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 Baños
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.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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,

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

Dehydrogenation of Ethane

Total Balance: Input = Output

Molecular Species Balance:

C2 H6 : Input – Cons umed = Output

C2H4: Generated = Output

Generated = Output
H2 :
Atomic (Elemental) Species Balance:

C-Balance: Input =
Output

H-Balance: Input =
SLIDE
Output
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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 unk no wns

+ No. independent chemical reactions

– No. of independent molecular species

– No. other equations relating unknown variables

= No. degrees of freedom

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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 unk no wns

– No. independent atomic species

– No. of independent nonreactive molecular species

– No. other equations relating unknown variables

= No. degrees of freedom

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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 unk no wns

+ 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

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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?

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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 (CCl 4 ) is vaporized into a stream of
air.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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 , N 2 , CCl 4 )

Independent: 2 (O 2 or N 2 , CCl 4 )

Atomic Species Analysis

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

Independent 2 (O or N, Cl or C)

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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 O 2 react to form Cl 2 and H 2 O.

Sufficient air (21 mole% O 2 , 79 % N 2 ) is fed to provide 3 5%

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

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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 O 2 in air but
not consumed during the
reaction
Cl 2 produced during the
process
produced during the process
H2 O

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

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

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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 n t = n 2 + n 3 + n 4 + n 5 + n 6

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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 mol O 
(O 2 )T  100 mol HCl
 2 mol HCl   25 mol
2 2

O
(O 2 ) A  25mol O 2 1.35  33.75mol O 2

 1molair 
n1  33.75mol O2  0.21mol  160.7 mol
air  2
O
160.7 molair mol air
Required air   1.607
100 mol HCl
mol HCl
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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) – n 2 = 0
n 2 = 1 5 mol HCl

O 2 Balance: Input – Consumed – Output = 0

(33.75 mol) – 8 5 mol HCl react (0.5/2) – n 3 = 0
n 3 = 12.5 mol O 2

N2 Balance: Output = Input

n 4 = 160.7 mol air (0.79 mol N 2 /1 mol air)
n 4 = 1 2 7 mol N 2

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

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

Cl 2 Balance: Generated – Output = 0

8 5 mol HCl react (1/2) – n 5 = 0
n 5 = 42.5 mol Cl 2

H2O Balance: Generated – Output = 0

8 5 mol HCl react (1/2) – n 6 = 0
n 6 = 42.5 mol H 2 O

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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 n i (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

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

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

From % excess O 2 ======> n 1

From fractional conversion ======> n 2

Atomic Species Balance:

H-Balance: 100(1) = n 2 + 2n 6

O-Balance: n 1 (0.21)(2) = 2n 3 + n 6

Cl-Balance: 100(1) = n 2 + 2n 5

N-Balance: n 1 (0.79)(2) = 2n 4

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

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

From % excess O 2 ======> n 1

From fractional conversion ======> n 2

Extent of Reaction:

HCl: n 2 = 1 0 0 – (2)

Cl 2 : n 5 = 0 + (1)

H2O: n 6 = 0 + (1)

N2 : n 4 = 0.79n 1 ± (0)

O2 : n 3 = 0.21n 1 – (0.5)
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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% C 2 H 5 Br 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 1 6 5 mol/s,
what is the extent of reaction?

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

Example 10-2. Production of Ethyl Bromide

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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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

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

Example 10-2. Production of Ethyl Bromide

Determine the limiting reactant:

 C2H4 
Stoichiometric Ratio :  S 
HBr
1.0
Actual  C 2 H 4 x 165mol / s/ s) 1x
HBr (1  x)(165mol
Ratio :  A  x 
 
Solve x and n 2 using any 2 of the 3 atomic species balances:

C-Balance
H-Balance
Br -
Balance

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

Example 10-2. Production of Ethyl Bromide

C-Balance:

   2 mol C 
2
165 mol  x mol C H 4
 n 2 0.310 2  n2 0.517 2
 
s mol   1mol C2 H4   
330x  1.654n2

Br-Balance:

mol 1  x  mol HBr  1mol Br 

165 s 
mol  1mol HBrn

2
0.1731  n 2 0.5171
165(1  x)  
0.69n2

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

Example 10-2. Production of Ethyl Bromide

Solving simulateneously,

x = 0.545 mol C 2 H 4 /mol ; n 2 = 108.77 mol/s

Solving for the actual ratio of C 2 H 4 and HBr in the feed:

 C 2 H 4 0.545
HBr  
 1  1.0
A 0.545
Therefore, HBr is limiting.
% excess C2 actual  stoichiometric
4  actual 100
H

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

Example 10-2. Production of Ethyl Bromide

Actual feed for C 2 H 4 :

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

Theoretical requirement for C 2 H 4 based on stoichiometry:

mol 1 0.545 mol HBr  1mol C 2 H 4  mol

165    75.08
s mol  1mol HBr  s

% excess C2 89.93  75.08
4  75.08 100  19.8%
H

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

Example 10-2. Production of Ethyl Bromide

Fractional conversion of HBr:

X HBr amount reacted input  output

 
amount fed input
X HBr

165 1 0.545
1651 0.545
The  can be determined based on C2 H 4 , HBr, C2H5Br:
108.770.173  0.749
C2 H4 : 0.310(108.77) = (165)(0.545) – 
HBr: 0.173(108.77) = (165)(1-0.545) – 
C 2 H 5Br 0.517(108.77) = 0 – 
:
Solving for  = 56.2
: mol/s
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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