Chapter 5: Extent of Reaction

= - + -
Steady state system:
0 = - + -

= + -

Input (1) Output (2)

Reactor N2 + 3H2 2NH3
1,2 2,3
1,2

nN2,out = nN2,in Consumption

, = , +
nNH3,out = nNH3,in + Generation

, ,
Extent of reaction: =

27
Chapter 5: Species Mole Balances, SMB

Extent of reaction (Batch process):

, , , = , +
=

Extent of reaction (Continuous process):

, , , = , +
=

Species Material Balances
f =Conversion factor of the limited reactant

()
= = 100%
()
, , ,
= =

28
Chapter 5: Species Mole Balances

Example 5.7: Reaction in Which the Fraction Conversion is Specified:

The chlorination of methane occurs by the following reaction
CH4 + Cl2 CH3Cl + HCl
You are asked to determine the product composition if the conversion of
the limiting reactant is 67%, and the feed composition in mole % is given as:
40% CH4, 50%Cl2,and 10% N2.
Assumptions: The reactor is Open, Steady state process
Solution:

Species moles % 1 2
feed Reactor
CH4 40% 1,Cl 2,Cl
2 2
Cl2 50% 1,CH 2,CH
4 4
1,N 2,N
N2 10% 2 2

fLR 67%
29
Chapter 5: Species Mole Balances
1 2
Reactor
1,Cl 2,Cl
2 2
1,CH 2,CH
4 4
1,N 2,N
2 2
CH4 + Cl2 CH3Cl + HCl 2,HCl
2,CH Cl
3

30
Chapter 5: Species Mole Balances

Example 10.2: A Reaction in Which the Fraction Conversion is to Be

Calculated:
H2S is toxic in very small quantities and is quite corrosive to process
equipment.
A proposed process to remove H2S is by reaction with SO2:
2H2S(g) + SO2(g) 3S(s) + 2H2O(g)

In a test of the process, a gas stream containing 20% H2S and 80% CH4
was combined with a stream of pure SO2.
The process produced 5000 kg of S(s), and in the product gas the ratio of
SO2 to H2S was equal to 3, and the ratio of H2O to H2S was 10.

You are asked to determine the fractional conversion of the limiting

reactant, and the feed rates of the H2S and SO2 streams.
Assumptions: The reactor is Open, Steady state process.
Solution:

31
Chapter 5: Species Mole Balances
Species moles % feed
2,SO2 2
CH4 80%
Product
H2S 20% 1 1 3
1,H2S =0.20
Reactor
4,S 5000 kg 3,H2S
3,SO2 /3,H2S 1,CH4 =0.80
3 3,CH4
3,H2O /3,H2S 10
1,H2S 4 3,H2O
1,CH4
4,S =5000 kg 3,SO2
2H2S(g) + SO2(g) 3S(s) + 2H2O(g) n4,s= 156.25 mol
Moles, Kmol MW Mass, Kg
n1 H2S 114.6 34 3896.4
Input

n1 CH4 458.48 16 7335.68

n2 SO2 83.3 64 5331.2
Sum input 656.38 Kmol 16563.3 Kg
n3 H2S 10.42 34 354.28
n3 CH4 458.48 16 7335.68
Output

n3 H2O 104.2 18 1875.6

n3 SO2 31.2 64 1996.8
n4 S 156.25 32 5000
Sum out 760.55 Kmol 16562.4 Kg

32
Chapter 5: Process Involving Multiple Reactions

Example 5.8: Material Balances Involving Two Ongoing Reactions

Formaldehyde (CH2O) is produced industrially by the catalytic oxidation of
methanol (CH3OH) according to the following reaction:
CH3OH + O2 CH2O + H2O (1)
Unfortunately, under the conditions used to produce formaldehyde an
undesired reaction occurs, that is:
CH2O + O2 CO + H2O (2)
Assume that methanol and twice the stoichiometric amount of air needed
for complete conversion of the CH3OH to the desired products (CH2O and
H2O) are fed to the reactor.
Also assume that 90% conversion of the methanol results, and that a 75%
yield of formaldehyde occurs based on the theoretical production of CH2O
by Reaction 1.
Determine the composition of the product gas leaving the reactor.
Solution:

33
Chapter 5: Process Involving Multiple Reactions
2 (Air)
2,O2 21% Assume that CH3OH 2,O2 =0.21
2,N2 79% requires twice the
2,N2 =0.79
. , CH3OH 90% stoichiometric amount of
2,O2
CH2O 75%
Air are fed to the reactor. 2
2,N2
CH3OH + O2 CH2O + H2O (1) Product
CH2O + O2 CO + H2O (2)
1 Formaldehyde 3
1,CH3OH Reactor
3,CH3OH
3,CH2O
3,H2O
3,CO
3,O2
3,N2

