CHME 201:

Intro. to Chem. Eng. I

Chapter 4: Reactive
Material Balances
Sections 4.6-4.8
 Balances on Reactive Systems

◼ Component material balance no longer takes

the form
INPUT = OUTPUT

◼ Must account for the disappearance of

reactants and appearance of products through
stoichiometry.

2
 Stoichiometric Equations (1)
◼ The stoichiometric equation of a chemical
reaction is a statement of the relative
amounts of reactants and products that
participate in the reaction.
2 SO2 + O2 → 2 SO3
◼ A stoichiometric equation is valid only if
the number of atoms of each atomic
species is balanced.
2S→2S
4O+2O→6O
3
 Stoichiometric Equations (2)

◼ A stoichiometric ratio of two molecular

species participating in a reaction is the
ratio of their stoichiometric
coefficients.
◼ For this reaction: 2 SO2 + O2 → 2 SO3
2 mol SO3 generated / 1 mol O2 consumed
2 mol SO3 generated /2 mol SO2 consumed

4
 Tutorial

C4H8 + 6 O2 → 4 CO2 + 4 H2O

◼ Is this stoichiometric equation balanced?
Answer: Yes
◼ What is the stoichiometric coefficient of CO2?
Answer: 4
◼ What is the stoichiometric ratio of H2O to O2?
Answer: 4/6
◼ How many lb-mol O2 react to form 400 lb-mol CO2?
6 lbmol O2
400 lbmol CO2  = 600 lbmol O2
4 lbmol CO2

◼ 100 lbmol/min C4H8 is fed and 50% reacts. At what rate is water
formed? lbmol C 4H8 4 lbmol H2O lbmol H2O
100  0.50  = 200
min 1 lbmol C 4H8 min
5
 Limiting and Excess Reactants

◼ Two reactants are said to be in stoichiometric proportion if the

ratio (moles A present/moles B present) equals the
stoichiometric ratio from the balanced reaction equation.

2 SO2 + O2 → 2 SO3

◼ the feed ratio that would represent stoichiometric

proportion is nSO2/nO2 = 2:1
◼ If reactants are fed in stoichiometric proportion,
and the reaction proceeds to completion, all
reactants are consumed.
6
 Limiting and Excess Reactants

◼ Stoichiometric Proportion – Reactants are

present in a ratio equivalent to the ratio of the
stoichiometric coefficients.
A + 2B → 2C

7
 Limiting and Excess Reactants

◼ Limiting reactant – A reactant is limiting if it is

present in less than stoichiometric proportion
relative to every other reactant(s).
A + 2B → 2C

◼ Excess reactant – All other reactants besides the limiting

8
reactant.
 Example

If the reactants are not in stoichiometric proportion

one of them will be excess, the other will be limiting

Limiting reactant is the reactant which is present in less than its

stoichiometric proportion relative to every other reactant

2 SO2 + O2 → 2SO3
if Feed = 4 g-moles SO2, 1 g-mole O2
for 2 g-moles SO2 1 g-mole O2 required
for 4 g-moles SO2 2 g-mole O2 required,
but we have only 1 g-mole O2
O2 will finish first, O2 is the limiting reactant,
SO2 excess reactant
9
 Limiting and Excess Reactants

◼ fractional excess (fXS) – ratio of the excess to the

stoichiometric proportion (n A ) − (n A )
fXS = feed stoich

A + 2B → 2C (n A )stoich
5− 4
= = 0.25
4

10
 Limiting and Excess Reactants

◼ fractional conversion (f) – ratio of the amount

of a reactant reacted to the amount fed.
(n A )reacted
fA =
A + 2B → 2C (n A ) fed
0
fA = = 0.0
5
(nB )reacted
fB =
(nB ) fed
0
fB = = 0.0
8 11
 Limiting and Excess Reactants

◼ fractional conversion (f) – ratio of the amount of a

reactant reacted, to the amount fed. (n A )reacted
fA =
A + 2B → 2C (n A ) fed

1
fA = = 0.2
5

(nB )reacted 2
fB = fB = = 0.25
(nB ) fed 8 12
 Limiting and Excess Reactants

◼ fractional conversion (f) – ratio of the amount of

a reactant reacted, to the amount fed.
(n A )reacted
fA =
A + 2B → 2C
(n A ) fed

2
fA = = 0.4
5
(nB )reacted
fB = 4
(nB ) fed fB = = 0.5
8 13
 Limiting and Excess Reactants

◼ fractional conversion (f) – ratio of the amount of

a reactant reacted, to the amount fed. (n )
fA = A reacted

A + 2B → 2C
(n A ) fed

3
fA = = 0.6
(nB )reacted 6 5
fB = fB = = 0.75
(nB ) fed 8 14
 Limiting and Excess Reactants

◼ fractional conversion (f) – ratio of the amount of

a reactant reacted, to the amount fed.
(n A )reacted
fA =
A + 2B → 2C (n A ) fed

(nB )reacted 8
4
fA = = 0.8
fB = fB = = 1.0 5
(nB ) fed 8 15
 Tutorial

Ethylene Oxidation:
2C2H4 + O2 → 2C2H4O
◼ Assume an equimolar reactant feed of 100 kmol.
◼ What is the limiting reactant?
◼ What is the percentage excess of each reactant?

