CME 210 Principles of Chemical

Engineering

Fall 2016-2017

Dr. Ioannis Zuburtikudis

Chapter 4

1
Example: Extent of Reaction, Atomic
Balance and Molecular Species Balance
Methods
Problem
• Ammonia is burned to form nitric oxide and water.
4NH 3  5O 2  4NO  6H 2O
• The fractional conversion of oxygen is 0.5. The inlet molar flow
rate is 5 mol/h of NH3 and 5 mol/h of oxygen. Calculate the exit
component molar flow rates using the three methods:
 Extent of reaction method
 Atomic balance approach
 Molecular species balance approach
Solution

2
 Cont. Solution Example
Extent of reaction method
• The material balance can be written using
the extent of reaction method as follows:
ni  ni0  
Where  NH3  4,  O2  5,  NO2  4, and  H2O  6
Material balance of each component is then:
NH 3 : nNH3  nNH0
3
 4
O2 : nO2  nO0 2  5
NO : nNO  nNO
0
 4

H 2 O : nH2O  nH0 2O  6

Total number of moles at the outlet of the reactor:

n  n0  (4  5  4  6)  n0  
where 3
n0  nNH
0
3
 n 0
O2  n 0
NO  n 0
H2 O
 Cont. Solution Example
The total material balance equation is:
n  n0  
Inlet molar feed rates:
0
nNH 3
 5 mol/h, n0
O 2
 5 mol/h, n 0
NO  0, nH
0
2O
0
The reactor single pass conversion based on oxygen component is given by:
nO0 2  nO2
Conversion  f  , substituting known quantities.
nO0 2
5  nO2
0.5  , the exit number of moles of oxygen is: nO2 = 2.5 mol .
5
Substituting nO in oxygen component mole balance equation and solve for 
2

nO2  n  5
0
O2

2.5  5  5
The extent of reaction is   0.5
Substituting the value of   0.5 and the initial molar flow rates of each component into
components mole balance equations, the final results are then:
4
nO2  2.5 mol/h , nNH3  3 mol/h , nH 2O  3 mol/h , nNO  2 mol/h
 Cont. Solution Example
• Atomic balance approach
• Atomic balance on atoms involved in the
reaction (N, O, H), this is based on reactor
inlet and outlet streams and not on the
stoichiometry of the reaction equation
N: 5  nNH3  nNO
O: 2(5)  2(nO2 )  nH2O  nNO
H: 3(5)  3nNH3  2nH 2O
The single pass conversion, f O2
nO0 2  nO2 5  nO2
f O2   0.5  , nO = 2.5mol
nO0 2 5 2

Substituting nO in the O atomic balance and rearranging equations:

2

5  nNH3  nNO (1)

5
5  nH 2O  nNO (2)
15  3nNH3  2nH 2O (3)
 Cont. Solution Example
Subtracting equation 2 from equation 1 leads to:
0  nNH3  nH 2O , hence,
nNH3  nH 2O
Substitution of nNH3  nH 2O in equation 3
15  3nNH3  2nNH3
5nNH3  15 , nNH = 3mol
3

Since nNH3  nH 2O , accordingly, nH O = 3mol

2

Substitute nH O in equation 2 to get value of nNO

2

5  nH 2O  nNO
5  3  nNO , nNO  2 mole
The final results are:
nO2  2.5 mol/h , nNH3  3mol/h , nH 2O  3 mol/h , nNO  2 mol/h

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 Cont. Solution Example
Molecular species approach
• Molecular species balances can be done
Moles reacted as reacted
Mole the following:
Conversion  f  0.5  
• The limiting reactantMoles in the feed
is oxygen: 5
Moles of O2 reactedMoles
Conversion  f  0.5 
= 0.5 × 5=Mole
reacted 2.5reacted
mol
Moles in the feed 5
• Moles
Moles of of
O2Oexiting
2 reacted = 0.5 ͯ 5
the reactor = 5=2.5 mol
– 2.5 = 2.5 mol
• Moles of O2 exiting the reactor = 5 – 2.5 = 2.5 mol
44 mol
molNH NHconsumed
3 consumed
• Moles
Moles of of
NHNH consumed
3 consumed
3  =
2.5 molO consumed 
2 O2 consumed 
2.5 mol 3  2 mol
 2 mol
55mol
mol ofofO2O consumed
consumed
•
2
Moles of NH 3 leaving
Moles of NH3 leaving
the reactor = in – consumed =
the reactor = in – consumed = 5 – 2 = 3 mol
5 – 2 = 3 mol
• Moles H2O generated = 6 mol
molHH O generated
2O2generated
Moles H2O generated  2.5 molO 2 consumed
2.5 mol 
O2 consumed  3 mol
 3 mol
5 mol of O consumed
5 mol of 2O2 consumed
• Moles of NO generated = 4 mol NO generated
2.5 mol O2 consumed 4 mol NO generated  2 mol
Moles of NO generated  2.5 mol O2 consumed  5 mol of O2 consumed  2 mol
5 mol of consumed
7
The final values of exit stream component molar flow rates are:
nO2  2.5 mol/h , nNH3  3 mol/h , nH 2O  3 mol/h , nNO  2 mol/h
4.7 Balances on Reactive Processes
Methods of Solving Material Balance involving Chemical Reaction

 Molecular species balances approach (the approach always used for nonreactive
systems).
 Atomic species balance approach.
 Extent of reaction approach.

