MATERIAL BALANCES

FOR PROCESSES WITH

CHEMICAL REACTIONS
Part C
Main Reference:
“Elementary Principles of Chemical Processes”
by Felder and Rousseau 3rd Edition

Prepared by: CGAlfafara

Edited by: JACapunitan
1
 Degree of Freedom
Analysis for Reactive
Systems

2
 Degree of Freedom Analysis for
Reactive Systems

• DF analysis may be useful for mass balance problems involving

multiple process units, recycle or bypass
• A little “trickier” than non-reactive systems
• Requires an understanding of the following concepts:

– independent equations
– independent species
– independent chemical reactions

3
 Independent equations
 algebraic equations are independent if you cannot obtain
anyone of them by adding or subracting multiples of any of
the others
examples

Equation (1) and (2) are NOT INDEPENDENT

because (equation 2) = 3 x (equation 1)

Equation s are NOT INDEPENDENT because

(equation 3) = [(equation 1) x 2] – (equation 2)

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 Independent species

 If two molecular species are in the same ratio to

each other whenever they appear in the
process, balances on those species will not be
independent

 If two atomic species are in the same ratio to each

other whenever they appear in a process,
balances on these species will not be
independent

5
 Independent Molecular species
 If two molecular species are in the same ratio to each
other whenever they appear in the process,
balances on those species will not be independent

* In one stream the ratio of O2 to N2 are the same

• It looks like DF= 3 unknowns – 3 equations = 0, but it is actually
unsolvable because O2 and N2 are NOT INDEPENDENT molecular
species
• Verify by performing component balances for O2 and N2
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 Independent Molecular species
 If two molecular species are in the same ratio to each
other whenever they appear in the process,
balances on those species will not be independent
example
0.017 mol W /mol
0.983 mol DA /mol

n1 (mole) n2 (mole) n4 (mole) 100 moles

0.04 mol W /mol 0.023 mol W /mol 0.017 mol W /mol
0.96 mol DA /mol 0.017 mol W /mol
0.977 mol DA /mol 0.983 mol DA /mol 0.983 mol DA /mol

Components W and DA
are NOT INDEPENDENT
molecular species in the
split point streams n3 (mole) (H2O) 7
 Independent species
Example

 N2 and O2 are NOT INDEPENDENT molecular species, because they are in the same
ratio wherever they appear on the flow chart (3.76 mol N2/ 1mol O2)

 Atomic N and atomic O are NOT INDEPENDENT atomic species because they are always
in the same proportion to each other in the process (3.76/1)
 Atomic C and atomic Cl are NOT INDEPENDENT atomic species because they always
appear in the ratio of 4 moles Cl/1mole C in the process

 There are 2 independent molecular species: (N2 or O2) and CCl4

 There are 2 independent atomic species (N or O) and (C or Cl)

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Independent species

Example

9
 Independent species

Example

CH4, CO, CO2, H2O, O2, N2 (N or O), C, H

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INDEPENDENT CHEMICAL REACTIONS
 Chemical reactions are independent if the
stoichiometric equation of any one of them
cannot be obtained by adding or subtracting
multiples of the stoichiometric equations of
the others
example

Above stoichiometric equations are NOT INDEPENDENT because

2* (equation 2) + (equation 1) = (equation 3)

11
 Solution Strategies for Solving Material
Balance Problems for Processes
with Chemical Reaction

O (1) Molecular Species Balances

O (2) Atomic Species Balances

O (3) Extent of Reaction

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Degree of Freedom for the 3 Types of
Material Balance Strategies
Molecular Species
Balances
Atomic Species
Balances
Extent of Reaction

13
Sample Problem to Illustrate the Application of the 3 Approaches
for Solving Material Balances for Reactive Processes

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Sample Problem to Illustrate the Application of the 3 Approaches
for Solving Material Balances for Reactive Processes

SOLUTION STRATEGY: unknowns can be solved by any of the following:

(1) Molecular Species Balances

(2) Atomic Species Balaces
(3) Extent of Reaction

• Each approach gives the same results; however, one approach may be more
convenient than the others
• Recommendation: <???> … be comfortable with any of the three
15 approaches
 DF Analysis for the 3 Approaches

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 DF Molecular Species Balances

DF formula for molecular species balances

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 DF Atomic Species Balances

DF formula for atomic species balances

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 DF Extent of Reaction

DF formula for extent of reacion

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 Molecular Species Balances

20
Sample Problem to Illustrate Molecular Species Balances for
Solving Material Balances for Reactive Processes

DF formula for molecular species balances

SOLUTION STRATEGY:

component balances
stoichiometric relationships

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Sample Problem to Illustrate Molecular Species Balances for
Solving Material Balances for Reactive Processes

Basis: 100 kmol

Ethane Feed Input + generation = output + consumption

Input + generation = output + consumption

Input + generation = output + consumption

22
Sample Problem to Illustrate Molecular Species Balances for
Solving Material Balances for Reactive Processes

Basis: 100 kmol

Ethane Feed Input + generation = output + consumption

Input + generation = output + consumption

23
 Atomic Species Balances

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Sample Problem to Illustrate Atomic Species Balances for Solving
Material Balances for Reactive Processes

SOLUTION STRATEGY:

Input (atoms) = output (atoms)

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Sample Problem to Illustrate Atomic Species Balances for Solving
Material Balances for Reactive Processes

Basis: 100 kmol

Ethane Feed Input (atoms) = output (atoms)

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 Extent of Reaction

27
Sample Problem to Illustrate Extent of Reaction for Solving
Material Balances for Reactive Processes

DF formula for extent of reacion

SOLUTION STRATEGY:

obtain “extent of reaction from

known exit stream(s)

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Sample Problem to Illustrate Extent of Reaction for Solving
Material Balances for Reactive Processes

Basis: 100 kmol Ethane Feed

FELDER’S GUIDELINES FOR SELECTING A METHOD FOR SOLVING MASS
BALANCES PROBLMES FOR REACTIVE PROCESSES

• ATOMIC BALANCES generally lead to the most

straightforward procedure, specially when more than one
reaction is involved

• EXTENTS OF REACTION are convenient for chemical

equilibrium problems and when equation involving software
is 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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END