A reactant is limiting if it is present in less than stoichiometric proportion relative to every other
 reactant.

 n C2H4  2 Oxygen is in excess


 nO
 2


=
stoich 1
(n ) − (n )
O2 feed O2 stoich
fXS ,O2 =
 n C2H4  (n )
 =1
O2 stoich

 nO  100 − 50
 2  feed 1 = = 1.00 = 100%
Ethylene is the limiting reactant
50 16
 Extent of Reaction

◼ extent of reaction (ξ) – an extensive quantity describing the

progress of a chemical reaction . ν – stoichiometric
coefficients: νA = -1, νB = -2, νC = 2
ni = ni0 +  i 
A + 2B → 2C
=0




nC = nC0 + 2
nA = nA0 −  nB = nB0 − 2 17
 Extent of Reaction

◼ extent of reaction (ξ) – an extensive quantity describing the

progress of a chemical reaction .
ν – stoichiometric coefficients: νA = -1, νB = -2, νC = 2
A + 2B → 2C
ni = ni0 +  i 

=0


nA = 5−  = 5 nB = 8 −2 = 8 nC = 0 +2 = 0
18
 Extent of Reaction

◼ extent of reaction (ξ) – an extensive quantity describing the progress of a

chemical reaction .
ν – stoichiometric coefficients: νA = -1, νB = -2, νC = 2 ni = ni0 +  i 

A + 2B → 2C

nA = 5−  = 4 nB = 8 −2 = 6 nC = 0 +2 = 2
 =1
19
 Extent of Reaction

◼ extent of reaction (ξ) – an extensive quantity describing the progress of a

chemical reaction .
ν – stoichiometric coefficients: νA = -1, νB = -2, νC = 2
ni = ni0 +  i 
A + 2B → 2C

nA = 5−  = 3 nB = 8 − 2 = 4 nC = 0 + 2 = 4
20
=2
 Home take example

2C2H4 + O2 → 2C2H4O
◼ Assume an equimolar reactant feed of 100 kmol.
◼ If the reaction proceeds to a point where 60 kmol of O2 is left, what is the
fractional conversion of C2H4? What is ξ?
Solution
nC2H4 = nCo2H4 +  C2H4 
nO2 = nOo 2 + O2 
 nC2H4 = 100 + (− 2)40
nC2H4 = 20
60 = 100 + (− 1)
 = 40

(n )
C2H4 reacted 100 − 20
f= = = 0.8
(n )
C2H4 fed 100
21
 Example

◼ Acrylonitrile produced by reaction of ammonia,

propylene, and O2 at 30% conversion of limiting
reactant. Which component is the limiting?
C3 H 6 + NH 3 + 32 O2 → C3 H 3 N + 3H 2O

22
 Solution

◼ Acrylonitrile produced by reaction of ammonia,

propylene, and O2 at 30% conversion of limiting reactant:
limiting
C3 H 6 + NH 3 + 32 O2 → C3 H 3 N + 3H 2O
determine limiting reactant

(n NH 3 nC3 H 6 ) feed
= (0.12 / 0.1) = 1.20
(n NH 3 nC3 H 6 )stoich
= (1 1) = 1
(n O2 nC3 H 6 ) feed
= (0.780  0.21 0.100 ) = 1.64
(n O2 nC3 H 6 )stoich
= (1.5 1) = 1.5
23
 Tutorial

Acrylonitrile produced by reaction of ammonia, propylene, and O2 at 30% conversion

of limiting reactant. Which component(s) are in excess and what its (their) fractional
excess?
limiting f XS = 0.20 f XS = 0.093
Solution
C3 H 6 + NH 3 + 32 O2 → C3 H 3 N + 3H 2O
 
determine fractional excesses
 1 mol NH3 
( )
n NH3
stoich
= 10.0 mol C3 H6 
 1 mol C 3 H 6 
= 10.0 mol NH 3
(NH ) −(NH )
(f XS )NH = (NH )
3
3 0
= 12.0−10.0
3 stoich

10.0
3 stoich
= 0.20
 1.5 mol O 
( O )stoich
n 2
= 10.0 mol C 3 6  1 mol C H  = 15.0 mol O2
H
3
2

