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CHE 31.

INTRODUCTION TO CHEMICAL ENGINEERING CALCULATIONS

Lecture 10
Solving Material Balances Problems
Involving Reactive Processes

Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Material Balances on Reactive Processes

Material balances on processes involving chemical reactions


may be solved by applying:

1. Molecular Species Balance a material balance


equation is applied to each chemical compound
appearing in the process.

2. Atomic Species Balance the balance is applied to each


element appearing in the process.

3. Extent of Reaction expressions for each reactive


species is written involving the extent of reaction.

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Molecular and Elemental Balances

For steady-state reactive processes,

Input + Generation = Output + Consumption


The generation and consumption terms in the molecular
balance equation is usually obtained from chemical
stoichiometry.

But for an atomic balance, for all cases

Input = Output

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Dehydrogenation of Ethane

Consider the dehydrogenation of ethane in a steady-state


continuous reactor,

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Dehydrogenation of Ethane

Total Balance: Input = Output

Molecular Species Balance:

C2H6: Input Consumed = Output

C2H4: Generated = Output

H2: Generated = Output

Atomic (Elemental) Species Balance:

C-Balance: Input = Output

H-Balance: Input = Output

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Degrees of Freedom of Analysis for Reactive Processes

Molecular Species Balance

+ No. identified/labeled unknowns

+ No. independent chemical reactions

No. of independent molecular species

No. other equations relating unknown variables


-------------------------------------------------------------------------

= No. degrees of freedom

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Degrees of Freedom of Analysis for Reactive Processes

Atomic Species Balance

+ No. identified/labeled unknowns

No. independent atomic species

No. of independent nonreactive molecular species

No. other equations relating unknown variables


-----------------------------------------------------------------------------

= No. degrees of freedom

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Degrees of Freedom of Analysis for Reactive Processes

Extent of Reaction

+ No. identified/labeled unknowns

+ No. independent chemical reactions

No. of independent reactive molecular species

No. of independent nonreactive molecular species

No. other equations relating unknown variables


-----------------------------------------------------------------------------

= No. degrees of freedom

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Independent Chemical Reactions, Molecular and Atomic Species

Chemical reaction: A chemical reaction is independent if it


cannot be obtained algebraically from other chemical
reactions involved in the same process.

Molecular Species: If two molecular species are in the same


ratio to each other wherever they appear in a process, then
these molecular species are not independent.

Atomic Species: If two atomic species occur in the same


ration wherever they appear in a process, balances on those
species will not be independent equations.

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Independent Chemical Reactions, Molecular and Atomic Species

Consider the following reactions:

A =======> 2B

B =======> C

A =======> 2C

Are these chemical reactions independent?

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Independent Chemical Reactions, Molecular and Atomic Species

Consider a continuous process in which a stream of liquid


carbon tetrachloride (CCl4) is vaporized into a stream of air.

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Independent Chemical Reactions, Molecular and Atomic Species

Molecular Species Analysis

Total: 3 (O2, N2, CCl4)

Independent: 2 (O2 or N2, CCl4)

Atomic Species Analysis

Total: 4 (O, N, C, Cl)

Independent 2 (O or N, Cl or C)

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

In the Deacon process for the manufacture of chlorine, HCl


and O2 react to form Cl2 and H2O.

Sufficient air (21 mole% O2, 79% N2) is fed to provide 35%
excess oxygen and the fractional conversion of HCl is 85%.

Determine the amount of air required per mole of HCl fed


into the process.Calculate the mole fractions of the product
stream components using:

a. molecular species balances


b. atomic species balances
c. extent of reaction

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

Identify the components of the product stream:

HCl since not all will be converted (based


on fractional conversion)

O2 since it is supplied in excess

N2 it goes with the O2 in air but not


consumed during the reaction

Cl2 produced during the process

H2O produced during the process

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

To get mole fractions of components in the product stream:

yi = ni/nt

For the identified components:

yHCl = n2/nt
yO2 = n3/nt
yN2 = n4/nt
yCl2 = n5/nt
yH2O = n6/nt

where nt = n2 + n3 + n4 + n5 + n6

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

DEGREES OF FREEDOM ANALYSIS: Molecular Balance

Unit: Reactor

unknowns (n1,n2,n3,n4,n5,n6) +6
independent chemical reaction +1
independent molecular species 5
other equations:
2
35% excess O2 & fractional HCl conversion
Degrees of freedom 0

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
17
LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

Method I: Molecular Species Balance

35% excess O2:


0.5 molO 2
(O 2 )T 100mol HCl 25molO 2
2 mol HCl
(O 2 ) A 25mol O 2 1.35 33.75molO 2

1molair
n1 33.75mol O 2 160.7 molair
0.21mol O 2
160.7 mol air molair
Required air 1.607
100 mol HCl mol HCl

