ADDIS ABABA UNIVERSITY

ADDIS ABABA INSTITUTE OF TECHNOLOGY

SCHOOL OF CHEMICAL AND BIOENGINEERING
Introduction to Chemical Engineering

CHAPTER 4
MATERIAL BALANCES
Material balance on reactive processes
Part-2
By: wubiye mesfin 1
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES
 Material balances that involves chemical reactions
can be analyzed using three different methods:
1. Molecular species balances method (the
approach always used for non-reactive
systems)
2. Atomic species balances method
3. Extent of reaction method
 Each method leads to the same results, but any one
of them may be more convenient for a given
calculation.
 So it is important to become comfortable with all methods.
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES
 Remember the seven general procedures of
material balances, i.e.,
1. Drawing the flowchart and labeling
2. Scaling up/down the flowchart
3. Choosing basis of calculation
4. Stating the problem
5. Putting all in one unit
6. Analyzing the degree of freedom (DOF)
7. Solving the problem
 These procedures are also applied for balances
on reactive processes with the degree of freedom
analysis for reactive systems differing from the
nonreactive ones.
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4.2 METHODS OF MATERIAL BALANCES
ON REACTIVE PROCESSES
 To carry out degree of freedom analysis for reactive systems, it is
must first to understand the concept of:
 Independent Equations,
Equations
 Independent Species, and
 Independent Chemical Reactions.
Reactions
Independent Equations & Independent Species
 If two molecular species in the same ratio to each other
wherever they appear in a process and the ratio is
incorporated in the flowchart labeling, balanced on those
species will not be independent equation.
 Similarly, if two atomic species occurs in the same ratio
wherever they appear in a process, balances on those species
will not be independent equations.
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES
Independent Equations & Independent Species
EXAMPLE 1:
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES
Independent Equations & Independent Species
EXAMPLE 2:

ANSWER:
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES
INDEPENDENT CHEMICAL REACTIONS
1. Chemical reactions are independent if the
stoichiometric equation of any one of them cannot be
obtained by adding and subtracting multiples of the
stoichiometric equations of the others.
2. Applicable ONLY for molecular species balances and
extent of reaction methods.
EXAMPLE 1: Consider the reactions,
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES
INDEPENDENT CHEMICAL REACTIONS
EXAMPLE 2:

ANSWERS:
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES

1. Molecular Species Balances Method

 Must contain generation and/or consumption
terms One generation or
consumption term
 DOF analysis in general is: must either be
specified or calculated
No. of unknown labeled variables for each independent
rxn, which is why each
rxn adds a degree of
 No. of independent chemical reactions freedom to the system.
 No. of independent molecular species balances
 No. of other equations relating the unknowns
 No. of Degree of Freedom
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES

1. Molecular Species Balances Method

Example: Dehydrogenation of Ethane (C2H6 C 2H 4 + H 2)
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES
1. Molecular Species Balances Method

SOLUTION: Dehydrogenation of Ethane (C2H6 C 2H 4 + H 2)

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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES
2. Atomic Species Balances Method
 INPUT = OUTPUT (Atomic species can neither be
generated or consumed in chemical reactions).
 DOF analysis in general is:
No. of unknown labeled variables
 No. of indep. atomic species balances
 No. molecular balances of indep. nonreactive species
 No. of other equations relating the unknowns
 No. of Degree of Freedom
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES
2. Atomic Species Balances Method
Example: Dehydrogenation of Ethane (C2H6 C 2H 4 + H 2)

Solution:
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES

2. Atomic Species Balances Method

Solution:

(1)
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES

2. Atomic Species Balances Method

Solution:
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES

3. Extent of Reaction Method

 Using expressions for flow rates (amounts) of each species in
terms of extent of reaction.

DOF analysis in general is:

No. of unknown labeled variables
 No. of independent reactions (in terms of  )
 No. of ind. reactive species (in terms of  )
 No. molecular balances of indep. nonreactive species
 No. of other equations relating the unknowns
 No. of Degree of Freedom
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES
3. Extent of Reaction Method
Example: Dehydrogenation of Ethane (C2H6 C 2H 4 + H 2)

Solution:
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES

EXERCISE
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4.2 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES

SOLUTION:
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4.2.1 METHODS OF MATERIAL BALANCES ON
REACTIVE PROCESSES INVOLVING RECYCLE

Reactant Conversion
 Two definitions of reactant conversion are
used in the analysis of chemical reactors with
product separation and recycle of
unconsumed reactants:

Overall Conversion =

reactant input to process  reactant output from process

reactant input to process
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4.2.1 METHODS OF MATERIAL BALANCES ON REACTIVE

PROCESSES INVOLVING RECYCLE

Reactant Conversion
Overall Conversion:

REACTOR SEP.