(O ) −(O )
(f XS )O = (O )
2
2 0
= 16.4−15.0
2 stoich

15.0
2 stoich
= 0.093

24
 Example
◼ Acrylonitrile produced by reaction of ammonia, propylene, and O2 at 30% conversion
of limiting reactant. How much propylene leaves the reactor?
Solution limiting use fractional conversion to
C3 H 6 + NH 3 + 32 O2 → C3 H 3 N + 3H 2O determine amount of propylene that
leaves the reactor

(
nC3 H 6 = (1 − f ) nC3 H 6 ) feed
= (1 − 0.30)(10.0 mol C3 H 6 ) = 7.0 mol C3 H 6

25
 Example

◼ Acrylonitrile produced by reaction of ammonia, propylene, and O2 at 30% conversion

of limiting reactant. What is the extent of reaction?
Solution
limiting f XS = 0.20 f XS = 0.093

C3 H 6 + NH 3 + 32 O2 → C3 H 3 N + 3H 2O ni = ni0 +  i 
 
determine extent of reaction
by applying mole balance to
propylene

(n )
C3 H 6 feed = 10 mol C3 H 6
nC3 H 6 = 7.0 mol C3 H6

(
nC3 H 6 = nC3 H 6 ) feed
+ (− 1)
7.0 mol = 10.0 mol − 

 = 3 mol 26
 Chemical Equilibrium

◼ Irreversible reaction
◼ reaction proceeds only in a single direction A → B
◼ concentration of the limiting reactant eventually
approaches zero (time duration can vary widely)

Equilibrium composition of an irreversible reaction is that

which corresponds to complete conversion of the limiting
reactant.

27
 Chemical Equilibrium

◼ Reversible reaction
◼ reaction proceeds in both directions A ↔ B
◼ net rate (forward – backward) eventually
approaches zero (again, time can vary widely)

Equilibrium composition of a reversible

reaction is that which corresponds to the
equilibrium conversion.
28
 Chemical Equilibrium

◼ The equilibrium constant, K(T), depends on

temperature (T).
◼ The composition at equilibrium depends on T
aA + bB  cC + dD
For solutions For gases
K (T ) =
C  D 
c d
=
c
y y
C
d
D
PCc PDd yCc y Dd
K (T ) = a b = a b
A B
a b a
y y
A
b
B
PA PB y A yB

CiV Pi ni
yi = = = ni = ni0 + i
CtotalV Ptotal ntotal 29
 Chemical Equilibrium

y CO2 yH2
nCO = (nCO )0 + (− 1) = (1 −  ) K(T ) =
y COyH2O
( )
nH 2O = nH 2O 0 + (− 1) = (2 −  )
ni
nCO2 = (n ) + (1) = 
CO2 0
yi =
ntotal
nH 2 = (n ) + (1) = 
H2 0

ntotal = nCO + nH 2O + nCO2 + nH 2 = 3

ni = ni0 + i
30
 Equilibrium Composition
Also assume: K(1105 K) = 1.00
( )( ) = 1
ni = ni0 + i
(1 −  )(2 −  )
nCO = 1 −  = 0.333
 = (1 −  )(2 −  )
2

nH2O = 2 −  = 1.333
 2 = 2 − 2 −  +  2
nCO =  = 0.667
2 − 3 = 0 2

nH2 =  = 0.667
 = 0.667mol
ntotal = 3
 Equilibrium Composition
ni
yi =
ntotal
ntotal = 3

nCO = 1 −  = 0.333  yCO = 0.333 / 3 = 0.111

nH 2O = 2 −  = 1.333  y H 2O = 1.333 / 3 = 0.444
nCO2 =  = 0.667  yCO2 = 0.667 / 3 = 0.222
n = = 0.667  y H 2 = 0.667 / 3 = 0.222
H2

32
 Equilibrium Composition
limiting reactant is CO
at equilibrium   = 0.667mol
y CO = 0.333 / 3 = 0.111
ni = ni0 + i
y H2O = 1.333 / 3 = 0.444
nCO = 1 + (− 1)(0.667)
y CO2 = 0.667 / 3 = 0.222 = 0.333 mol
y H2 = 0.667 / 3 = 0.222
ntotal = 3 fractional conversion at equilibrium

f = 1.001−.000.333 = 0.667

33
 Multiple Reactions
C2 H 4 + 12 O2 → C2 H 4O
C2 H 4 + 3O2 → 2CO 2 + 2H2O
for j reactions of i species, ni = (ni )0 +   ij j
mole balance becomes
( ) + (− 1) + (− 1)
j
nC2 H 4 = nC2 H 4
 0 1 2

nO2 = nO2 ( ) + (− ) + (− 3)