Each approach leads to the same results, but any one of them may be more convenient
for a given calculation.

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4.7 Balances on Reactive Processes
Molecular Species Balances

 Balances on reactive molecular species must contain generation

and or consumption terms.
 Note: Once a generation or a consumption term has been calculated for a species
in a given reaction, the generation and consumption terms of all other species in
that reaction follow directly from the stoichiometric equation.

9
4.7 Balances on Reactive Processes
Molecular Species Balances

 Example

10
4.7 Balances on Reactive Processes
Molecular Species Balances

 Example (contd.)

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4.7 Balances on Reactive Processes
Atomic Species Balances

 All balances on atomic species are of the form input = output.

12
4.7 Balances on Reactive Processes
Atomic Species Balances

 Example

13
4.7 Balances on Reactive Processes
Atomic Species Balances
 Example (contd.)

Same solution as before

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4.7 Balances on Reactive Processes
Extent of Reaction

 Substitute known feed and product flow rates and solve for the
extents of reaction.

15
4.7 Balances on Reactive Processes
Extent of Reaction

 Recall the equation for extent of reaction:

Same solution as before

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4.7 Balances on Reactive Processes
Guidelines

 Atomic species balances are the most straightforward solution

procedure especially when more than one reaction is involved.
 Extents of reaction are convenient for chemical equilibrium problems
and when using equation solving software.
 Molecular species balances require more complex calculations and
should be used only for simple systems of one reaction.

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Chemical Reactor Stoichiometry
Multiple reactions, Yield, and Selectivity
 The terms yield and selectivity are used to describe the degree to which a
desired reaction predominates over competing side reactions.

 Example: It is desired to produce ethylene C2H4 by the reaction:

C2H6 C2H4 + H2 (1)
Side reactions: C2H6 + H2 2 CH4 (2)
C2H4 + C2H6 C3H6 + CH4 (3)

 Objective is to maximize the production of the desired product (C2H4) and

minimize the production of undesired products (CH4 , C3H6).

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4.6 Chemical Reactor Stoichiometry
Multiple reactions, Yield, and Selectivity
 Yield may also be defined in different ways: moles of desired product
divided by either moles reactant fed or moles of reactant consumed in
reactor. Be aware of the working definition.

 Selectivity :

 Notice that for multiple reactions (batch or continuous steady state), there
will be an extent of reaction for each reaction, and the a chemical species
may be a reactant in one reaction and a product in another.

is the stoichiometric coefficient of substance i in reaction j.

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 Extent of Reaction and Multiple
Reactions
• Generally, the synthesis of chemical products does not involve a single
reaction but rather multiple reactions. For instance, the goal would be to
maximize the production of the desirable product and minimize the
production of unwanted by-products. For example, ethylene is produced
by the dehydrogenation of ethane:
C2 H 6  C2 H 4  H 2
C2 H6  H 2  2CH 4

C2 H 4  C2 H6  C3H6  CH 4

• Yield and Selectivity are used to describe the degree to which a desired
reaction predominates over competing side reactions in a multi-reaction
system. Yield has various definitions:

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑓𝑜𝑟𝑚𝑒𝑑

Yield = 𝑚𝑜𝑙𝑒𝑠 𝑓𝑜𝑟𝑚𝑒𝑑 𝑖𝑓 𝑡ℎ𝑒𝑟𝑒 𝑤𝑒𝑟𝑒 𝑛𝑜 𝑠𝑖𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠 20
𝑎𝑛𝑑 𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑒𝑙𝑦
 Extent of Reaction and Multiple
Reactions
moles of desired product formed
Yield 
moles of reactant fed

moles of desired product formed

Yield 
moles of reactant consumed
The selectivity of a component is the number of moles of desired component
to number of moles of 00undesired component.
moles of desired product formed
Selectivit y 
moles of undesired product formed

The concept of extent of reaction can also be applied to multiple reactions,

with each reaction having its own extent. If a set of reactions takes place in a
batch or continuous, steady-state reactor, we can write the following equation
for species 𝑖:
ni  nio   ij j
j

where: 21
 ij is the stoichiometric coefficient of substance i in reaction j.
 j is the extent of reaction for reaction j.
 Example Ethane Combustion
Problem
• The following reactions take place in a reactor, where CO is the
undesired product.
C2 H6  3.5O2  2CO2  3H 2O