RECYCLE
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4.2.1 METHODS OF MATERIAL BALANCES ON REACTIVE

PROCESSES INVOLVING RECYCLE

Reactant Conversion

Single-Pass Conversion =
reactant input to reactor  reactant output from reactor
reactant input to reactor

REACTOR SEP.

RECYCLE
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4.2.1 METHODS OF MATERIAL BALANCES ON REACTIVE

PROCESSES INVOLVING RECYCLE

Reactant Conversion
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4.2.1 METHODS OF MATERIAL BALANCES ON REACTIVE

PROCESSES INVOLVING RECYCLE

Example:
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4.2.1 METHODS OF MATERIAL BALANCES ON REACTIVE

PROCESSES INVOLVING RECYCLE
Solution:
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4.2.1 METHODS OF MATERIAL BALANCES ON REACTIVE

PROCESSES INVOLVING RECYCLE

Solution:
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4.2.1 METHODS OF MATERIAL BALANCES ON REACTIVE

PROCESSES INVOLVING RECYCLE

Solution:
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4.2.1 METHODS OF MATERIAL BALANCES ON REACTIVE

PROCESSES INVOLVING RECYCLE

Solution:
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4.2.1 METHODS OF MATERIAL BALANCES ON REACTIVE

PROCESSES INVOLVING RECYCLE

Solution:
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4.2.1 METHODS OF MATERIAL BALANCES ON REACTIVE
PROCESSES INVOLVING RECYCLE

Solution:
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4.2.1 METHODS OF MATERIAL BALANCES ON REACTIVE
PROCESSES INVOLVING RECYCLE

Solution:
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4.2.2 METHODS OF MATERIAL BALANCES ON REACTIVE
PROCESSES INVOLVING RECYCLE AND PURGE

PURGING
 A problem may arise in processes that involving recycle. Suppose a
material that enters with the fresh feed or is produced in a reaction
remains entirely in a recycle stream, rather than being carried out in a
process product.
 If nothing were done about this situation, the substance would
continuously enter the process and would have no way leaving; it
would therefore steadily accumulate, making the attainment of steady
state impossible.
 To prevent this buildup, a portion of the recycle stream must be
withdrawn as a purge stream to rid the process of the substance in
question.
4.2.2 METHODS OF MATERIAL BALANCES ON REACTIVE
44

PROCESSES INVOLVING RECYCLE AND PURGE

PURGING
The flowchart shown below for the production of ethylene oxide from
ethylene. The reaction is 2C2H4+O2 2C2H4O

Fig.
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4.2.2 METHODS OF MATERIAL BALANCES ON REACTIVE
PROCESSES INVOLVING RECYCLE AND PURGE
PURGING
 If there were no nitrogen (or any other inert and insoluble
substance) in the feed, there would be no need for a purge
stream.
 However ,there is nitrogen. It enters the system at a rate of 113
mol/s and leaves the system at the same rate in the purge
stream.
 If the system were not purged, nitrogen would accumulate at
this rate until something (probably unpleasant) occurred to
shut down the process.