0
1
2 1 2

nC2 H 4O = (n ) + (1)
C2 H 4O 0 1

( ) + (2)
nCO2 = nCO2 0 2

nH 2O = (n ) + (2 )
H 2O 0 2
34
 Take Home Example
◼ For the following reactions: A → 2B
A →C
100 moles A fed to a batch reactor. If the product composition is:
10 mol A, 160 mol B, 10 mol C
nB = nBo +  B11
What is 160 = 0 + 21
1. ξ1 1 = 80

nA = nAo +  A11 +  A 2 2 nC = nCo + C 2 2

2. ξ2 10 = 100 − 1 − 2 OR 10 = 0 +  2
2 = 90 − 1 = 10  2 = 10 35
 Yield and Selectivity

• The terms Yield and Selectivity are used to

describe the degree to which a desired reaction
predominates over competing side reactions.
• They are defined as follows:
moles of desired product formed
yield =
moles formed at 100% conversion of limiting reactant with no side reactions

Desired
Undesired
moles of desired product formed
selectivity = 36
moles of undesired product formed
 Example

The reactions Desired

Undesired
take place in a continuous reactor at steady state. The feed
contains 85.0 mole% ethane (C2H6) and the balance inert (I).
The fractional conversion of ethane is 0.501, and the fractional
yield of ethylene is 0.471. Calculate the molar composition of
the product gas and the selectivity of ethylene to methane
production.

37
Solution

38
Solution (Cont.)

39
 Step-by-Step to Solve Material Balance
Problems Involving Reactive Systems

To solve material balance problems involving reactive systems, you can

follow the following step-by-step procedure:
1. Choose a basis of calculation
2. Draw a flowchart of the process by drawing a box for each unit in the
process and lines with arrows for each input an output stream.

3. Write the values and units of all known stream variables at the
locations of the streams on the chart (e.g., 20 kg CO/h, 15.5 mol%
NO at 323 K and 1.5 atm). Try to incorporate process specification(s)
in the labeling.
4. Assign algebraic symbols to unknown stream variables and write
these variable names and their associated units on the chart.

5. If given mixed mass and mole units for a stream, convert all
quantities to be in moles.
6. Express what is needed to calculate in terms of the labeled variables.
Thus, you will know the number of unknowns on each unit in the
process.

7. Determine the limiting reactant.

8. Choose the material balance method to write the material balance

equations for each species.

9. Solve the system of equations to determine the values of the

unknowns, and calculate the requested variables.

10. If an amount of a stream other than that found using the basis of
calculation is assigned, scale the calculated quantities accordingly.
 4.7 Balances on reactive systems

In general, systems that involve chemical reactions may be

analyzed using
(a) molecular species balances (the approach always used for
nonreactive systems),
(b) atomic species balances, and
(c) extents for reaction.

Each approach leads to the same results, but any one of them may
be more convenient for a given calculation so it is a good idea to
become comfortable with all three.
 4.7 Balances on reactive systems
Balances on Molecular
Figure 4.7-1 shows a flowchart for the dehydrogenation of ethane in a steady-state
continuous reactor.
The reaction is C2 H 6 → C2 H 4 + H 2
One hundred kmol/min of ethane is fed to the reactor. The molar flow rate of H2 in
the product stream is 40 kmol/min.

A number of different balances could be written on this process, including balances on total mass, C2H6,
C2H4, and H2. Of these, only the first has the simple form input = output: since the three given species all
participate in the reaction, the balance equation for each of them must include a generation term (for
C2H4) or a consumption term (for C2H6).
Notice, however, that balances equations may also be written for atomic carbon and atomic hydrogen,
regardless of the molecular species in which the carbon and hydrogen atoms happen to be found.
Balances on atomic species can be written input = output, since atoms can neither be created (generation
= 0) nor destroyed (consumption = 0) in a chemical reaction.
 4.7c Molecular Species
Balances
If molecular species balances are used to determine unknown stream variables
for a reactive process, the balances on reactive species must contain generation
and/or consumption terms.

C2 H 6 → C2 H 4 + H 2
 Molecular H2 Balance: generation = output
 kmol H 2 generated 
Gen H 2   = 40 kmol H 2 / min
 min 

C2H6 Balance: input = output + consumption

100 kmol C2 H 6  kmol C2 H 6   kmol C2 H 6 consumed 

= n 1   + ConsC2 H 6  
min  min   min 

C2H4 Balance: generation = output

 kmol C2 H 4 generated    kmol C2 H 4 
Gen C2 H 4   = n2  
 min   min 
46
Atomic Species Balances
 Balances on Molecular and
Atomic Species

Atomic C Balance: input = output

100 kmol C2H6 2 mol C kmol C2H6 2 mol C kmol C2H4 2 mol C
= n 1 + n 2
min 1 mol C2H6 min 1 mol C2H6 min 1 mol C2H4

100 kmol C / min = n 1 + n 2

Atomic H Balance: input = output

100 kmol C2H6 6 mol H 40 kmol H2 2 mol H

=
min 1 mol C2H6 min 1 mol H2

kmol C2H6 6 mol H kmol C2H4 4 mol H

+ n 1 + n 2
min 1 mol C2H6 min 1 mol C2H4

600 kmol H / min = 80 kmol H / min+ 6n 1 + 4n 2

48
4.7e Extent of Reaction
Given that all three methods of carrying out material balances on reactive systems –
molecular species balances, atomic species balances, and extents of reaction –
necessarily yield the same results, the question is which one to use for a given process.

