CHPE3112

Chapter 4
Fundamentals of Material
Balances

Process Classification
 Batch process:
 Batch processes are commonly used for A->B
small scale processes.
Batch reactor

 Continuous process: A

B
A->B

 Continuous processes are much more common in industrial

applications, Why?
 Examples: CSTR (Continuous Stirred Tank Reactor), distillation
columns, tubular reactors, etc…
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 Process Classification, cont
 Semibatch Process:
 Any process that is neither batch nor continuous, is called
Semibactch!

A
or B
A->B A->B

Process Classification, cont

 Processes are also classifieds according to change with time
as steady state or unsteady State (transient).

 Steady state: NO change of any process variable (T, P, flow

rates, concentrations, etc,,,) with time.

 Unsteady state (transient): If any of the process variables

changes with time.

 By their nature; batch and semibatch processes are unsteady

state operations

 Continuous processes can be steady state or unsteady state.

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2
 The General Balance Equation
 Law of conservation of mass, “mass can neither be created nor
destroyed”

•Generation
Input output
•Consumption
•Accumulation

Input-Output + Generation -Consumption = Accumulation

crossing system within system boundary

boundary
5

Special cases of the general balance equation

 For non-reactive systems, generation and consumption terms are

zero.

 For steady state conditions (no change with time), accumulation

term is zero.

 Thus for non-reactive systems at steady state, the general balance

equation reduces to:

Input = Output
 This is the simplest form of the general balance equation.

3
 Process Flowcharts (Flow Diagrams)
 A flowchart includes units of the process and the streams
connecting between these units. Information such as (molar flow
rate, mass flow rate, compositions, etc.) and conditions such as
(Temp, Pressure) are shown on corresponding streams
 If the information (variable) is known, the value is written in the
corresponding place of the flow chart.

 If stream information is not known, a variable (name) is assigned

for the unknown value such as (ṅ1, ṅ2 , xA, yA, …etc), and written
with proper units in the corresponding place of the flowchart.

If you know the stream composition

but not the flow rate:

 When unknowns are dependent, they are not assigned a new name,
they should be written in terms of the unknown(s) they depend on.

If you know the stream flow rate

but not the composition:

4
 Process flowchart for material balance

Process Flow Diagram

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5
 Degree of Freedom Analysis
Dependent vs. Independent equations:
2x + y = 4 •Dependent equations
4x + 2y = 8
2x + y = 7 •Independent equations
x+y=5 •Two unknowns and two equations

an independent equation, is the equation that can NOT be derived by

any linear combination of the other equations .

2x+ y+ z =12 •Independent equations

3x+2y-2z =10 •Three unknowns and two equations
Degree of Freedom is : number of unknowns-number of
independent equations (ndf=nunknowns-nindependent eqns)

11

Three Possibilities for ndf

ndf = 0
 The number of unknowns equals the number of independent equation,
the problem can be solved and has (only one) solution.

ndf > 0
 The number of unknowns is more than the number of independent
equation, system is underspecified, the problem has infinite number of
solutions.

ndf < 0
 The number of independent equations is more than the number of
unknowns. Either flowchart is incompletely labeled or system is
overspecified with redundant and possibly inconsistent relations.

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6
 When solving material balance problems:
I. ONLY Independent balances should be counted for degree of freedom
analysis.
II. The maximum number of independent balances for non-reactive process
equals the number of species (components) in the input and output
streams.
III. Some unknowns can be calculated from physical or chemical properties
without the need for balance, in addition sometimes a relation between
some unknowns is provided, this should be counted in the degree of
freedom as “other relations” : ndf = nunknowns-nindep eqns - Other Relations
IV. Always start with balances that involve the least number of unknowns.

13

Dilution Problem:
It is desired to produce an 8 wt% NaOH solution by diluting a stream of the 20 wt%
solution with a stream of pure water. Calculate the mass ratio of pure water/20 wt%
solution needed to be mixed to prepare the 8 wt% NaOH solution.

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7
TEST YOURSELF:
It is needed to prepare a 28 wt.% sulfuric acid by mixing 20 wt% sulfuric acid and 40
wt% sulfuric acid. Calculate the ratio of the 20 wt% acid to the 40 wt% acid that
should be mixed to prepare the 28 wt% acid.