34
Chapter 5: Process Involving Multiple Reactions

Example 5.9: Analysis of a Bioreactor

A bioreactor is a vessel in which biological conversion is carried out. The
following overall reactions occurs:
Reaction 1: C6H12O6 2C2H5OH + 2CO2
Reaction 2: C6H12O6 2C2H3CO2H + 2H2O
In a batch process, a tank is charged with 4000 kg of a 12% solution of
glucose(C6H12O6) in water. After fermentation, 120 kg of CO2 are produced
and 90 kg of unreacted glucose(C6H12O6) remains in the solution. What are
the weight (mass) percent of ethanol(C2H5OH) and propenoic
acid(C2H3CO2H) in the solution at the end of the fermentation process?
Assume that none of the glucose(C6H12O6) is assimilated(digested) into the
bacteria.
Solution:

35
Chapter 5: Process Involving Multiple Reactions
C6H12O6 2C2H5OH + 2CO2 (1)
C6H12O6 2C2H3CO2H + 2H2O (2)
, =4000 kg Soln ,2 =120 kg CO2
,6126 =0.120 Unreacted C6H12O6
,2 =0.88 ,6126 =90 kg
C6H12O6 H2O CO2 C2H5OH C2H3CO2H
MW(g/mol) 180 18 44.0 46 72
, =4000 kg
,2 ,2
,6126 ,6126
,232
,2
,25

36
Chapter 5: Element Material Balances, EMB

Species Moles Balances: , = , +

Element Material Balances, EMB: Number of atoms enter the

reaction EQUAL number of atoms leave the reaction
Input (atoms)= Output (atoms)

CO2 + H2O H2CO3

For most problems it is easier to apply mole balances, but for some
problems, such as problems with complex or unknown reaction
equations, element balances are preferred.

37
Chapter 5: Element Material Balances, EMB

Example 5: Carbon dioxide is absorbed in water in the process shown

below. The reaction is
CO2 + H2O H2CO3
Apply the element balance to find the unknowns in the flow chart?
3 =100 mol
2,CO 3,H CO =0.05
2 2 2 3
3,H O = 0.95
1 3
2
3,H CO
2 3
Absorber 3,H O
1,H O 2
2

38
Chapter 5: Element Material Balances

Example 5.11: Hydrocracking

Researchers in the field oil industry study the hydrocracking of pure components,
such as octane (C8H18) to understand the behavior of cracking reactions.
In one such experiment for the hydrocracking of octane (C8H18) , the cracked
products had the following composition in mole percent: 19.5% C3H8, 59.4% C4H10,
and 21.1% C5H12.
You are asked to determine the molar ratio of hydrogen consumed to octane reacted
for this process.
Solution:

39
Chapter 5: Element Material Balances
3
Species Product 2,H2 3,C3H8
Moles 2
percentage 3,C4H10
1 3 3,C5H12
C3H8 19.5% Lab
3,C3H8 =0.195
C4H10 59.4% 1,C8H18 Reactor
3,C4H10 =0.594
C5H12 21.1%
3,C5H12 =0.211

40
Chapter 5: Material Balances Involving Combustion

CH4+ Air CO2 (g)+ 2H2O (g) + Energy

Wet basis: all the gases resulting from a combustion process including the
water vapor, known as Flue or stack gas.

Dry basis: all the gases resulting from a combustion process not9including
the water vapor.

Complete combustion: the complete reaction of the hydrocarbon fuel

producing CO2, SO2, and H2O.

Partial combustion: the combustion of the fuel producing at least some

CO.

Theoretical air (or theoretical oxygen): the minimum amount of air (or
oxygen) required to be brought into the process for complete combustion.
Sometimes this quantity is called the required air (or oxygen).
41
Chapter 5: Material Balances Involving Combustion
Excess air (or excess oxygen): excess air (or oxygen) is the amount of air
(or oxygen) in excess of that required for complete combustion.

excess air
% Excess air = 100
required air
excess O2 0.21 excess O2
= 100 = 100
required O2 0.21 required O2

O2 excess = O2,in (enter the process) O2 required

O2 in(enter the process)O2 required
% Excess air = 100
O2 required

The calculated amount of excess air does not depend on how much material is
actually burned but what is possible to be burned. Even if only partial
combustion takes place.