• There are no hard and fast rules but we suggest the following guidelines:

➢ Atomic species balances generally lead to the most straightforward solution

procedure, especially when more than one reaction is involved.
➢ Extents of reaction are convenient for chemical equilibrium problems and when
equation- solving software is to be used.
➢ ~Molecular species balances require more complex calculations than either of
the other two approaches and should be used only for simple systems involving
one reactions.
fCH4 = 0.9
 Product Separation and Recycle

◼ Two definitions of reactant conversion

are used in the analysis of chemical
reactors with product separation and
recycle of unconsumed reactants.
overall conversion input to process - output from process
=
of a reactant input to process

single pass conversion input to reactor - output from reactor

=
of a reactant input to reactor
 Product Separation and Recycle

overall conversion input to process - output from process

=
of a reactant input to process

single pass conversion input to reactor - output from reactor

=
of a reactant input to reactor

63
 Product Separation and Recycle

overall  75 mol A/min - 0 

=  100% = 100%
conversion of A  75 mol A/min 

single pass  100 mol A/min - 25 mol A/min 

=  100% = 75%
conversion of A  100 mol A/min 

64
 Product Separation and Recycle

overall  75 mol A/min - 0 

=  100% = 100%
conversion of A  75 mol A/min 

single pass  100 mol A/min - 25 mol A/min 

=  100% = 75%
conversion of A  100 mol A/min 

65
Product Separation and Recycle

66
Product Separation and Recycle

95% overall
conversion

C3H8 → C3H6 +H2

67
 Product Separation and Recycle

95% overall
conversion

C3H8 → C3H6 +H2

Calculate the composition of the product, the ratio (moles

recycled)/(mole fresh feed), and the single-pass conversion.
68
 Product Separation and Recycle
95% overall
conversion

C3H8 → C3H6 +H2

Overall

Process
ndf = 3 unknowns (n6, n7, n8)
– 2 independent atomic balances (C and H)
– 1 relation (overall conversion)
=0
From here onwards, consider n6, n7, n8 known
for further degree-of-freedom analysis 69
 Product Separation and Recycle
95% overall
ndf = 2
conversion

C3H8 → C3H6 +H2

Mixing

point
ndf = 4 unknowns (n9, n10, n1, n2)
– 2 balances (C3H8 and C3H6)
=2

70
 Product Separation and Recycle
ndf = 3 95% overall
ndf = 2
conversion

C3H8 → C3H6 +H2

reactor


ndf = 5 unknowns (n3, n4, n5, n1, n2)

– 2 balances (C and H)
=3

71
 Product Separation and Recycle
ndf = 3 ndf = 0 95% overall
ndf = 2
conversion

C3H8 → C3H6 +H2

separator


ndf = 5 unknowns (n3, n4, n5, n9, n10)

– 3 balances (C3H8, C3H6, and H2)
– 2 relations (reactant and product recovery fractions)
=0

72
 Product Separation and Recycle
95% overall
conversion

C3H8 → C3H6 +H2

overall
conversion
relationship
n6 = (1 − 0.95)(100 mol ) = 5 mol C3H8
73
 Product Separation and Recycle
95% overall
conversion
n6 = 5 mol C3H8

C3H8 → C3H6 +H2

overall
C atomic balance

(100 mol )(1mol

3mol C
CH
3 8
) = (5 mol C H )(
3 8
3mol C
1 mol C3H8 )+ n ( 3mol C
7 1 mol C3H6 )
n7 = 95 mol C3H6 74
 Product Separation and Recycle
95% overall
conversion
n6 = 5 mol C3H8
n7 = 95 mol C3H6

C3H8 → C3H6 +H2

overall
H atomic balance
(100 mol )(1 mol
8 mol H
CH ) = (5 mol C H )( 3 8
8mol H
1 mol C 3H8 )
( ) ( )
3 8

+ (95 mol C 3H6 ) 1 mol C 3H6 + n8

6 mol H 2 mol H
1 mol H2
n8 = 95 mol H2 75
 95% overall
conversion
n6 = 5 mol C3H8
n7 = 95 mol C3H6
n8 = 95 mol H2

