) + ( ) + ( 3) ) + (+ 1) = (n
1 2 1 C 2H4 O 0 1

+ ( 1)1 + ( 1)2
2

nCO2 = nCO2 nH2O

( ) + (+ 2) = (n ) + (+ 2)
0 H2O 0

MultipleReactions
C2 H 4 + 1 O C2 H 4O 2 2
forj reactionsofi species, molebalancebecomes

C2 H 4 + 3O2 2CO2 + 2H2O

ni = (ni )0 + ij j
j

yield =

molesdesiredproductformed molesformed at 100% conversion with no side reactions


molesdesiredproductformed molesundesiredproductformed

selectivity =

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MultipleReactions
100molesAfedtoabatchreactor productcomposition:10molA,160B,10C

Whatis 1. fA? 2. YB? 3. SB/C? 4. 1,2

A 2B AC

fA =

100 10 = 0.9 100

MultipleReactions
100molesAfedtoabatchreactor productcomposition:10molA,160B,10C

Whatis 1. fA? 2. YB? 3. SB/C? 4. 1,2

A 2B AC
YB = 160 = 0.889 (100 10 )( 2 1)

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100molesAfedtoabatchreactor productcomposition:10molA,160B,10C

Whatis 1. fA? 2. YB? 3. SB/C? 4. 1,2

A 2B AC

SB /C =

160 = 16 10

100molesAfedtoabatchreactor

A 160B, B 10C productcomposition:10molA,

Whatis 1. fA? 2. YB? 3. SB/C? 4. 1,2

A 2B A C
nB = nBo + B11 160 = 0 + 21 1 = 80

nA = nAo A + A 1 1 + A 2 2 10 = 100 1 2 2 = 90 1 = 10

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BalancesonReactiveProcesses
Continuous, of ethane , steady ystate dehydrogenation y g Total mass balance still has INPUT = OUTPUT form Molecular balances contain consumption/generation Atomic balances (H and C) also have simple form
C2H6 C 2H4 + H2

BalancesonReactiveProcesses
Continuous,steadystatedehydrogenationofethane Firstconsidermolecularbalances: MolecularH2 balance:generation=output generationH2 =40kmol H2/min C2H6 balance:input=output+consumption 100kmol C2H6/min=n1 +(C2H6 consumed) C2H4 balance:generation=output (C2H4 generated) t d)=n2
C 2H6 C 2H4 + H2

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BalancesonReactiveProcesses
Continuous,steadystatedehydrogenationofethane

At i Cb l i t=output t t Atomic balance: input

C 2H6 C 2H4 + H2

100molC2H6

2molC 1molC 2H6

& ( )= n

2molC 1 1molC 2H6

& ( )+ n

2molC 2 1molC 2H4

)
)

AtomicHbalance:input=output

100 mol C2 H 6

6 mol H 1 mol C 2 H 6

) = 40(

2 mol H 1 mol H 2

&( )+ n

6 mol H 1 1 mol C 2 H 6

& ( )+ n

4 mol H 2 1 mol C 2 H 4

IndependentEquations
To understand the number of independent species balances in a

reacting system requires an understanding of independent algebraic equations. Algebraic equations are independent if you cannot obtain any of them by adding/subtracting multiples of the others.

x + 2y = 4[1] 3x + 6y = 12[2]

x + 2y = 4 [3] 2x z = 2 [4] 4 y + z = 6[5]


2[3] [4]=[5]

3[1]=[2]

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IndependentEquations
To understand the number of independent species balances p p

in a reacting system requires an understanding of independent algebraic equations. Algebraic equations are independent if you cannot obtain any of them by adding/subtracting multiples of the others.

x + 2y = 4[1] 3x + 6y = 12[2]

3(4 2y ) + 6y = 12

(12 6y ) + 6y = 12
12 = 12

IndependentSpecies
If two molecular or atomic species are in the same ratio to p

each other where ever they appear in a process and this ratio is incorporated in the flowchart labeling, balances on those species will not be independent equations.

&1 = n &3 n & 1 = 3.76n &3 3.76n

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IndependentChemicalReactions
When using balances or extents of g molecular species p

reaction to analyze a reactive system, the degree of freedom analysis must account for the number of independent chemical reactions among the species entering and leaving the system.

IndependentChemical Reactions
Chemical reactions are independent if the stoichiometric p

equation of any one of them cannot be obtained by adding and subtracting multiples of the stoichiometric equations of the others.

