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BKF2343
MATERIAL AND ENERGY
BALANCE

Sem II 2016/2017

Chapter 2
Balances on Reactive
Processes (Part I)
1
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Learning Outcomes
 Calculate a fractional excess, fractional conversion, yield and
selectivity of a chemical reaction process.
 
 Perform and analyze material balance calculations on reactive
processes using atomic species balance, molecular species balance
and extent reaction balance.
+ 3

Chemical Reaction Stoichiometry

Limiting and Excess

Multiple
Reactant, Fractional Chemical
Stoichiometry Reaction, Yield
Conversion and Extent of Equilibrium
and Selectivity
Reaction

Balance on Reactive System

+
Balances on Reactive Systems
 WITHOUT CHEMICAL REACTION:
INPUT = OUTPUT
 In reactive system, must account for the CONSUMPTION of reactants
and GENERATION of products through stoichiometry.

 WITH CHEMICAL REACTION:

Generati Consump
Input on tion Output
+
Stoichiometric Equations
 The stoichiometric equation of a chemical reaction is a
statement of the relative amounts of reactants and products that
participate in the reaction.

2 SO2 + O2 → 2 SO3

 A stoichiometric equation is valid only if the number of

atoms of each atomic species is balanced.

2S→2S
4O+2O→6O
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Stoichiometric Equations
 A stoichiometric ratio of two molecular species participating in a
reaction is the ratio of their stoichiometric coefficients:

2 SO2 + O2 → 2 SO3

2 mol SO3 generated

1 mol O2 consumed

2 mol SO3 generated

2 mol SO2 consumed

 A stoichiometric ratio can be used as a conversion factor to

calculate the amount of reactant (or product) consumed (or
generated) using another given amount of product or reactant.
+ Try this
2 SO2 + O2 → 2 SO3

 What is the stoichiometric ratio of SO3 to SO2?

1 mol SO3 generated
1 mol SO2 consumed

 If 1000 kmol of SO3 is to be produced, how many O2 required?

500 kmol O2

 If 1600 kg/hr of SO3 is to be produced, how many O2 (kg/hr) required?

320 kg/hr O2

 If 100 mol/min of SO2 is to be fed into a reactor, producing 40

mol/min SO3, how many SO2 left leaving at the reactor outlet?
60 mol/min
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Stoichiometric proportion
 Two reactants are said to be in stoichiometric proportion if the
feed ratio (moles A present/moles B present) equals the
stoichiometric ratio.
2 SO2 + O2 → 2 SO3
 E.g There must be 2 moles of SO2 for every 1 mole of O2 present in
the feed of the reactor (nSO2/nO2 = 2:1) so that the feed ratio can be
said to be in stoichiometric proportion.

 If reactants are fed in stoichometric proportion, and the reaction

proceeds to completion, all reactants are consumed.
+
Limiting and Excess Reactant
 A reactant is said to be “limiting’’ if it is present in less than its
stoichiometric proportion relative to every other reactant.

 The reactant that would run out if a reaction proceeded to

completion is called the limiting reactant, and the other
reactants are termed excess reactants.

 If all reactants are present in stoichiometric proportion, then

no reactant is limiting (or all of them are limiting reactants).
+ Example

C2H2 + 2H2 ------> C2H6

10 kmol/h of acetylene (C2H2) and 30 kmol/h of hydrogen (H2)

are fed to the reactor.
Determine the limiting reactant.

Feed Ratio vs. Stoichiometric Ratio

(10 kmol/h C2H2: 30 kmol/h H2) (1 mol C2H2: 2 mol H2)

Since H2 is excess therefore C2H2 is the limiting reactant

+
Fractional Excess and Percentage Excess
 fractional excess (fXS) – ratio of the excess to the stoichiometric
proportion.

n -n
Fractional Excess  feed stoich
n stoich

n -n
Percentage Excess  feed stoich
 100%
n stoich
+ Example

C2H2 + 2H2 ------> C2H6

10 kmol/h of acetylene (C2H2) and 30 kmol/h of hydrogen (H2)

are fed to the reactor.
Determine the limiting reactant and fractional excess.

Feed Ratio vs. Stoichiometric Ratio

(10 kmol/h C2H2: 30 kmol/h H2) (1 mol C2H2: 2 mol H2)

Since H2 is excess therefore C2H2 is the limiting reactant

Fractional excess of H2 = (30-20)/20 = 0.5

We say 50% excess H2 in the feed.

