Material Balances with Reactions:

Chemical Reaction and

Stoichiometry
Module 06

1
Learning Outcomes
q Understand the concept of stoichiometry
q Identify excess and limiting reactants
q Calculate conversion, yield, selectivity

2
Recall: Reactor Unit Operation

Dough Cookies
Reactor

3
Recall: Material Balance Equation
• Conservation Laws
• Mass (except in nuclear reactions)
• Moles are NOT conserved when there are reactions!
• Volume is generally NOT conserved
• Energy (1st Law of Thermodynamics)
• For any conserved property,
In – Out + Gen = Acc
• IN: sum of all flow rates into the system
• OUT: sum of all flow rates going out of the system
• GEN: formation or consumption within the system
• ACC: net rate of change of the property in the system (zero at steady-state)

4
Recall: Material Balance Equation
• For steady-state processes involving reactive species:
Input + Generation = Output + Consumption
• The generation and consumption terms in the molecular balance
equation is usually obtained from chemical stoichiometry.
• Atomic balance
Input = Output

5
Reaction Stoichiometry
• Refers to calculation of weights of substances involved in chemical
reactions
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
• a & b, c & d à molecules (moles) of A & B, C & D
• Balanced chemical equation:
• Number and types of atoms
• Sum of masses
• Stoichiometric ratios
• Obtained from numerical coefficients of chemical equations (conversion factors)
• Multiple reactions
𝑎! 𝐴 + 𝑏! 𝐵 → 𝑐𝐶
𝑎" 𝐴 + 𝑏" 𝐵 → 𝑑𝐷

6
Sample Problem 01
• Balance the reaction of pyrites and oxygen to form ferric oxide and
sulfur dioxide.

pyrites + oxygen → ferric oxide + sulfur dioxide

FeS2 + O2 → Fe2O3 + SO2

4FeS2 + 11O2 → 2Fe2O3 + 8SO2

7
Sample Problem 02
• How many kg SO2 and Fe2O3 will 100 kg FeS2 produce? How much O2
is needed?

4FeS2 + 11O2 → 2Fe2O3 + 8SO2

Additional Information: (Molecular Weights)

FeS2 = 119.979 kg/kmol
Fe2O3 = 159.692 kg/kmol
SO2 = 64.065 kg/kmol

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Reaction Stoichiometry
• Gravimetric Factor
• Stoichiometric masses
aA + bB → cC + dD
• Mass A = a x MWA
Mass A a ( MWA )
=
Mass C c ( MWC )
Mass D d ( MWD )
=
Mass B b ( MWB )
• Useful to calculate mass balance without writing the balanced
chemical equation

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Sample Problem 03
• How many kg SO2 and Fe2O3 will 100 kg FeS2 produce? How much O2
is needed?

4FeS2 + 11O2 → 2Fe2O3 + 8SO2

Additional Information: (Molecular Weights)

FeS2 = 119.979 kg/kmol
Fe2O3 = 159.692 kg/kmol
SO2 = 64.065 kg/kmol

10
Excess and Limiting Reactants
• Stoichiometric ratios à theoretical
• Excess and limiting reactants
• One reactant supplied in excess to hasten or promote the reaction
• Other reactant is the limiting one (will run out if process goes to completion)

n feed − nstoich n feed − nstoich

fractional excess = % excess = x100%
nstoich nstoich
• Check: calculate mole ratios in feed, then compare with stoichiometric ratios

11
Sample Problem 04
• 5 gmol FeS2 reacts with 10 gmol O2, determine the limiting and excess
reactants. What is the fractional and percent excess of the excess
reactant?

4FeS2 + 11O2 → 2Fe2O3 + 8SO2

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Sample Problem 05
• Example: hydrogenation of acetylene to form ethane:
C2H2 + 2H2 → C2H6
Suppose that 20.0 kmol/h of acetylene and 50.0 kmol/h hydrogen are
fed to the reactor, determine the limiting reactant, and calculate for the
fractional excess of the other reactant.

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Conversion, Yield, Selectivity
• Conversion
• Fraction of the limiting reactant transformed or converted into products
(degree of completion)
• For multiple products: conversion to a specific product has to be specified

moles reacted
fractional conversion =
moles fed

• Ex: 100 moles fed and 90 moles reacted

• Ex: 20 mol/min of a reactant is fed and the percentage conversion is
80%

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Conversion, Yield, Selectivity
A + B → C (desired product)
A + B → D (side product)
• Selectivity
moles of desired product formed
selectivity =
moles of undesired product formed

• Yield
• Ratio of the actual amount of desired product formed to the amount of
product had the reaction gone to completion
• Undesired side reactions, incomplete reactions, chemical equilibrium à
reduce yield

15
Sample Problem 06
• Consider the following pair of reactions
A → 2B (desired)
A → C (undesired)
Suppose 100 mol of A is fed to a batch reactor and the final product
contains 10 mol of A, 160 mol of B, and 10 mol of C. Calculate:

a. The fractional conversion of A.

b. The percentage yield of B.
c. The selectivity of B relative to C.

16
Ideal and Industrial Reactions
• Comparison of Ideal and Industrial Reactions
Ideal (Theoretical Reaction)
complete
Stoichiometric amounts are
used
Pure materials are used
Assumed to occur at only one
condition
No competing side reactions
are involved
Stoichiometric amounts of
products are obtained
Industrial Reaction
Seldom complete
Some reactants are in excess
Raw materials are impure or
mixed with other substances
Occurs over a wide range of
temperature, pressure, and
concentration
Several reactions may occur
simultaneously
Products will contain side
products and unreacted or
excess reactants
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Sample Problem 07 (Homework)
4FeS2 + 11O2 → 2Fe2O3 + 8SO2
• Condition A:
• If the reaction is only 95% complete, what are the amounts of compounds present after the
reaction?
• Condition B:
• If the reaction is complete and 20% excess oxygen is used, find the kg of compounds after
reaction.
• Condition C:
• If the reaction is complete and 20% excess air is used, find the kg of compounds after reaction.
• Condition D:
• If the reaction is complete, pure oxygen is used, and the pyrites contain 10% impurities, find the
amounts of products.
• Condition E:
• If 90% of the pyrites produces SO2 while 10% produces SO3, and all the necessary oxygen is
provided, find the amounts of the products.
4FeS2 + 15O2 → 2Fe2O3 + 8SO3 (side product) MW:
FeS2 = 119.979 kg/kmol
Fe2O3 = 159.692 kg/kmol
SO2 = 64.065 kg/kmol
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Material Balances with Reactions

• Two approaches:
• Molecular species balance
• Applied to each chemical compound involved in the process
• Generation/Consumption (from stoich)
• Atomic species balance
• Applied to each element appearing in the process
• Conserved (input=output)

19
Sample Problem 08
• Dehydrogenation Reaction of Ethane
C2H6 → C2H4 + H2
100 kmol/min of ethane is fed to the reactor and the molar flow rate of
H2 in the product stream is 40 kmol/min.

Compute for the molar composition of the product stream using

molecular balance and atomic balance.

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