C3H8 → C3H6 +H2

separator
given relations

n6 = (0.00555)n3 → n3 = 900 mol C 3H8

n10 = (0.0500 )n7 → n10 = 4.75 mol C 3H6 76
Product Separation and Recycle
95% overall
conversion
n3 = 900 mol C3H8 n6 = 5 mol C3H8
n7 = 95 mol C3H6
n8 = 95 mol H2
C3H8 → C3H6 +H2

 n10 = 4.75 mol C3H6

separator
propane balance
n3 =n6 +n9 →n9 = 895 mol C3H8
77
Product Separation and Recycle
95% overall
conversion
n3 = 900 mol C3H8 n6 = 5 mol C3H8
n7 = 95 mol C3H6
n8 = 95 mol H2
C3H8 → C3H6 +H2

n9 = 895 mol C3H8

 n10 = 4.75 mol C3H6



mixer
propane balance

100+n9 =n1 →n1 = 995 mol C3H8

78
 Product Separation and Recycle
95% overall
conversion
n1 = 995 mol C3H8 n3 = 900 mol C3H8 n6 = 5 mol C3H8
n7 = 95 mol C3H6
n8 = 95 mol H2
 C3H8 → C3H6 +H2

n9 = 895 mol C3H8

 n10 = 4.75 mol C3H6




mixer
propylene balance

n10 =n2 →n2 = 4.75 mol C3H6

79
 Product Separation and Recycle
95% overall
conversion
n1 = 995 mol C3H8 n3 = 900 mol C3H8 n6 = 5 mol C3H8
n7 = 95 mol C3H6
n2 = 4.75 mol C3H6
n8 = 95 mol H2
 C3H8 → C3H6 +H2


n9 = 895 mol C3H8

 n10 = 4.75 mol C3H6



reactor
C atomic balance
(995 mol C3H8 )(1 mol
3mol C
CH ) + (4 .75 mol C H )( 3 mol C
3 6 1 mol C H )
= (900 mol C3H8 )(1 mol ) 4 1 mol C H )
(
3 8 3 6

3mol C
CH + (n ) 3 mol C
3 8 3 6

n4 = 99.75 mol C3H6 80

 Product Separation and Recycle
95% overall
conversion
n1 = 995 mol C3H8 n3 = 900 mol C3H8 n6 = 5 mol C3H8
n4 = 99.75 mol C3H6 n7 = 95 mol C3H6
n2 = 4.75 mol C3H6
n8 = 95 mol H2
 C3H8 → C3H6 +H2


n9 = 895 mol C3H8

 n10 = 4.75 mol C3H6


 reactor
H atomic balance
(995 mol C3H8 )(1 mol
8 mol H
CH ) + (4 .75 mol C 3 6 1 mol C H )
H )( 6 mol H

= (900 mol C3H8 )(1 mol ) ( )+ n ( )

3 8 3 6

8 mol H
CH + (99
3 8
.75 mol C H ) 6 mol H
3 6 1 mol C H 3 6
2 mol H
5 1 mol H2

n5 = 95 mol H2 81
 Product Separation and Recycle
95% overall
conversion
n1 = 995 mol C3H8 n3 = 900 mol C3H8 n6 = 5 mol C3H8
n4 = 99.75 mol C3H6 n7 = 95 mol C3H6
n2 = 4.75 mol C3H6
n5 = 95 mol H2 n8 = 95 mol H2
 C3H8 → C3H6 +H2


n9 = 895 mol C3H8

 n10 = 4.75 mol C3H6



single-pass
conversion
fsingle −pass =
(995 mol C 3H8 ) − (900 mol C 3H8 )
 100% = 9.55%
(995 mol C3H8 ) 82
 Product Separation and Recycle
fsingle−pass = 9.55% 95% overall
conversion
 n3 = 900 mol C3H8 n6 = 5 mol C3H8
n1 = 995 mol C3H8
n4 = 99.75 mol C3H6 n7 = 95 mol C3H6
n2 = 4.75 mol C3H6
n5 = 95 mol H2 n8 = 95 mol H2
 C3H8 → C3H6 +H2


n9 = 895 mol C3H8

 n10 = 4.75 mol C3H6



recycle
ratio
n9 + n10 (895 mol ) + (4.75 mol )
R= = = 9.0 mol
mol recycle

(100 mol feed) (100 mol ) fresh feed

83
 4.8. Combustion Reaction
◼ Combustion: Rapid reaction of fuel with oxygen
(burning).
◼ The combustion products are usually H2O, CO2,
and possibly CO and SO2
 Composition on Wet and
Dry Bases
◼ The compositions of the combustion
products (that include water) are called
“compositions on wet basis”
◼ If you exclude water, you will get
“compositions on dry basis”
 Example

If a stack gas contains on a wet mol basis:

60.0% N2, 15.0% CO2, 10.0% O2, 15.0% H2O
Calculate the molar composition of this gas on a
dry basis
Solution:
◼ Dry basis analysis:
◼ 60/(60+15+10) = 0.706 mol N2/mol
◼ 15/(60+15+10) = 0.176 mol CO2/mol
◼ 10/(60+15+10) = 0.118 mol O2/mol

86
 4.8b Theoretical and
Excess Air
◼ Theoretical Oxygen: The moles or molar
flow rate of O2 needed for complete
combustion of all the fuel fed to the reactor

◼ Theoretical Air: The quantity of air that

contains the theoretical oxygen;
1 𝑚𝑜𝑙𝑒 𝐴𝑖𝑟
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝐴𝑖𝑟 = 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑂2
0.21 𝑚𝑜𝑙𝑒 𝑂2
◼ Excess Air: The amount by which the air
fed to the reactor exceeds the theoretical air.

𝒎𝒐𝒍𝒆𝒔 𝒂𝒊𝒓 𝒇𝒆𝒅 − 𝒎𝒐𝒍𝒆𝒔 𝒂𝒊𝒓 𝒕𝒉𝒆𝒐.

𝑷𝒆𝒓𝒄𝒆𝒏𝒕 𝑬𝒙𝒄𝒆𝒔𝒔 𝑨𝒊𝒓 = × 𝟏𝟎𝟎%
𝒎𝒐𝒍𝒆𝒔 𝒂𝒊𝒓 𝒕𝒉𝒆𝒐.

➔
𝒎𝒐𝒍𝒆𝒔 𝒂𝒊𝒓 𝒇𝒆𝒅 = 𝒎𝒐𝒍𝒆𝒔 𝒂𝒊𝒓 𝒕𝒉𝒆𝒐 × [𝟏 + 𝒇𝒂𝒄𝒕𝒊𝒐𝒏 𝒆𝒙𝒄𝒆𝒔𝒔 𝒂𝒊𝒓]
 Example
One hundred mol/h of butane (C4H10) and 5000 mol/h of air are fed into a combustion reactor.
Calculate the percent excess air.

C 4H10 + 13 O2 → 4CO2 +5H2 O

2
nC4H10 = 100 mol/hr; nair = 5000 mol/hr
𝑷𝒆𝒓𝒄𝒆𝒏𝒕 𝑬𝒙𝒄𝒆𝒔𝒔 𝑨𝒊𝒓?
 100 mol C4H10  6.5 mol O2 
(n ) =   = 650
mol O2

O2 theoretica l
 hr  mol C4H10  hr

 650 mol O2  4.76 mol air  mol air

(nair )theoretica l =    = 3094
 hr  mol O2  hr

5000−3094
% excess air= 100% = 61.6%
3094
 Combustion Reactors

◼ Procedure for writing/solving material balances for a combustion reactor

1. When you draw and label the flowchart, be sure the outlet stream (the
stack gas) includes
a. unreacted fuel (unless the fuel is completely consumed)
b. unreacted oxygen
c. water and carbon dioxide (and CO if combustion is incomplete)
d. nitrogen (if air is used as the oxygen source)
2. Calculate the O2 feed rate from the specified percent excess oxygen
or air
3. If multiple reactions, use atomic balances

90
 Combustion of Ethane

Ethane is burned with 50% excess air. The percentage

conversion of the ethane is 90%; of the ethane burned,
25% reacts to form CO and the balance reacts to form CO2.
Calculate the molar composition of the stack gas on a dry
basis and the mole ratio of water to dry stack gas.

C2H6 + 7 O2 → 2CO2 + 3H2 O

2
C2H6 + 5 O2 → 2CO+ 3H2 O
2

 91
 Combustion of Ethane
C2H6 + 7 O2 → 2CO2 + 3H2 O
Basis: 100 mol C2H6 Fed 2
C2H6 + 5 O2 → 2CO+ 3H2 O
2

 fC2H6 = 0.9

degree-of-freedom
analysis 25% of the ethane burned forms CO

ndf = 7 unknowns
- 3 atomic balances
- 1 nitrogen balance
- 1 excess air specification
- 1 ethane conversion specification
- 1 CO/CO2 ratio specification
=0
 Combustion of Ethane
C2H6 + 7 O2 → 2CO2 + 3H2 O
2
C2H6 + 5 O2 → 2CO+ 3H2 O
2

 fC2H6 = 0.9
excess air
specification
25% of the ethane burned forms CO

 100 mol C2H6  3.5 mol O2 

(n )
O2 theoretica l
=    = 350 mol O2
  mol C2H6 
0.21n0 = 1.5(350 mol O2 ) 𝒎𝒐𝒍𝒆𝒔 𝒂𝒊𝒓 𝒇𝒆𝒅
n0 = 2500 mol air = 𝒎𝒐𝒍𝒆𝒔 𝒂𝒊𝒓 𝒕𝒉𝒆𝒐 × [𝟏 + 𝒇𝒂𝒄𝒕𝒊𝒐𝒏 𝒆𝒙𝒄𝒆𝒔𝒔 𝒂𝒊𝒓]
 Combustion of Ethane
C2H6 + 7 O2 → 2CO2 + 3H2 O
2
C2H6 + 5 O2 → 2CO+ 3H2 O
2