A 2B [1] B C[2] A 2C[3]


2[2]+[1]=[3]

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SolvingReactiveSystems
There are 3 possible methods for solving balances around a reactive

system: 1. Molecular species balances require more complex calculations than the other methods and should be used only for simple (single reaction) systems. 2. Atomic species balances generally lead to the most straightforward solution procedure, especially when more than one reaction is involved 3. Extents of reaction are convenient for chemical equilibrium problems.

MolecularSpeciesBalances
Tousemolecularspeciesbalancestoanalyzeareactivesystem,the

balancesmustcontaingenerationand/orconsumptionterms.
Thedegreeoffreedomanalysisisasfollows:

#unknownlabeledvariables +#independentchemicalreactions #independentmolecularspeciesbalances #other relating h equations i l i unknown k variables i bl #ofdegreesoffreedom

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MolecularSpeciesBalances
C 2H6 C 2H4 + H2
atsteadystate

2unknownlabeledvariables +1independentchemicalreactions 3independentmolecularspeciesbalances 0otherequationsrelatingunknownvariables 0degreesoffreedom

MolecularSpeciesBalances
atsteadystate

C2 H 6 C2 H 4 + H 2

H2 Balance:generation=output

genH 2 = 40 kmol H 2
C2H6 Balance:input=output+consumption
C2 H 6 H2 &1 + 40 kmol 1000 kmol =n min min C2 H 6 &1 = 60 kmol n min

)(

1 kmol C 2 H 6 1 kmol H 2

C2H4 Balance:generation=output
H2 & 2 = 40 kmol n min

)(

1kmolC 2H4 1kmolH2

C 2H4 & 2 = 40 kmol n min

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AtomicSpeciesBalance
C 2H6 C 2H4 + H2
Allatomicspeciesbalancestaketheform
INPUT=OUTPUT

Degreeoffreedomanalysis,ndf =

#unknownlabeledvariables #independent p atomicspecies p balances #molecularbalancesonindependentnonreactivespecies #otherequationsrelatingunknownvariables

AtomicSpeciesBalance

Allatomicspeciesbalancestaketheform
INPUT=OUTPUT

Degreeoffreedomanalysis,ndf =0=

2unknownlabeledvariables 2independentatomicspeciesbalances 0molecularbalancesonindependentnonreactive species 0otherequationsrelatingunknownvariables

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AtomicSpeciesBalance
C 2H6 C 2H4 + H2
CBalance:input=output

(100

kmol C 2 H 4 min

)(

2 kmol C 1 kmol C 2 H 6

&( )= n

2 kmol C 1 1 kmol C 2 H 6

& ( )+ n

2 kmol C 2 1 kmol C 2 H 4

&1 + n &2 100 kmol = n

HBalance:input=output

(100

kmolC2H4 min

)(

6kmolH 1kmolC2H6

) = (40 & ( +n

kmolH2 min

)(

2kmolH 1kmolH2

6kmolH 1 1kmolC2H6

) & ( )+ n

4kmolH 2 1kmolC2H4

& 1 + 4n &2 600kmol = 80kmol + 6n

AtomicSpeciesBalance
C 2H6 C 2H4 + H2

Solvesimultaneously
&1 + n &2 C :100kmol = n & 1 + 4n &2 H :600kmol = 80kmol + 6n & 1 = 60kmolC2H6 / min n & 2 = 40kmolC2H4 / min n

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ExtentofReaction
The3rd methodbywhichtodeterminemolarflowsinareactivesystem

isusingexpressionsforeachspeciesflowrateintermsofextentsof reaction (). ni = (ni )0 + ij j


j

Degreeoffreedomanalysisforsuchanapproach:

ndf =#ofunknownlabeledvariables +#independentreactions #independentnonreactivespecies #otherrelationshipsorspecifications

IncompleteCombustionofCH4
Methaneisburnedwithairinacontinuoussteadystatereactortoyield

amixtureofcarbonmonoxide,carbondioxide,andwater.

CH4 + 3 O2 CO + 2H2 O
2

CH 4 + 2O2 CO2 + 2H2 O Thefeedtothereactorcontains7.80mol%CH4,19.4mol%O2,72.8 mol%N2.Methaneundergoes90.0%conversion,andtheeffluentgas contains8molCO2 permoleCO.