15

Distillation Problem:
Two thousand kilograms per hour of a mixture of Methanol (M) and water (W) containing
60 wt% methanol is to be separated using a distillation column into two fractions. The mass
flow rate of the top stream is 1176 kg/h and the mass fraction of methanol in the top stream
is 0.95, calculate the flow rate and composition of the bottom stream.

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8
Solution:

17

Absorption Problem :
A gas mixture containing 15 mole% A and 85 mole% inert gas is fed to an absorption column
where it is contacted with a pure liquid solvent B which absorbs A but not the Inert. The mole
ratio of solvent stream to the gas stream entering the column is 2:1. The composition of the
gas leaving the absorber is: 2.5 mol% A, 1.5 mol% B and the balance is inert. Calculate the
mol% of the solute “A” in the leaving solvent stream and the % Recovery of A in this process.

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Solution:

19

Extraction Problem :
Acetic Acid (AA) is to be separated from water (W) using the solvent Hexane (H) in an
extraction process. Hexane can be assumed immiscible in water. A stream of 200 kg/h of 14
wt% acetic acid (balance is water) and a stream of pure hexane are fed to the extractor. The
acetic acid compositions in the Organic phase (Extract) and Aqueous phase (Raffinate) are
12wt% and 0.5 wt% respectively. Calculate the flow rates of the Solvent, Extract and
Raffinate streams and the percent recovery of acetic acid in this process. “See Problem 4.7”

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Solution:

21

Example 4.2-4
Air is bubbled through a drum of liquid hexane at a rate of 0.10 kmol/min. The gas stream
leaving the drum contains 10 mole% hexane vapor. Air may be considered insoluble in liquid
hexane. Use an integral balance to estimate the time required to vaporize 10 m3 of the liquid.
Given: SGHex = 0.659, MWHex= 86.2

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Solution:

23
do examples 4.2-2 and 4.2-3 in your textbook

Example 4.3-1

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Solution:

25

Example 4.3-2

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Example:4.3-4: A stream of humid air enters a condenser in which 95% of the water vapor
in the air is condensed. The flow rate of the condensate is measured and found to be 225 L/h. Dry air
may be taken to contain 21 mol% Oxygen with the balance Nitrogen. Calculate the flow rate of the gas
stream leaving the condenser and the mole fractions of oxygen, nitrogen and water in this stream.

Gas stream
Humid air ṅ4 mol O2 /h
ṅ1 mol DA/h Condenser ṅ5 mol N2/h
0.21 mol O2/mol ṅ6 mol H2O/h

0.79 mol N2/mol

225 L H2O/h
ṅ2 mol H2O/h
ṅ3 mol H2O/h ; [95% of water in feed]

Degree of freedom analysis:

 Number of Unknowns?
 Number of independent balances?
 Other relations:

27

If we had been given an additional information; for example that the entering air Contains 10 mol %
water. Then the flowchart will be as follows

ṅ1 mol humid air/h Gas stream

0.1 mol H2O/mol ṅ3 mol O2 /h
Condenser
0.9 mol DA/mol ṅ4 mol N2/h
0.21 mol O2/mol DA ṅ5 mol H2O/h
0.79 mol N2/mol DA)
225 L H2O/h
ṅ2 mol H2O/h ;
[95% of water in feed]

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Solution:

29

Recycle and Bypass

A A+B B
fresh feed Combined
AB
feed
Mixing A
Point
Recycle stream

Unit
Splitting
Point
Bypass Stream

DOF analysis can be done on overall system, the unit, mixing or splitting points.
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 Example 4.5-1- Air Conditioning Unit
Fresh air containing 4.0 mole % water vapor is to be cooled and
dehumidified to a water content of 1.70 mole % water. A stream of fresh
air is combined with a recycle stream of previously dehumidified air and
passed through the cooler. The combined stream entering the unit contains
2.30 mole % water. Taking a basis of 100 mol of dehumidified air.
Calculate the moles of fresh feed, moles of water condensed, and moles
of dehumidified air recycled.
Process Flowchart and DOF Analysis :

31

Solution:

32 Practice Problems “Single Unit Processes”: 4.5-a,4.7, 4.12 ,4.20 & 4.32

16
 Balance on Multiple-Unit Processes
 So far we dealt with a single unit process, and the system was
mainly the unit itself for all the balances.
 Consider the two unit process, where several subsystem
boundaries can be defined for writing balance equations.
Feed 2

Feed 1 UNIT UNIT Product 3

1 2

Product 1 Product 2 Feed 3

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DOF analysis will help us to decide the sequence of these balances.