C2 H6  2.5O2  2CO+3H 2O

The feed to reactor consists of 100 mol C2 H6 and 500 mol O 2 . The product stream was
analyzed and found to contain 20 mol C2 H6 , 120 mol CO 2 , 40 mol CO , 240 mol O 2 , and
240 mol H 2O . The reactor conversion is 80%. Calculate the yield and selectivity.
Solution
moles of desired product formed 120 mole CO 2
Yield    0.6
moles formed if there were no side reactions 200 mole CO 2 should be formed
and limiting reactant reacted completely

moles of desired product formed 120 mole CO2

Yield    1.2
moles of reactant fed 100 mole C2 H6
22
moles of desired product formed 120 mol CO2
Yield    1.5
moles of reactant consumed 100  20
 Cont. Solution Example
• The selectivity is the number of moles of
desired product (carbon dioxide) to the
number of moles of undesired product
formed.
moles of desired product formed 120mole CO2
Selectivit y   3
moles of undesired product formed 40mole CO

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 Example Oxidation Reaction
Problem
• Ethylene is oxidized to ethylene oxide (desired) and carbon dioxide
(undesired). Express the moles (or molar flow rates) of each of the five
species in the product stream in terms of the extent of reaction. The
following reactions are taking place:
1
C2 H 4  O 2  C2 H 4 O
2

C2 H 4  3O2  2CO2  2H 2O

Solution
Analysis: The process flow sheet is shown in Figure E5.8. Assign an extent of reaction
for each reaction; 1 for the first reaction and  2 for the second reaction.

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 Cont. Solution Example
1
The first reaction: C2 H 4  O2  C2 H 4O 1
2
The second reaction: C2 H 4  3O2  2CO2  2H2 O 2
Mole balance using the extent of reaction approach:
C2 H 4 : nC2 H4  nC02 H4  1  2
1
O2 : nO2  nO0 2  1  32
2
C2 H 4 O : nC2 H4O  0  1
CO 2 : nCO2  0  2 2

H 2 O : nH 2O  0  2 2

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4.6 Chemical Reactor Stoichiometry
Example 4.6-3: Yield and Selectivity in a Dehydrogenation Reactor

Solution:

Basis: 100 mol

of Feed

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Chemical Reactor Stoichiometry
Solution (contd.):

the inert does not contribute

to the reaction

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Chemical Reactor Stoichiometry
Solution (contd.):

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Balances on Reactive Processes
Example 4.7-1: Incomplete Combustion of Methane

Solution:

Basis: 100 mol

of Feed

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Balances on Reactive Processes
Solution (contd.):

 First utilize the given methane conversion to determine nCH4:

 All methods involve writing a balance on nonreactive N2 : input = output

nN2 = 72.8 mol N2
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Balances on Reactive Processes
Solution (contd.):
Atomic Species Balances
 Now there are only 3 unknowns (nCO, nH2O, nO2 ).
 Balances on atomic Carbon and atomic hydrogen involve only one
unknown, but a balance on atomic oxygen involves 3 unknowns.

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Balances on Reactive Processes
Solution (contd.):
Atomic Species Balances

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Balances on Reactive Processes
Solution (contd.):
Extents of Reaction

Recall the equation for the reactive species

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Balances on Reactive Processes
Solution (contd.):
Extents of Reaction

 Once again, the same flow rates have been calculated.

 For your exercise, solve using molecular species balances. See how atomic
species balances lead to the least cumbersome solution.

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Balances on Reactive Processes
Product separation and Recycle

A B
 Two main definitions in processes with recycle:

Complete conversion
with recycle

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Balances on Reactive Processes
Test Yourself
What are the overall and single-pass conversions for the process in the figure?

Answers:
Overall = 100/110 = 0.909 mol A consumed/mol A fed
Single pass = 100/200 = 0.500 mol A consumed/mol A fed

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Balances on Reactive Processes
Purging

acts as a separator

Problems may occur in processes that involve recycle.

Material (inert or impurity) that enters the process in feed stream may remain
entirely in it accumulation in reactor and no steady state.

A purge stream is a small stream bled off from a recycle loop to prevent
building of inerts or impurities in the system.
Remark : At the purge point, all streams have the same composition and only
one independent material balance exists.
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Balances on Reactive Processes
Example 4.7-3: Recycle and Purge in the Synthesis of Methanol

General Rule: The combined feed to the reactor is a convenient stream to

use as a basis for recycle problems if the stream composition is known.

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Balances on Reactive Processes
Solution: Basis: 100 mol of Combined Feed to the Reactor

 Reactive systems: overall process and reactor subsystem (reaction occurs within).
 Nonreactive subsystems: Recycle-fresh feed mixing point
Condenser
Purge-recycle splitting point
39
Balances on Reactive Processes
Solution (contd.): start with reactor analysis

40
Balances on Reactive Processes
Solution (contd.): proceed to condenser

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4.7 Balances on Reactive Processes

42
4.7 Balances on Reactive Processes

 Scale factor:
155 kmol CH3OH/h
n3

(155/14)= 11.1

 So, scale up:

multiply all streams
by 11.1.

Remember:
Compositions will
not change

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