+ Example

C2H2 + 2H2 ------> C2H6

20 kmol of acetylene (C2H2) and 50 kmol of hydrogen (H2)

are fed to the reactor. 6 kmol of C2H2 has reacted. What is the
conversion of C2H2 ? How much of C2H2 presence after the
reaction occurred?
+
Fractional conversion (f)
 fractional conversion (f) – ratio of the amount of a reactant reacted,
to the amount fed.

 n A  reacted
f 
 n A  fed

 n A  reacted
Percentage conversion   100%
 n A  fed
+ Example

C2H2 + 2H2 ------> C2H6

80 kmol of acetylene (C2H2) and 200 kmol of hydrogen (H2) are

fed to the reactor. The conversion of C2H2 is 50%. How much
of H2 and C2H2 presence after the reaction occurred? How
much C2H6 produced after the reaction occurred?
+
Extent of Reaction
n i  n io  v i ξ
or
i n
n  io  v i ξ
ξ= extent of reaction (an extensive quantity describing the progress of a
chemical reaction .)

ni = moles of species i present in the system after the reaction occurred

nio = moles of species i in the system when the reaction starts

vi = stoichiometry coefficient for species i in the particular chemical reaction

equation (+ve for product, -ve for reactant)

+ Example

C2H2 + 2H2 ------> C2H6

80 kmol of acetylene (C2H2) and 200 kmol of hydrogen (H2) are

fed to the reactor. The conversion of C2H2 is 50%. How much
of H2 and C2H2 presence after the reaction occurred? How
much C2H6 produced after the reaction occurred?
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Try this
 Methanol is synthesized from carbon monoxide and hydrogen in a
catalytic reactor. The feed to the process contains 32 mole% CO, 60
mole% H2 and 8 mole% N2. A conversion of 20% of the limiting
reactant is achieved. Determine the production rate of products.
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Try this
 A catalytic reactor is used to produce formaldehyde (HCHO) from
methanol in the reactor:
CH3OH  HCHO + H2
The conversion of 60% is achieved in the reactor and the production
rate of formaldehyde is 900 kg/hr. Calculate the feed rate of methanol
to the process. Determine the product composition.
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Multiples Reaction
 Some of the chemical reaction has a side reaction which
is formed undesired product- multiple reaction
occurred.
 Effects of this side reaction might be:
1. Economic loss
2. Less of desired product is obtained for a given quantity of raw
materials
3. Greater quantity of raw materials must be fed to the reactor to obtain
a specified product yield.
+ Exercise

C2H6 ---> C2H4 + H2

C2H6 + H2 ----> 2 CH4

The reaction takes place in a continuous reactor at steady

state. The feed contains 85 mole% ethane (C2H6) and the
balance is inert (I). Derive the extent of reaction equations.
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Extent for multiple reactions

 Concept of extent of reaction can also be applied for multiple
reaction
 Each independent reaction will have its own extent.

ni  nio   vi j
j ij
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Yield and Selectivity
The terms yield and selectivity are used to describe the degree to
which desired reaction predominates undesired side reaction.

 Yield definition is different depending on the process specification

Moles of desired product formed

Yield =
Moles of reactant fed

Moles of desired product formed

Yield =
Moles of reactant consumed

 Selectivity

Moles of desired product

Selectivity =
Moles of undesired product
+ Exercise

C2H6 ---> C2H4 + H2

C2H6 + H2 ----> 2 CH4

The reaction takes 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 of the ethane fed, the fractional yield of ethylene
based on ethane fed is 0.471. Calculate the molar
composition of the product gas and the selectivity of
ethylene to methane production.
+ Three (3) Methods to Solve Material
Balance of Reactive Processes

Atomic Species
Balance

Extent of
Reaction

Molecular
Species Balance
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Exercise
Consider the dehydrogenation of ethane in a steady-sate continuous reactor.
C2H6  C2H4 + H2

100 kmol/min of ethane is fed to the reactor. The molar flow rate of H2 in the
product stream is 40 kmol/min.
Solve for the products composition by using 3 different methods in solving
balance for reactive process.
+

C2H6 -------> C2H4 + H2

100 kmol C2H6/min Reactor 40 kmol H2/min

n1 kmol C2H6/min
n2 kmol C2H4/min
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Atomic Species Balance
 All atomic balance is INPUT=OUTPUT

 Balance on atomic C (input= output)

100 kmol C2H6 2 kmol C n1 kmol C2H6 2 kmol C

= + n2(2)
1 kmol C2H6 1 kmol C2H6

200=2n1 + 2n2
100=n1 + n2 [1]
 Balance on atomic H (input = output)
100(6)=40(2) + 6n1+4n2
520 = 6n1 + 4n2 [2]
Solve simultaneous equation,
n1= 60 kmol C2H6/min; n2= 40 kmol C2H4/min
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Extent of Reaction
 Write extent of reaction for each species

C2H6 : n1 = 100-ξ
C2H4 : n2 = ξ
H2 : 40 = ξ

Solve for n1 and n2 (ξ =40)

n1= 60 kmol C2H6/min; n2= 40 kmol C2H4/min

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Molecular Species Balance
H2 balance (Gen=Output):
H2 Gen= 40 kmol H2/min