Example 4.4-1 Two-Unit Process

A labeled flowchart of a continuous steady state two unit process is shown below. Each stream
contains two components A and B, in different proportions. Three streams whose flow rates
and/or compositions are not known are labeled 1, 2, and 3. Calculate the unknown flow rates
and compositions of streams 1,2 & 3. 40.0 kg/h 30.0 kg/h
0.9 kg A/kg 0.6 kg A/kg
0.1 kg B/kg 0.4 kg B/kg

100.0 kg/h
Unit 1 1 2 Unit 2 3
0.5 kg A/kg
0.5 kg B/kg
30.0 kg/h
0.3 kg A/kg
0.7 kg B/kg

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 DOF Analysis
40.0 kg/h 30.0 kg/h
0.6 kg A/kg
0.9 kg A/kg
0.1 kg B/kg ① 0.4 kg B/kg
③ ②
100.0 kg/h ṁ1 kg/h ṁ2 kg/h ṁ3 kg/h
Unit1 x1 kg A/kg x2 kg A/kg
Unit 2 x3 kg A/kg
0.5 kg A/kg (1-x1) kg B/kg (1-x2) kg B/kg (1-x3) kg B/kg
0.5 kg B/kg ④
30.0 kg/h
0.3 kg A/kg
0.7 kg B/kg

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Solution:

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 Example 4.4-2 Extractive Distillation Process
M (Solvent) M (Solvent)

Feed Raffinate 1
Mixer Mostly W , some A &M
Mixer
50wt%A , 50wt% W Raffinate 2
Mostly W, some M & A
Settler 1 Settler 2

Extract 1 Extract 2
Mostly M &A, some W Mostly M & A, some W

Overhead product
Combined extracts Mostly A, some M & W

Distillation column

A : Acetone (solute)
W : Water (diluent) Bottom effluent
M : MIBK (solvent) Mostly M, some A & W

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100 kg M 75 kg M

Raffinate 1 Raffinate 2
100 kg
mA2 kg A 43.1 kg
0.5 A
Extractor 1 Extractor 2
mM2 kg M 0.053 kg A/kg
0.5 W 0.016 kg M/kg
mw2 kg W
0.931 kg W/kg

Extract 1 Extract 2
m1 kg m3 kg
0.275 kg A/kg 0.09 kg A/kg
xM1 kg M/kg 0.88 kg M/kg
(1 - 0.275 - xM1) kg w/kg 0.03 kg w/kg

m5 kg
0.97 kg A/kg
mA4 kg A
0.02 kg M/kg
mM4 kg M
0.01 kg w/kg
mw4 kg W
Distillation
Column

mA6 kg A
mM6 kg M
38 mw6 kg W

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 DOF Analysis 75 kg M
100 kg M

Raffinate 1 Raffinate 2
100 kg
mA2 kg A 43.1 kg
0.5 A
Extractor 1 Extractor 2
mM2 kg M 0.053 kg A/kg
0.5 W 0.016 kg/kg
② ③
mw2 kg W
0.931 kg W/kg
6
Extract 1 Extract 2
m1 kg m3 kg
0.275 kg A/kg 0.09 kg A/kg
xM1 kg M/kg 0.88 kg M/kg
(1 - 0.275 - xM1) kg w/kg 0.03 kg w/kg

4
m5 kg
mA4 kg A
5 0.97 kg A/kg
0.02 kg M/kg
mM4 kg M
0.01 kg w/kg

Distillation
mw4 kg W

column
mA6 kg A
① mM6 kg M
mw6 kg W

Solution (DOF):

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 Material Balance Sequence
 Start balance around the two extractor to get (m1 & XM1)
 Then do balance around First or second extractor to get
(mA2,mM2 & mw2)
 Then do balance around mixing point to get (mA4, mM5 &
mw4)
 At this point we can go NO Further!, so the problem is
underspecified and can’t be solved!.

 Practice HW: If m5 is given as 45 kg, calculate ALL the

unknowns in the flowchart and bring the solution with you
next class.