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fCH4 =0.9

CH4 + 3 O2 2

CO + 2H2 O

CH4 + 2O2 CO2 + 2H2 O


mol%N2.Methaneundergoes90.0%conversion,andtheeffluentgas contains8molCO2 permoleCO. ndf =5unknowns p reactions +2independent 5expressionsfor(CH4,O2,CO,CO2,H2O) 1nonreactivespeciesbalance(N2) 1specifiedmethaneconversion =0
Thefeedtothereactorcontains7.80mol%CH4,19.4mol%O2,72.8

CH4 + 3 O2 CO + 2H2 O
2

fCH4 =0.9

CH4 + 2O2 CO2 + 2H2 O

N2 balance:nonreactivespecies,INPUT=OUTPUT
N2 nN2 = 0.728 mol mol (100mol ) = 72.8molN2

CH4 conversionspecification:
CH4 nCH4 = (1 0.900 ) 0.0780 mol l) = 0.780 mol l CH4 mol (100 mol

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CH 4 + 3 2 O2 CO + 2 H 2 O CH 4 + 2 O2 CO2 + 2 H 2O

Extentofreactionmolebalances:
nCH4 = nCH4

( )

nCO = (nCO )0 + (+ 1)1 nCO2 = nCO2 nH2O nO2


0

+ ( 1)1 + ( 1)2

0.78 = 7.80 1 2 nCO = 1 nCO2 = 8nCO = 2 nH2 O = 21 + 22 nO 2 = 19.4 3 1 22 2

( ) + (+ 1) = (n ) + (+ 2) + (+ 2) = (n ) + ( ) + ( 2)
2 H2O 0 1 O2 0 3 2 1 2

ProductSeparationandRecycle
Twodefinitionsofreactantconversionareusedintheanalysisof

chemicalreactorswithproductseparationandrecycleofunconsumed reactants.
overall conversion sin glepass inputtoprocessoutputfromprocess = reactant inputtoprocess

input to reactor output from reactor = reactant conversion inputtoreactor

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overall 75molA/min0 = 100% = 100% conversion 75molA/min sin glepass 100molA/min25molA/min = 100% = 75% conversion 100molA/min

CatalyticPropaneDehydrogenation

C 3H8 C3H6 + H2

95%overall conversion

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CatalyticPropaneDehydrogenation
C 3H8 C 3H6 + H2

95%overall conversion

Overall Process
ndf =3unknowns(n6,n7,n8) 2independentatomicbalances(CandH) 1relation(overallconversion) =0 considern6,n7,n8 knownforfurtherDOFanalyses

CatalyticPropaneDehydrogenation
ndf =2
C 3H8 C 3H6 + H2

95%overall conversion

Mixing point
ndf =4unknowns(n9,n10,n1,n2) 2balances(C3H8 andC3H6) =2

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CatalyticPropaneDehydrogenation
ndf =3 ndf =2
C 3H8 C 3H6 + H2

95%overall conversion

reactor
ndf =5unknowns(n3,n4, n5, n1,n2) 2balances(CandH) =3

CatalyticPropaneDehydrogenation
ndf =3 ndf =0 ndf =2
C 3H8 C 3H6 + H2

95%overall conversion

separator
ndf =5unknowns(n3,n4, n5, n9,n10) 3balances(C3H8,C3H6,andH2) 2relations(reactantandproductrecoveryfractions) =0

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CatalyticPropaneDehydrogenation
C 3H8 C 3H6 + H2

95%overall conversion

overall
conversion relationship

n6 = (1 0.95)(100 mol l) = 5 mol l C 3H8

CatalyticPropaneDehydrogenation
n6 = 5 mol C3H8

95%overall conversion

C 3H8 C 3H6 + H2

overall
Catomicbalance

3molC (100mol)(1mol C H

3 8

) = (5molC H )(
3 8

3molC 1molC 3H8

)+ n (

3molC 7 1molC 3H6

n7 = 95molC 3H6

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CatalyticPropaneDehydrogenation
n6 = 5 mol C3H8 n7 = 95 mol C3H6

95%overall conversion

C 3H8 C 3H6 + H2

overall
Hatomicbalance

8molH (100mol)(1mol C H

3 8

) = (5molC H )(
3 8

6molH + (95molC 3H6 ) 1mol C 3H6 + n8

8molH 1molC 3H8

) (

2molH 1molH2

n8 = 95mol H2

CatalyticPropaneDehydrogenation
n6 = 5 mol C3H8 n7 = 95 mol C3H6 n8 = 95 mol H2

95%overall conversion

C 3H8 C 3H6 + H2

separator
givenrelations

n6 = (0.00555)n3 n3 = 900 mol C 3H8

n10 = (0.0500 )n7 n10 = 4.75molC 3H6

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CatalyticPropaneDehydrogenation
n3 = 900 mol C 3H8