 Material balance calculation on the system involving recycle and

purge follow the procedures given in the pervious section.
 When labeling the flowchart, note that the purge stream and the
recycle stream before and after the purge takeoff all have the same
composition.
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4.2.3 Material balance in combustion
•Combustion—the rapid reaction of a fuel with oxygen
•combustion products are (CO2, H2O, and possibly CO and SO2).
•The significance of these reactions lies in the tremendous quantities of
energy they release energy that is used to boil water to produce steam,
which is then used to drive the turbines that generate most of the world’s
electrical power.
•Most of the fuel used in power plant combustion furnaces is either coal
(carbon, some hydro - gen and sulfur, and various noncombustible
materials), fuel oil (mostly high molecular weight hydrocarbons, some
sulfur), gaseous fuel (such as natural gas, which is primarily methane), or
liquefied petroleum gas, which is usually propane and/or butane.
•When a fuel is burned, carbon in the fuel reacts to form either CO2 or CO,
hydrogen forms H2O, and sulfur forms SO2
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Examples:
C +O2 CO2 Complete combustion of carbon
C3H8 + 5 O2 3CO2 + 4 H2O Complete combustion of propane
C3H8 + 5 O2 3 CO + 4 H2O Partial combustion of propane
CS2 + 3 O2 CO2 + 2 SO2 Complete combustion of carbon disulfide
Dry air has the following average molar composition:
N2 78.03%
O2 20.99%
Ar 0.94%
CO2 0.03%
H2, He, Ne, Kr, Xe 0.01%
Total= 100.00%
Example 1: Wet Basis to Dry Basis.
A stack gas contains 60.0 mole% N2, 15.0% CO2, 10.0% O2, and the balance H2O.
Calculate the molar composition of the gas on a dry basis.
Solution:
Basis: 100 mol Wet Gas
60.0 mol N2 60/85= 0.706 molof N2/mol of dry gas
15.0 mol CO2 15/85 = 0.176 mol of CO2/mol of dry gas
10.0 mol O2 10/85 = 0.118 mol of O2/mol of dry gas
85.0 mol dry gas
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Theoretical and Excess Air

•Theoretical oxygen is the amount needed for complete combustion of reactants
to form CO2 and H2O.
•Air that contains the theoretical amount of oxygen is called theoretical air.
Theoretical air does not depend on how much of a reactant is converted.
• The difference between the amount of air initial fed and the theoretical air is
known as excess air. Therefore, percentage excess air is defined as,
% excess air = {[Air (fed) - Air (theoretical)]/Air (theoretical)}×100.
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Example 3: 25%excess air is supplied to burn methane completely, take 100moles of
CH4 as a basis and calculate the amount of air fed to the reactor and moles of each
component in the stack gas.
Solution:
Given: basis of 100moles CH4 find:
25% excess air moles of air fed to reactor
complete conversion of methane moles each component in the stack gas
CH4 + 2O2 CO2 + 2H2O

100% CH4 n1mol CO2

reactor n2 mol H2O
n3 mol O2
n mole air n4 mol N 2
0.21%molO2
0.79% molN2 /mole air
nO2 = 2* moles CH4fed = 200moles, 200 O2 * mol of air/0.21molO2=952 mol of air

%excess air= moles air fed – moles of air theoretical × 100 = moles air-952 *100
moles of air theoretical 952
moles air fed = 1190mole
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To calculate moles of component in the stack
gas
nout= nin+ vi£ £=100
nCH4 = 100-1*£=0
CO2 : n1 =0+1*£ =100mole
H2O: n2 = 0+2*£ = 200mole
O2 : n3 =0.21*1190-2*£ = 49.9 mole
N2 : n4 = 0.79*1190= 940mole

Example 4:
Ethane (C2H6) is burned with 50% excess air. The percentage
conversion of the ethane is 90%; of the ethane burned, 25% reacts to
form CO and the balance to form CO2. Calculate the composition of
the fuel gas and the ratio of water to dry fuel gas.
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EXAMPLE 5: Material balances on a distillation column

A mixture containing 45% benzene (B) and 55% toluene (T) by mass is fed to a
distillation column. An overhead stream of 95 wt% B is produced, and 8% of
the benzene fed to the column leaves in the bottom stream. The feed rate is
2000 kg/h. Determine the overhead flow rate and the mass flow rates of
benzene and toluene in the bottom stream.
Solution
Basis : Given Feed Rate
The labeled flowchart is as follows.
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There are three unknowns on the chart - D, wB, and wT - and therefore three equations are
needed. We are entitled to write only two material balances since two species are involved
in the process; the third equation must therefore come from additional given information
(the amount of benzene in the bottom stream.) The latter relation is.

B in bottom stream = 0.080 (B in feed)

⇓
wB (kg B/h) = 0.080[(0.45)(2000) kg/h]
⇓
wB = 72 kg B/h (Write 72 in place of wB on the chart)

Toluene and total mass balances each involve two unknowns, D and wT, but a benzene
balance involves only one, D.

Benzene Balance

( 0 .4 5 )( 2 0 0 0 ) kg B = 0.95 D + wB
h
⇓ wB = 72 kg B/h
⇓
D = 870 kg/h
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Total Mass Balance (A toluene balance could be used equally well)

2000 kgh = D + wB + wT

D = 870 kg/h
wB = 72 kg/h wT=1060 kg T/h
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END OF CHAPTER 4