42
Chapter 5: Material Balances Involving Combustion
Example 5.12: Excess Air
Fuels other than gasoline are being eyed for motor vehicles because they
generate lower levels of pollutants than does gasoline. Compressed propane
is one such proposed fuel.
Suppose that in a test 20 kg of C3H8 is burned with 400 kg of air to
produce 44 kg of CO2 and 12 kg of CO.
What was the percent excess air?
Solution: C H + 5O 3CO + 4H O (g)
3 8 2 2 2

43
Chapter 5: Material Balances Involving Combustion
Example 5.13: A Fuel Cell to Generate Electricity From Methane
Fuel cell is an open system into which fuel and air are fed, and the outcome
are electricity and waste products. Figure bellow is a sketch of a fuel cell in
which a continuous flow of methane (CH4) and air (O2 plus N2) produce
electricity plus CO2 and H2O.
Special membranes and catalysts are needed to promote the reaction of
CH4.
Based on the data given in Flow chart, you are asked to calculate the
composition of the products in stream 3.
Solution:

44
Chapter 5: Material Balances Involving Combustion
Air H2O CO2 CH4 1 Lab
2 2, =300 kg
MW(g/mol) 29 18 44.0 16 2,
1,CH4 =16.0 kg Reactor 2,O2
1,CH4 3 2,N2
3 3,CO2 2,O2 =0.21
3,N2 2,N2 =0.79
3,O2
3,H2O

45
Chapter 5: Material Balances Involving Combustion

Example 6: Combustion of Ethane

Ethane is burned with 50% excess air. The percentage conversion of the
ethane is 90%.
The ethane burned: 25% reacts to form CO and 75 % reacts to form CO2?
Calculate the molar composition of the stack gas on a dry and wet basis and
the mole ratio of water to dry stack gas?
C2H6+ 7 2O2 2CO2 + 3H2O
C2H6+ 5 2O2 2CO + 3H2O 3,26
3,CO2
1 3
Combustion 3,CO
Unit 3,N2
1,26 =100 mol
3,O2
2 3,H2O
50%
2,
2,O2 =0.21
2,N2 =0.79
46
Chapter 5: Material Balances Involving Combustion
3,26
C2H6+ 7 2O2 2CO2 + 3H2O 3 3,CO2
1
C2H6+ 5 2O2 2CO + 3H2O Combustion 3,CO
excess air = 50% Unit 3,N2
1,26 =100 mol
fC2H6 =90% 3,O2
25% C2H6 reacts to form CO 2 3,H2O
75 % C2H6 reacts to form CO2 50%
2,
2,O2 =0.21
2,N2 =0.79

47
Chapter 5: Material Balances Involving Combustion

Example 7: Combustion of a Hydrocarbon Fuel of Unknown Composition

A hydrocarbon gas is burned with air. The dry-basis product gas
composition is 1.5 mole% CO, 6.0% C02,8.2% 02, and 84.3% N2. There is no
atomic oxygen in the fuel.
Calculate the ratio of hydrogen to carbon in the fuel gas and speculate on
what the fuel might be?
Calculate the percent excess air fed to the reactor?
Output composition
on a dry basis
3 3 =100 mol (dry gas )
1 Combustion 3,CO2 Elements Moles %
Unit 3,CO Input
1,
1, 3,O2 CO 1.5%
2 3,N2 CO2 6.0%
2, O2 8.2%
2,O2 =0.21 4,H2O
N2 84.3%
2,N2 =0.79

48
Chapter 5: Material Balances Involving Combustion
Output composition on a dry basis 3 3 =100 mol (dry gas )
1 Combustion 3,CO2 = 1.5 mol
1, Unit 3,CO = 6.0 mole
1, 3,O2 = 8.20 mol
2 3,N2 =84.3 mol
2,
2,O2 =0.21 4,H2O
2,N2 =0.79

49
Chapter 5: Material Balances Involving Combustion

Example 5.14: Combustion of Coal

A local utility burns, the moisture in the input fuel was 3.90%.
The air on the average contained 0.0048 kg H2O/kg dry air.
The refuse showed 14.0% unburned coal, with the remainder being ash.

You are asked to check the consistency of the data before they are stored in
a database. is the consistency satisfactory?
What was the average percent excess air used?
Input composition on a dry basis Output composition
Elements Input Moles % on a dry basis
C 83.05% Elements Moles
H 4.45 % Input %
O 3.36% CO2+SO2 15.4%
N 1.08% CO 0
S 0.70% O2 4%
Ash 7.36% N2 80.6%
50
Chapter 5: Material Balances Involving Combustion
1 =100 kg

1, =83.05 kg 3
1, =4.45 kg 1 3 3,CO2
1,O =3.36 kg
Lab
3,N2
1,N = 1.08 kg Reactor
3,O2
1,S =0.70 kg 3,H2O
1,Ash =7.36 kg 2
2, =300 kg
2,
2,O2 =0.21
2,N2 =0.79

51
52