95%overall conversion

n6 = 5 mol C3H8 n7 = 95 mol C3H6 n8 = 95 mol H2

C 3H8 C 3H6 + H2

separator
n10 = 4.75 molC 3H6

propanebalance

n3 = n6 + n9 n9 = 895 molC 3H8

CatalyticPropaneDehydrogenation
n3 = 900 mol C 3H8

95%overall conversion

n6 = 5 mol C3H8 n7 = 95 mol C3H6 n8 = 95 mol H2

C 3H8 C 3H6 + H2

mixer
n9 = 895 molC 3H8 n10 = 4.75 molC 3H6

propanebalance

100 + n9 = n1 n1 = 995 molC3H8

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CatalyticPropaneDehydrogenation
n1 = 995molC3H8
n3 = 900 mol C 3H8

95%overall conversion

n6 = 5 mol C3H8 n7 = 95 mol C3H6 n8 = 95 mol H2

C 3H8 C 3H6 + H2

mixer
n9 = 895 molC 3H8 n10 = 4.75 molC 3H6

propylenebalance

n10 = n2 n2 = 4.75 molC3H6

CatalyticPropaneDehydrogenation
n1 = 995 molC 3H8 n2 = 4.75 molC 3H6
n3 = 900 mol C 3H8

95%overall conversion

n6 = 5 mol C3H8 n7 = 95 mol C3H6 n8 = 95 mol H2

C 3H8 C 3H6 + H2

reactor
n9 = 895 molC 3H8 n10 = 4.75 molC 3H6

Catomicbalance

3mol C 3 mol C (995mollC3H8 )(1mol 75 mol l C 3H6 )(1mol C H C H ) + (4.75 3molC 3molC = (900molC3H8 )(1molC H ) + (n4 )(1molC H )
3 8 3 8 3 6

3 6

n4 = 99.75molC 3H6

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CatalyticPropaneDehydrogenation
n1 = 995 molC 3H8 n2 = 4.75 molC 3H6
n3 = 900 mol C 3H8
n4 = 99.75 mol C 3H6

95%overall conversion

n6 = 5 mol C3H8 n7 = 95 mol C3H6 n8 = 95 mol H2

C 3H8 C 3H6 + H2

reactor
n9 = 895 molC 3H8 n10 = 4.75 molC 3H6

Hatomicbalance

8molH 6molH (995molC3H8 )(1mol C H ) + (4.75molC 3H6 )(1molC H ) 6molH 8molH = (900molC 3H8 )(1mol C H ) + (99.75molC 3H6 )(1molC H
3 8 3 6 3 8

3 6

)+ n (

2molH 5 1molH2

n5 = 95molH2

CatalyticPropaneDehydrogenation
n1 = 995 molC 3H8 n2 = 4.75 molC 3H6
n3 = 900 mol C 3H8 n4 = 99.75 mol C 3H6 n5 = 95 mol H2

95%overall conversion

n6 = 5 mol C3H8 n7 = 95 mol C3H6 n8 = 95 mol H2

C 3H8 C 3H6 + H2
n9 = 895 molC 3H8 n10 = 4.75 molC 3H6

singlepass conversion

fsingle pass =

(995 mol C3H8 ) (900 mol C3H8 ) 100% = 9.55% (995molC3H8 )

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CatalyticPropaneDehydrogenation
n1 = 995 molC 3H8 n2 = 4.75 molC 3H6
n3 = 900 mol C 3H8 n4 = 99.75 mol C 3H6 n5 = 95 mol H2

fsingle pass = 9.55%

95%overall conversion

n6 = 5 mol C3H8 n7 = 95 mol C3H6 n8 = 95 mol H2

C 3H8 C 3H6 + H2
n9 = 895 molC 3H8 n10 = 4.75 molC 3H6

Recycleratio

R=

n9 + n10 (895mol) + (4.75mol) molrecycle = = 9.0 mol freshfeed (100molfeed) (100mol)

Purging
Necessarywithrecycletopreventaccumulationofaspeciesthatisboth

presentinthefreshfeedandisrecycledratherthanseparatedwiththe d product.