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

HCl Balance: Input Consumed Output = 0


(100 mol) 0.85(100 mol) n2 = 0
n2 = 15 mol HCl

O2 Balance: Input Consumed Output = 0


(33.75 mol) 85 mol HCl react (0.5/2) n3 = 0
n3 = 12.5 mol O2

N2 Balance: Output = Input


n4 = 160.7 mol air (0.79 mol N2/1 mol air)
n4 = 127 mol N2

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

Cl2 Balance: Generated Output = 0


85 mol HCl react (1/2) n5 = 0
n5 = 42.5 mol Cl2

H2O Balance: Generated Output = 0


85 mol HCl react (1/2) n6 = 0
n6 = 42.5 mol H2O

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

Calculation for mole fractions:

Component i ni (moles) y

HCl 15.0 (15.0/239.5) = 0.063


O2 12.5 (12.5/239.5) = 0.052
N2 127.0 (127.0/239.5) = 0.530
Cl2 42.5 (42.5/239.5) = 0.177
H2O 42.5 (42.5/239.5) = 0.177
Total 239.5 1.000

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

DEGREES OF FREEDOM ANALYSIS: Atomic Balance

Unit: Reactor

unknowns (n1,n2,n3,n4,n5,n6) +6
independent atomic specie(s) 3
independent nonreactive molecular specie(s) 1
other equations:
2
35% excess O2 & fractional HCl conversion
Degrees of freedom 0

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
22
LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

From % excess O2 ======> n1

From fractional conversion ======> n2

Atomic Species Balance:

H-Balance: 100(1) = n2 + 2n6

O-Balance: n1(0.21)(2) = 2n3 + n6

Cl-Balance: 100(1) = n2 + 2n5

N-Balance: n1(0.79)(2) = 2n4

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
23
LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

DEGREES OF FREEDOM ANALYSIS: Extent of Reaction

Unit: Reactor
unknowns (n1,n2,n3,n4,n5,n6) +6
independent chemical reaction(s) +1
independent reactive molecular species 4
independent nonreactive molecular species 1
other equations:
2
35% excess O2 & fractional HCl conversion
Degrees of freedom 0

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
24
LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-1. Production of Chlorine (Deacon Process)

From % excess O2 ======> n1

From fractional conversion ======> n2

Extent of Reaction:

HCl: n2 = 100 (2)

Cl2: n5 = 0 + (1)

H2O: n6 = 0 + (1)

N2: n4 = 0.79n1 (0)

O2: n3 = 0.21n1 (0.5)

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-2. Production of Ethyl Bromide

The reaction between ethylene and hydrogen bromide to


form ethyl bromide is carried out in a continuous reactor.

C2H4 + HBr =====> C2H5Br

The product stream is analyzed and found to contain 51.7


mole% C2H5Br and 17.3% HBr. The feed to the reactor
contains only ethylene and hydrogen bromide.

Calculate the fractional conversion of the limiting reactant


and the percentage by which the other reactant is in excess.
If the molar flow rate of the feed stream is 165 mol/s, what
is the extent of reaction?

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-2. Production of Ethyl Bromide

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-2. Production of Ethyl Bromide

DEGREES OF FREEDOM OF ANALYSIS: Atomic Species

Unit: Reactor

unknowns (x and n2) +2


independent atomic specie(s) 2
independent nonreactive molecular specie(s) 0
other equations 0
Degrees of freedom 0

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-2. Production of Ethyl Bromide

Determine the limiting reactant:

C2 H 4
Stoichiometric Ratio : 1.0
HBr S
C2 H 4 x 165mol / s x
Actual Ratio :
HBr A (1 x)(165mol / s) 1 x

Solve x and n2 using any 2 of the 3 atomic species balances:

C-Balance
H-Balance
Br-Balance

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
29
LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-2. Production of Ethyl Bromide

C-Balance:

mol x molC2 H 4 2mol C


165 n 2 0.310 2 n 2 0.517 2
s mol 1mol C2 H 4
330x 1.654n 2

Br-Balance:

mol 1 x mol HBr 1mol Br


165 n 2 0.1731 n 2 0.517 1
s mol 1mol HBr
165(1 x) 0.69n 2

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
30
LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-2. Production of Ethyl Bromide

Solving simulateneously,

x = 0.545 mol C2H4/mol ; n2 = 108.77 mol/s

Solving for the actual ratio of C2H4 and HBr in the feed:

C2 H 4 0.545
1.0
HBr A 1 0.545
Therefore, HBr is limiting.

actual stoichiometric
% excess C 2 H 4 100
actual

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-2. Production of Ethyl Bromide

Actual feed for C2H4:

(165 mol/s)(0.545) = 89.93 mol/s

Theoretical requirement for C2H4 based on stoichiometry:

mol 1 0.545 mol HBr 1mol C 2 H 4 mol


165 1mol HBr 75.08
s mol s

89.93 75.08
% excess C2 H 4 100 19.8%
75.08

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
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LECTURE 10. Solving Material Balance Problems Involving Reactive Processes

Example 10-2. Production of Ethyl Bromide

Fractional conversion of HBr:

amount reacted input output


X HBr
amount fed input
165 1 0.545 108.77 0.173
X HBr 0.749
1651 0.545
The can be determined based on C2H4, HBr, C2H5Br:

C2H4: 0.310(108.77) = (165)(0.545)


HBr: 0.173(108.77) = (165)(1-0.545)
C2H5Br: 0.517(108.77) = 0

Solving for : = 56.2 mol/s

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baos
33