ethane  fC2H6 = 0.9

conversion n0 = 2500 mol air

specification
 25% of the ethane burned forms CO

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

 Combustion of Ethane
C2H6 + 7 O2 → 2CO2 + 3H2 O
2
C2H6 + 5 O2 → 2CO+ 3H2 O
2

n1 =10.0 mol C2H6


fC2H6 = 0.9


n0 = 2500 mol air

CO/CO2 ratio 25% of the ethane burned forms CO
specification 

 2 mol CO gen 
n4 = (0.25)(0.9)(100 mol C2H6 )  = 45.0 mol CO
 1 mol C2H6 react 
 Combustion of Ethane
C2H6 + 7 O2 → 2CO2 + 3H2 O
2
C2H6 + 5 O2 → 2CO+ 3H2 O
2

n1 =10.0 mol C2H6


fC2H6 = 0.9
n4 = 45.0 mol CO
n0 = 2500 mol air

nitrogen 25% of 
the ethane burned forms CO
balance 

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

 Combustion of Ethane
C2H6 + 7 O2 → 2CO2 + 3H2 O
2
C2H6 + 5 O2 → 2CO+ 3H2 O
2
n1 =10.0 mol C2H6

n3 =1975 mol N2
 fC2H6 = 0.9
n4 = 45.0 mol CO
n0 = 2500 mol air 

atomic C 25% of 
the ethane burned forms CO
balance 

(100 mol C2H6 )(1mol

2 mol C
CH
2 6
)= n ( 2 mol C
1 1 mol C2H6 )+ n ( 1 mol C
4 1 mol CO ) + n5 (11molmolCOC )
2

n5 = 135 mol CO2

 Combustion of Ethane
C2H6 + 7 O2 → 2CO2 + 3H2 O
2
C2H6 + 5 O2 → 2CO+ 3H2 O
2
n1 =10.0 mol C2H6

n3 =1975 mol N2
 fC2H6 = 0.9
 n4 = 45.0 mol CO
n5 =135 mol CO2
n0 = 2500 mol air

atomic H 25% of 
the ethane burned forms CO
balance 


(100 mol C2H6 )(1mol

6 mol H
CH
2 6
) = (10 mol C H )( 2 6
6 mol H
1 mol C2H6 )+ n ( 2 mol H
6 1 mol H2O )
n6 = 270 mol H2O
 Combustion of Ethane
C2H6 + 7 O2 → 2CO2 + 3H2 O
2
C2H6 + 5 O2 → 2CO+ 3H2 O
2
n1 =10.0 mol C2H6

n3 =1975 mol N2
 fC2H6 = 0.9
 n4 = 45.0 mol CO
n5 =135 mol CO2
n0 = 2500 mol air
atomic O  n6 = 270 mol H2 O
balance 25% of 
the ethane burned forms CO



(525 mol O2 )(12mol
mol O
O ) = n ( 2 mol O
2 1 mol O ) + (45 mol CO )( 1 mol CO )
1 mol O

+ (135 mol CO2 )(12mol ) (1 mol H O )

2 2

mol O
CO +2
(2 70 mol H2 O ) 1 mol O
2

n2 = 232 mol O2
 Combustion of Ethane
C2H6 + 7 O2 → 2CO2 + 3H2 O
2
C2H6 + 5 O2 → 2CO+ 3H2 O
stack gas 2
n1 =10.0 mol C2H6
composition n2 = 232 mol O2
(dry basis) n3 =1975 mol N2
 fC2H6 = 0.9
 n4 = 45.0 mol CO
 n5 =135 mol CO2
n0 = 2500 mol air  n6 = 270 mol H2 O
25% of 
the ethane burned forms CO

 + 1974 + 45 + 135 = 2396
sum of dry gases = 10 + 232

y1 = 10 2396 = 0.00417 mol C 2 H 6 mol 270 mol H2 O
y2 = 232 2396 = 0.0970 mol O 2 mol 2396 mol dry stack gas
Composition
y3 = 1974 2396 = 0.824 mol N 2 mol mol H2 O
of dry gas = 0.113
y4 = 45 2396 = 0.019 mol CO mol
mol dry stack gas
y5 = 135 2396 = 0.0563 mol CO 2 mol
Read and solve the following:
• Section 4.7g: Purge. Then solve examples 4.7.3
• Solve example 4.8.4