ChE 1701
Fundamentals of Chemical Engineering
Md. Jahirul Islam
Assistant Professor
Department of Chemical Engineering
Dhaka University of Engineering and Technology, Gazipur
Chapter 4
Fundamentals of
Material Balances
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Balances on Reactive Systems
• Stoichiometry
The theory of proportions in which chemical
species combine with one another.
– Example: 2 SO2 + O2 → 2SO3
• Stoichiometric Ratio
Ratio of stoichiometric coefficients
– Example
2 mol SO3 produced 2 mol SO2 reacted
1 mol O2 reacted 2 mol SO3 produced
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Stoichiometry
2SO2 + O2 → 2SO3
Let, 1600 kg/h of SO3 is produced. What’s the amount of
oxygen required?
Solution:
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Test yourself
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Terminology
• Limiting reactants
Exist less than stoichiometric proportion
• Excess reactants
Exist more than stoichiometric proportion
• Example
𝟐𝐒𝐎𝟐 + 𝐎𝟐 → 𝟐𝐒𝐎3
(30 mol) (10 mol)
Excess Limiting
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Terminology
n − ns
• Fractional excess
ns
• Percent excess n −n s
× 100
ns
Example
– H2 + Br2 → HBr
– H2 ∶ 25 mol/hr
– Br2 ∶ 20 mol/hr
(25 – 20 )
– Fractional Excess H2 = = 0.25
20
– Percent Excess = 25 %
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Terminology
• Fractional conversion
– Chemical reactions are not always completed.
– Factional conversion
f = (moles reacted) / (moles fed)
– When fresh feed consists of more than one
material the conversion must be stated for a
single component, usually the limiting reactant.
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Fractional conversion
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Assignment
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Example Problem
Basis: 100 mol of feed
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Example Problem
• Find the amount of C3H6, NH3, and O2 in the feed.
• Find the limiting reactant.
• Find the % excess of excess reactants.
• For a fractional conversion of 30% of the limiting reactant
find the outlet composition.
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Terminology
reactant input to process − reactant output from process
Overall Conversion =
reactant input to process
reactant input to reactor − reactant output from reactor
Single Pass Conversion =
reactant input to reactor
• In general, high overall conversions can be achieved in
two ways:
– Design the reactor to yield a high single- pass
conversion, or
– Design the reactor to yield a low single- pass
conversion and follow it with a separation unit to
recover and recycle unconsumed reactant.
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Multiple Reaction, Yield, Selectivity
Multiple reaction : one or more reaction
• Side Reaction : undesired reaction
• Example: Production of ethylene
C2 H6 → C2 H4 + H2
Side Reactions
C2 H6 + H2 → 2CH4 + H2
2CH4 + C2 H6 → C3 H6 + CH4
• Design Objective
✓ Maximize desired products (C2 H4 )
✓ Minimize undesired products (CH4 , C3 H6 )
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Terminology
moles of desired product formed
Yield =
moles that would have been formed if
there were no side reactions and
the limiting reactant had reacted completely
moles of desired product formed moles of desired product formed
Yield = Yield =
moles of reactant fed moles of reactant consumed
moles of desired product formed
Selectively =
moles of undesired product formed
• Yield and Selectivity are used to describe the degree to which a desired reaction
predominates over competing side reactions.
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Determination of yield and selectivity
5
C2H6 + O2 → 2CO + 3H2O
2
7
𝐶2𝐻6 + 𝑂2 → 2𝐶𝑂2 + 3𝐻2𝑂
2
Undesired product: CO 80% Conversion
REACTOR
120 mol CO2
100 mol C2H6 40 mol CO
500 mol O2 240 mol O2
240 mol H2O
Yield = 0.6 or 1.2 or 1.5
Selectivity = 3.0
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Example Problem
• Basis:100 mol Feed
• Draw the block diagram of mol balance around reactor.
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Problem
• Express the outlet component amounts in terms of extent of reactions.
• Ethane conversion
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Problem
• Ethylene yield
• Selectivity
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Balances of Atomic and Molecular Species
• Methods for solving mass balances with reactions
– Using balances on molecular species
– Using balances of atoms
– Using the extent of reaction
• For multiple reactions, sometimes it is more convenient to use atomic
balances
• 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 reaction.
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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.
• The degree-of-freedom analysis is as follows:
• Once a generation or consumption term has been calculated for a
species in a given reaction, the generation and consumption terms for all
other species in that reaction may be determined directly from the
stoichiometric equation.
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Molecular Species Balances
• Degree-of-Freedom Analysis
• The hydrogen balance will be used to determine the rate of hydrogen
generation, and the outlet flow rates of ethane and ethylene will be
calculated from the balances on those species. Notice how the ethane
consumption and ethylene generation terms are determined directly
from the hydrogen generation term.
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Atomic Species Balances
• All balances on atomic species (C, H, 0, etc.) take the form "input =
output," since atomic species can neither be generated nor consumed in
chemical reactions (as opposed to nuclear reactions).
• The number of degrees of freedom is determined directly by subtracting
equations from labeled unknowns: no additional degrees of freedom
are contributed by the reactions.
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Atomic Species Balances
Degree-of-Freedom Analysis
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Extent of Reaction
• The third way to determine unknown molar flow rates for a reactive
process is to write expressions for each product species flow rate (or
molar amount) in terms of extents of reaction
• The degree-of-freedom analysis follows:
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Problem
Ethane is burned with air in a continuous steady-state combustion reactor to
yield a mixture of carbon monoxide, carbon dioxide, and water. The feed to
the reactor contains 10% C2 H6 . The percentage conversion of ethane is
80%, and gas leaving the reactor contains 8 mol CO2 per mol of CO.
determine the composition of the product.
5
C2 H6 + O2 → 2CO + 3H2 O
2
7
C2 H6 + O2 → 2CO2 + 3H2 O
2
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Exercise Problem
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Concept of Purge- why needed?
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Production of Ethylene Oxide
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Purging
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Definition
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Example 4.7-3
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Example 4.7-3, page 139
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Combustion Reaction
Combustion
• A rapid reaction of a fuel with oxygen
• Fuels : coal, fuel oil, gas fuel, solid fuel
• Complete combustion / incomplete combustion
• Wet basis composition / dry basis composition
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Composition on Wet and Dry Bases
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Composition on Wet and Dry Bases
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Terminology
Theoretical oxygen : Amount of oxygen needed for
complete combustion
• all carbon in the fuel is oxidized to CO2 and
• all the hydrogen is oxidized to H2 O
Theoretical air : The quantity of air that contains
theoretical oxygen
Air(theo) = 4.76 x O2 (theo)
Excess air : The amount by which the air fed to
reactor exceeds the theoretical air
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Combustion Reaction
• Lower heating value
• Higher heating value
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Test Yourself
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Problem
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Problem
• Find the amount of air feed
• Find the amount of ethylene react
• Find the amount of CO produced
• Find the amount of CO2 produced from atomic Carbon balance
• Find the amount of H2O produced from atomic hydrogen balance
• Find the amount of O2 produced from atomic oxygen balance
© Md. Jahirul Islam , AP