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Example 4.5-2-Evaporative Crystallization Process

The flowchart of a steady-state process to recover crystalline potassium chromate (K2CrO4 ) from an
aqueous solution of this salt is shown below.

water

4500 kg/h 49.4 % K2CrO4 CRYSTALLIZE Filter cake

EVAPORATOR
& FILTER
33.3% K2CrO4 Solid K2CrO4 & 36.4 % solution

Filtrate

36.4 % K2CrO4

Forty-five hundred kilograms per hour of a solution that is one-third K2CrO4 by mass is joined by a
recycle stream containing 36.4% K2CrO4 , and the combined stream is fed into an evaporator. The
concentrated stream leaving the evaporator contains 49.4% K2CrO4 ; this stream is fed into a
crystallizer in which it is cooled (causing crystals of K2CrO4 to come out of solution) and then
filtered. The filter cake consists of K2CrO4 crystals and a solution that contains 36.4% K2CrO4 by
mass; the crystals account for 95% of the total mass of the filter cake. The solution that passes
through the filter, also has 36.4% K2CrO4 , is the recycle stream.

1. Calculate the rate of evaporation, the rate of production of crystalline K2CrO4 , the feed rates that the
evaporator and the crystallizer must be designed to handle, and the recycle ratio (mass of recycle)
/(mass of fresh feed).
2. Suppose that the filtrate were discarded instead of being recycled. Calculate the production rate of
crystals. What are the benefits and costs of the recycling?
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 K : K2CrO4
W: Water

43

Solution:

44

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 Part 2-with NO Recycle

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Solution:

46
Practice Problems “Multiple-Unit Processes” : 4.29, 4.30

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 Balances on Reactive Systems
 Stoichiometry: Is the theory of the proportions in which chemical species combine
with one another in a chemical reaction.
 Consider the following reaction.
2 SO2 + O2 → 2 SO3
 The number precedes the formula for each species is called Stoichiometric coefficient.

 The ratio of the stoichiometric coefficients of two species in the balanced reaction is
called stoichiometric ratio. (reaction must be balanced before doing any calculation)

2 mol SO 3 genrated 2 moles SO 2 consumed

; and are stoichiometric ratios
1 mol O 2 consumed 2 moles of SO 3 genrated

 Stoichiometric ratios can be used as a conversion factors to calculate the

amount of reactants or products in a reaction.

47

TEST YOURSELF!
For the reaction: 2 SO2 + O2 → 2 SO3
If 1600 kg/h of SO3 (MW= 80) is produced, Calculate the mass flow rate (kg/h) of
O2 (MW= 32) needed to be fed.

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 Fractional & Percentage Conversion
(n A ) reacted
Fractional conversion of a species A is: f 
(n A ) fed

Percentage conversion = f x100%

PRACTICE
Consider the reaction C2H2 + 2H2 → C2H6 suppose 20.0 kmol of C2H2, and 50
Kmol of H2 and 50.0 kmol of C2H6 are charged into a batch reactor. If after some
time 30.0 kmol of H2 reacted. How much of each species will be present in the
reactor at this moment?
C2H2 + 2H2 → C2H6
@ t=0 20 50 50

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Extent of Reaction
 To generalize for any reaction; let us define νi to be the stoichiometric
coefficient of the i th species in the reaction.
 νi is negative for reactants (consumed) and positive for products (generated).

 Then; the moles or molar flow rate of species i is given by the following
equations:-

(ni)remaining = nio + νi ξ or (ṅi)out = ṅio + νi ξ

Where ξ (zeta) is the extent of reaction.
 The extent of reaction ξ can be calculated as:

ξ = moles of i reacted/|νi| “when i is a reactant”

ξ = moles of i produced /νi “when i is a product”

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Extent of Reaction Practice:
Consider the ammonia formation reaction N2 + 3H2 → 2NH3 If the feed to the reactor
consists of 100 mol/s N2, 300 mol/s H2 and 1 mol/s of Argon (an inert gas). For a fractional
hydrogen conversion of 0.60, calculate the extent of reaction , the out flow rate of hydrogen,
Nitrogen and Ammonia.