mixedfreshfeed andrecycleisa convenient basisselection

f single pass = 60% CO + 3H2 CH3 OH + H2 O 2

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MethanolSynthesis
ndf =7unknowns(n0,x0C,np,x5 5C,x5 5H,n3,n4)+1rxn

5independentspeciesbalances=3

f single pass = 60% CO2 + 3H2 CH3 OH + H2 O

MethanolSynthesis
ndf =4unknowns(n1,n2,n3,n4)+1rxn

4independent species balances p p 1singlepassconversion=0

f single pass = 60% CO + 3H2 CH3 OH + H2 O 2

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ndf =3unknowns(n5,x5C,X5H)

3independentspeciesbalances =0

f single pass = 60% CO2 + 3H2 CH3 OH + H2 O

ndf =3unknowns(n0,x0C,nr)

3independentspeciesbalances =0

f single pass = 60% CO + 3H2 CH3 OH + H2 O 2

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ndf =1unknowns(np)

1independent p species p balance =0

investigate molebalancesand theirsolutionin thetext

f single pass = 60% CO2 + 3H2 CH3 OH + H2 O

CombustionReactions
Combustion rapid p reactionofafuelwithoxygen. yg Valuableclassofreactionsduetothetremendousamount

ofheatliberated,subsequentlyusedtoproducesteamused todriveturbineswhichgeneratesmostoftheworlds electricalpower. Commonfuelsusedinpowerplants:


coal fueloil(highMWhydrocarbons) gaseousfuel(naturalgas) liquified petroleumgas(propaneand/orbutane)

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CombustionChemistry
Whenafuelisburned
CformsCO2 (complete)orCO(partialcombustion) HformsH2O SformsSO2 NformsNO2 (above1800C)

Airisusedasthesourceofoxygen.DRYairanalysis:
78.03mol%N2 20.99mol%O2 0.94mol%Ar 0.03mol%CO2 0.01mol%H2,He,Ne,Kr,Xe

usually ll safe f toassume: 79mol%N2 21mol%O2

CombustionChemistry
Stack(f (flue) gas p productg gasthatleavesafurnace. )g Compositionanalysis:
wetbasis waterisincludedinmolefractions drybasis doesnotincludewaterinmolefractions

Stackgascontains(mol)onawetbasis:
60.0%N2,15.0%CO2,10.0%O2,15.0%H2O Drybasisanalysis:

60/(60+15+10)=0.706molN2/mol 15/(60+15+10)=0.176molCO2/mol 10/(60+15+10)=0.118molO2/mol

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CombustionChemistry
Stackgascontains(mol)onadrybasis:
65%N2,14%CO2,10%O2,11%CO

assume100moledrygasbasis 7.53moleH2O 65moleN2 14moleCO2 10moleO2 11moleCO total=107.5mole

xH2 O =

7.53 = 0.0700 107.5 65 = 0.605 xN2 = 107.5 14 = 0.130 xCO2 = 107 5 107.5 10 xO 2 = = 0.0930 107.5 11 = 0.102 xCO = 107.5

TheoreticalandExcessAir
The less expensive reactant is commonly fed in excess of stoichiometric

reactant thereby increasing ratio relative to the more valuable reactant, conversion of the more expensive reactant at the expense of increased use of excess reactant. In a combustion reaction, the less expensive reactant is oxygen, obtained from the air. Conseqently, air is fed in excess to the fuel. Theoretical oxygen is the exact amount of O2 needed to completely combust the fuel to CO2 and H2O. Theoretical air is that amount of air that contains the amount of theoretical oxygen.

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TheoreticalandExcessAir
Excessairistheamountbywhichtheairfedtothe

reactorexceedsthetheoreticalair.
% excessair = molesairfed molesairtheoretical 100% molesairtheoretical

TheoreticalandExcessAir
C 4H10 + 13 O2 4CO2 + 5H2 O 2

nC4H10 =100mol/hr;nair =5000mol/hr

(n )

O2 theoretica l

6.5molO2 molO2 100molC 4H10 = = 650 hr hr molC 4H10

650 mol O2 4.76 mol air mol air (nair )theoretical = = 3094 hr molO2 hr
5000 3094 100% = 61.6% 3094

% excessair =

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CombustionReactors
Procedureforwriting/solving g/ gmaterialbalancesfora

combustionreactor
1.