51

Example 4.6-1: Reaction Stoichiometry

Acrylonitrile is produced in the reaction of propylene, ammonia and oxygen as follow:
3
C 3 H 6  NH 3  O2  C 3 H 3 N  3H 2 O
2
The feed contains 10 mol % propylene, 12 mol% ammonia, and 78 mol% air. A fractional
conversion of 30% of the limiting reactant is achieved. Taking 100 mol of feed as a basis,
determine:
a) Which reactant is limiting.
b) The percentage by which each of the other reactants is in excess.
c) The molar amounts of all product gas constituents for a 30 % conversion of the limiting
reactant.

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Solution:

53

Multiple Reactions, Yield & Selectivity

Consider the dehydrogenation of ethane to produce ethylene :
C2H6 → C2H4 + H2 (Desired Product)
once some hydrogen is produced, it can react with ethane to produce methane (undesired)
C2H6 + H2 → 2CH4 (side reaction)
moreover, ethylene can react with ethane to form methane and propylene (undesired)
C2H4 +C2H6 → C3H6 + CH4 (side reaction)

moles of desired product formed

yield 
moles that would have been formed if there were no side reactions
and the limiting reactant had reacted compleletely

moles of desired product formed

Selectivity 
moles of undesired product formed

CAUTION: There are more definitions for Yield & Selectivity in literature!
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 PRACTICE:

55

Solution:

56

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 Extent of reaction for multiple reactions
If a set of reactions takes place and νij is the stoichiometric coefficient of
substance i in reaction j (νij is negative for reactants and positive for
products)……then
ni out  ni 0   ij j
j

Consider the following pair of reactions in which ethylene is oxidized either to ethylene
oxide (desired) or to carbon dioxide (undesired):
C2H4 + ½ O2 → C2H4O
C2H4 + 3O2 → 2CO2 + 2H2O
The moles or molar flow rates of each of the five species involved in these reactions can
be expressed as:

(nC2H4)out =
(nO2)out =
(nC2H4O)out =
(nCO2)out =
57
(nH2O)out =

Example 4.6-3
The reactions : C2H6 → C2H4 + H2
C2H6 + H2 → 2CH4
Take place in a continuous reactor at steady state. The feed contains 85 mole % ethane
(C2H6) and the balance is inert (I). The fractional conversion of ethane is 0.501, and
the fractional yield of ethylene (C2H4) is 0.471; calculate the molar composition of the
product gas and the selectivity of ethylene to methane production.

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Solution:

59

Balances on Reactive Processes

 Three different methods can be used to carry out material balance for
reactive systems:
 Consider the reaction: C2H6 → C2H4 + H2

 Molecular Species Balances :(C2H6 , C2H4 & H2 )

 Each molecular species will either be consumed or produced in the reaction
(Consumption and/or Generation terms have to be included in the balance).
 Atomic species balances: (C & H)
 Atoms can neither be created nor destroyed in a chemical reaction.
 NO Consumption or Generation terms are included in the balance equation
 The general balance equation is reduced to INPUT = OUTPUT
 Extent of reaction method :(C2H6 , C2H4 & H2 )

ni out  ni 0   ij j
j
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 Dependant Species
Consider a process in which a stream of CCl4 is vaporized into a stream of air

ṅ1 mol O2/s ṅ1 mol O2/s

3.76 ṅ1 mol N2/s 3.76 ṅ1 mol N2/s
ṅ4 mol CCl4(v) /s

ṅ2 mol CCl4(l) /s ṅ5 mol CCl4(l) /s

o N2 & O2, N & O, Cl & C are Dependent species

Dependent Reactions:
A chemical reaction is dependent if it can be obtained by adding and/or subtracting
other reactions.
Is there a dependent reaction here?
[1] A →2B
[2] B → C
61 [3] A → 2C

Degree of Freedom Analysis (Reactive System)

 Molecular species balance:
Number of unknown labeled variables
+ Number of independent chemical reactions (one Gen. or Cons. for each)
- Number of independent molecular species balances
- Number of other equations relating unknown variables.

 Atomic species balances:

Number of unknown labeled variables
- Number of independent atomic species balances
- Number of independent non-reactive (Inert) molecular species balances.
- Number of other equations relating unknown variables.

 Extent of reaction:
Number of unknown labeled variables
+ Number of independent reactions (one extent of reaction for each one).
- Number of independent molecular species.
- Number of other equations relating unknown variables.

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Example 4.7-1: Methane is burned with air in a continuous steady state combustion reactor to
yield a mixture of carbon monoxide, carbon dioxide, and water. The reactions taking place are:

CH4  1.5 O2  CO  2H2O

CH4  2O2  CO2  2H2O
The feed to the reactor contains 7.8 mol% CH4 , 19.4 mol% O2 ,and 72.8 mol% N2. The percentage
conversion of methane is 90 %, and the gas leaving the reactor contains 8 mol CO2/mol CO.
a. Carry out a DOF analysis on the process.
b. Calculate the molar compositions of the product stream using molecular species balance, atomic
balances, and extent of reaction.

Basis : 100 mol feed nCH

4
nCO
7.8 mol CH4 nCO
19.4 mol O2 REACTOR 2
72.8 mol N2
nH O
2
nO
2
nN
2

63

Degree of freedom analysis ndf

nCH
4
nCO
7.8 mol CH4 nCO
19.4 mol O2 REACTOR 2
72.8 mol N2
nH O
2
nO
64 nN
2
2

32
Solution:

65

Practice:
For example 4.6-3, conduct DOF Analysis and calculate the number of moles for
each species in the product using:
Molecular Species Balance.
Atomic Species Balance

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 Product Separation and Recycle
Consider the following labeled flowchart for a simple chemical process based on the
reaction A → B

75 mol A/min 100 mol A/min 25 mol A/min 75 mol B/min

Reactor Separator
75 mol B/min

25 mol A/min

How much is the conversion of A?

reactant input to process - reactant output from process
overall conversion 
reactant input to process
75 - 0
overall conversion of A  100  100%
75

reactant input to reactor - reactant output from reactor

single pass conversion 
reactant input to reactor
100 - 25
single pass conversion   100  75%
100
67

Purging
Consider the production of ethylene oxide from ethylene
2C2H4 + O2 → 2C2H4O

Recycle Purge stream

40 mol C2H4/s 10 mol C2H4/s
20 mol O2/s 5 mol O2/s
452 mol N2/s 113 mol N2/s

Solvent
Fresh feed 100 mol C2H4/s 50 mol C2H4/s
60 mol C2H4/s 50 mol O2/s 25 mol O2/s
Reactor
30 mol O2/s 565 mol N2/s 565 mol N2/s
113 mol N2/s 50 mol C2H4O/s

Product
50 mol C2H4O/s
solvent

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 Example:4.7-2 Dehydrogenation of propane
Propane is dehydrogenated to form propylene in a catalytic reactor C3H8 → C3H6 + H2 , The
process is to be designed for a 95 % overall conversion of propane. The reaction products are
separated into two streams: the first, which contains H2, C3H6, and 0.555 % of the propane that
leaves the reactor is taken off as product; the second stream, which contains the balance of the
unreacted propane and 5 % of the propylene in the product stream is recycled to the reactor.
Calculate the composition of the product, the ratio (moles recycled/moles fresh feed), and the
single pass conversion.

Product
100 mole C3H8 n1 mol C3H8 n3 mol C3H8 n6 mol C3H8 (0.555 % of n3)
Reactor n4 mol C3H6 Separator n7 mol C3H6
n2 mol C3H6
n5 mol H2 n8 mol H2

n9 mol C3H8
n10 mol C3H6 ( 5 % of n7)

69

Solution:

70

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Solution:

71

Example 4.7-3:
Methanol is produced in the reaction of carbon dioxide and hydrogen according to the reaction:
CO2 + 3H2 → CH3OH + H2O
The fresh feed to the process contains hydrogen, carbon dioxide , and 0.40 mol % inert (I). The reactor
effluent passes to a condenser that removes essentially all of the methanol and water formed and none of
the reactants or inerts. The latter substances are recycled to the reactor. To avoid buildup of the inerts in the
system, a purge stream withdrawn from the recycle.
The feed to the reactor (not the fresh to the process) contains 28 mol % CO2, 70 mol % H2, and 2 mol %
inerts. The single pass conversion of hydrogen is 60 %. Calculate the molar flow rates and molar
compositions of the fresh feed, the total feed to the reactor, the recycle stream, and the purge stream for a
methanol rate of 155 kmol CH3OH/h.
Process flow chart, using a basis of 100 kmol combined feed