Whenyoudrawandlabeltheflowchart,besuretheoutlet stream(thestackgas)includes a. unreacted fuel(unlessthefueliscompletelyconsumed) b. unreacted oxygen c. waterandcarbondioxide(andCOifcombustionis i incomplete) l ) d. nitrogen(ifairisusedastheoxygensource) 2. CalculatetheO2 feedratefromthespecifed percentexcess oxygenorair 3. Ifmultiplereactions,useatomicbalances

CombustionofEthane
C2 H 6 + 7 2 O2 2CO2 + 3H 2 O C2 H 6 + 5 2 O2 2CO + 3H 2 O

fC2H6 =0.9 9

degreeoffreedom analysis

ndf =7unknowns 3atomicbalances 1nitrogenbalance 1excessairspecification 1ethaneconversionspecification 1CO/CO2 ratiospecification =0

25%oftheethaneburnedformsCO

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excessairspecification
C2 H 6 + 7 2 O2 2CO2 + 3 H 2 O C2 H 6 + 5 2 O2 2CO + 3 H 2 O

fC2H6 =0.9

25%oftheethaneburnedformsCO

(n )

O2 theoretical

100molC2H6 3.5molO2 = = 350molO2 molC2H6

0.21n0 = 1.5(350mol O2 ) n0 = 2500molair


Ethaneconversionspecification

n1 = (1 0.90 )(100 mol C2H6 ) = 10.0 mol C2H6

n 1 = 10.0molC2H6

CO/CO2 ratiospecification
C2H6 + 7 O2 2CO2 + 3H2 O
2

n 0 = 2500molair

fC2H6 =0.9

C H + 5 O 2CO + 3H2 O 2 6 2 2

25%oftheethaneburnedformsCO

2molCOgen n4 = (0.25)(0.9 )(100molC2H6 ) 1molC H react = 45.0molCO 2 6

Nitrogenbalance

n3 = (0.79 )(2500 mol air ) = 1975 mol N2


AtomicCbalance
2molC (100molC2H6 )(1mol C H

2 6

)= n (

2molC 1 1molC 2H6

)+ n (

1molC 4 1molCO

molC ) + n5 (11 molCO

n5 = 135molCO2

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n 1 = 10.0molC2H6

C2H6 + 7 O2 2CO2 + 3H2 O


2

fC2H6 =0.9
n 0 = 2500 molair

n 3 = 1975molN2

C H + 5 O 2CO + 3H2 O 2 6 2 2

atomicHbalance
6molH (100molC2H6 )(1mol C H
2 6

n 4 = 45.0molCO n 5 = 135molCO2

) = (10molC H )(
2 6

6molH 1molC2H6

)+ n (

2molH 6 1molH2O

n6 = 270molH2O
atomicObalance
2molO 1molO molO (525molO2 )(12mol O ) = n2 (1molO ) + (45molCO )( 1molCO ) 1molO molO + (135molCO2 )(12 molCO ) + (270molH2O )(1molH O )
2 2 2 2

n2 = 232molO2

C2H6 + 7 O2 2CO2 + 3H2 O


2

C2H6 + 5 O2 2CO + 3H2 O 2

n 1 = 10.0 molC 2H6 n 3 = 1975 molN 2 n 4 = 45.0 molCO n 5 = 135 molCO2 n 6 = 270 mol H2 O

fC2H6 =0.9 9
n 0 = 2500 molair

atomicObalance
2 2

25%oftheethaneburnedformsCO

molO 2molO 1molO (525molO2 )(12mol O ) = n2 (1molO ) + (45molCO )( 1molCO ) molO 1molO + (135 mol CO2 )(12 mol CO ) + (270 mol H2O )(1 mol H O )
2 2

n2 = 232molO2

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C2H6 + 7 O2 2CO2 + 3H2 O


2

C2H6 + 5 O2 2CO + 3H2 O 2

n 1 = 10.0 molC 2H6 n 2 = 232 molO 2 n 3 = 1975 molN 2 n 4 = 45.0 molCO n 5 = 135 molCO2 n 6 = 270 mol H2 O

fC2H6 =0.9 9
n 0 = 2500 molair

25%oftheethaneburnedformsCO

stackgascomposition(drybasis)

sum = 10 + 232 + 1974 + 45 + 135 = 2396 y 1 = 10 2396 = 0.00417 molC2H6 mol y 2 = 232 2396 = 0.0970 molO2 mol y 3 = 1974 2396 = 0.824 molN2 mol y 4 = 45 2396 = 0.019 molCO mol y 5 = 135 2396 = 0.0563 molCO2 mol

270molH2 O 2396moldrystackgas molH2 O = 0.113 mol drystackgas

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