C : for CO2
H : for H2

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 DOF Analysis
Overall System (atomic):
 Condenser (molecular)
Feed Mixing Point (molecular)
 Purge splitting point
Reactor (atomic)

CO2 + 3H2 → CH3OH + H2O

nr mol Recycle np mol purge
x5C mol CO2/mol x5C mol CO2/mol
x5H mol H2/mol x5H mol H2/mol
(1-x5C-x5H) mol I/mol (1-x5C-x5H) mol I/mol

n5 mol
x5C mol CO2/mol
x5H mol H2/mol
(1-x5C-x5H) mol I/mol

n1 mol CO2
n0 mol Fresh feed 100 kmol n2 mol H2
Reactor
x0C mol CO2/mol 0.28 mol CO2/mol 2.0 mol I
(0.996-x0C) mol H2/mol n3 kmol CH3OH/h
0.70 mol H2/mol
0.004 mol I/mol n4 mol H2O
0.02 mol I/mol
Product
n3 kmol CH3OH/h
73 n4 mol H2O

Ex. 4.7-3, solution

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Solution:

75

Solution:

76

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 Combustion Reactions
 Typical products of a combustion reactions are CO, CO2 & H2O
 Combustion reactions are always run with excess amount of air, to reduce CO and achieve
complete combustion of the fuel.

 Complete combustion means:

 All fuel is consumed or (100% conversion)
 All Carbon is oxidized to CO2 ( zero CO ) and all H2 “which is fuel” is oxidized to H2O.

 Theoretical Oxygen: The moles of Oxygen needed for complete combustion of all fuels ( if
more than one) fed to the reactor.

 Theoretical air: The quantity of air that contains the theoretical oxygen

moles air fed  moles airtheoretical

% Excess air  100
moles airtheoretical
Note that: %excess air = %excess oxygen
 Composition of combustion products is either reported on wet basis (including water)
or dry basis (excluding water).
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Example 4.8-1:
1) Wet basis ➯ 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.

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2) Dry basis ➯ Wet basis
An Orsat analysis ( a technique for stack gas analysis) yields the following dry basis
composition: N2 65 % , CO2 14 %, CO 11 % , and O2 10 % . A humidity measurements
shows that the mole fraction of H2O in the stack gas is 0.07. Calculate the stack gas
composition on a wet basis.

79

Solution:

80

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 Example 4.8-2
100 mol/h of butane (C4H10) and 5000 mol/h of air fed into a combustion
reactor. Calculate the percent excess air.
The balanced combustion C4H10+ 6.5 O24CO2 +5H2O
reactions are: C4H10+ 4.5 O24CO +5H2O

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Material Balances on Combustion Reactors

Example 4.8-3: Ethane is burned with 50 % excess air. The percentage
conversion of the ethane is 90 % . 25 % of the ethane burned reacts to form CO
and the balance reacts to form CO2 . Calculate the molar composition of the
stack gas on a dry basis and the mole ratio of water to dry stack gas.
The balanced combustion reactions are:
7
C2 H 6  O2  2CO2  3H 2 O
2
5
C2 H 6  O2  2CO  3H 2 O
2
For a Basis of 100 mole C2H6 feed
n1 C2H6 =
100 C2H6 n2 O2 =
n3 N2 =
REACTOR n4 CO =
50 % excess air
n5 CO2 =
n0 air =
0.21 mol O2/mol n6 H2O =
0.79 mol N2/mol

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Solution:

83

Example: 4.8-4 :A hydrocarbon gas is burned with air. The dry basis product gas
composition is 1.5 mole % CO, 6.0 % CO2, 8.2 % O2, and 84.3 % N2. There is no atomic
oxygen in the fuel. Calculate the ratio of hydrogen to carbon in the fuel gas and
speculate on what the fuel might be. Then calculate the percent excess air fed to the
reactor.
Using a basis of 100 mol Product dry gas, the flowchart is:

nc mol C
100 mol dry gas
nH mol H
Furnace 1.5 mol CO
na mol air 6 mol CO2
0.21 mol O2/mol 8.2 mol O2
0.79 mol N2/mol 84.3 mol N2
nw mol H2O

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Solution:

85 Practice Problems: 4.51 (a&b), 4.56(a&b), 4.59, 4.60 & 4.69-a

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