C2H6 Balance (input=output + cons.):

100 kmol C2H6/min = n1 kmol C2H6/min +
40 kmol H2 gen x (1 kmol C2H4 gen/1 kmol H2 gen)
n1= 60 kmol C2H6/min

C2H4 balance (Gen.=Ouput):

40 kmol H2 gen x (1 kmol C2H4 gen./ 1 kmol H2 gen) = n2
n2= 40 kmol C2H4/min
 + Degree-of-freedom for reactive 31

material balance
DOF: Molecular Species Balance DOF : Extent of reaction Balance
No. of unknowns variables
+ No. of independent chemical reaction No. of unknowns variables
- No. of independent molecular species balance
- No. of other equation relating the variable + No. of independent chemical reaction
==================== - No. of independent reactive species
No. of degree of freedom - No. of independent nonreactive species
==================== - No. of other equation relating the variable
=============================
DOF : Atomic Species Balance No. of degree of freedom
=============================
No. of unknowns variables
- No. of independent reactive atomic species balance
- No. of molecular balance on indep. nonreactive species
- No. of other equation relating the variable
=============================
No. of degree of freedom
=============================
• Different methods have different approach of degree-of-freedom
analysis
• We must understand the concept of independent atomic species,
independent molecular and independent chemical reactions
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Independent Molecular Species
 If two MOLECULAR species are in the SAME RATIO to each other wherever
they appear in a process (output and input streams), balance on those
species will not be independent (i.e. only one independent MOLECULAR
species balance is obtained).
n3 mol O2
3.76 n3 mol N2
n1 mol O2
n4 mol CCl4(v)
3.76 n1 mol N2

Process
n2 mol CCl4(l) Unit n5 mol CCl4(l)

 Since N2 and O2 have a same ratio on the input and output streams (3.76 mol
N2/mol O2), only ONE independent molecular species balance for these 2
species is considered. In this reaction, there will be TWO independent
molecular species balance (for CCl4 and for either O2 or N2).
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Independent Atomic Species
 If two ATOMIC species are in the SAME RATIO to each other wherever they
appear in a process (output and input streams), balance on those species will
not be independent (i.e. only one independent ATOMIC species balance is
considered).
n3 mol O2
3.76 n3 mol N2
n1 mol O2
n4 mol CCl4(v)
3.76 n1 mol N2
Process
n2 mol CCl4(l) Unit n5 mol CCl4(l)

 Atomic N and O are always in same proportion to each other on the input
and output streams (3.76:1), similar for atom C and Cl which always same
ratio too (1:4) on the input and those 2 output streams.

 Although FOUR atomic species exist, only TWO independent atomic species
balance can obtain for this case (for O or N and for C or Cl).
+
Independents Chemical Reactions
 Chemical reactions are independent if the stoichiometric equation
any one of them CANNOT be obtained by ADDING and SUBTRACTING
multiples of the stoichiometric equations of others.
 + DOF Analysis for Reactive System:
Molecular Species Balance

C2H6 -------> C2H4 + H2

100 kmol C2H6/min Reactor 40 kmol H2/min

n1 kmol C2H6/min
n2 kmol C2H4/min

 Degree-of-freedom analysis
OF: Molecular Species Balance
No. of unknowns variables 2 unknowns variables (n1, n2)
+ No. of independent chemical reaction + 1 independent chemical reaction
No. of independent molecular species balance - 3 independent molecular species balance (C2H6, C2H4, H2)
No. of other equation relating the variable - 0 other equation relating the variable
====================
=============================
No. of degree of freedom
====================
0 Degree of freedom
=============================
+ DOF Analysis for Reactive System:
Extent of Reaction

C2H6 -------> C2H4 + H2

100 kmol C2H6/min Reactor 40 kmol H2/min

n1 kmol C2H6/min
n2 kmol C2H4/min

DOF : Extent of reaction Balance  Degree-of-freedom analysis

2 unknowns variables (n1,n2)
No. of unknowns variables
+ 1 independent chemical reaction
+ No. of independent chemical reaction
- 3 independent reactive species (C2H6, C2H4, H2)
- No. of independent reactive species
- 0 independent nonreactive species
- No. of independent nonreactive species
- 0 other equation relating the variable
- No. of other equation relating the variable
============================
=============================
0 Degree of freedom
No. of degree of freedom
============================
=============================
+ DOF Analysis for Reactive System:
Atomic Species Balance

C2H6 -------> C2H4 + H2

100 kmol C2H6/min Reactor 40 kmol H2/min

n1 kmol C2H6/min
n2 kmol C2H4/min

DOF : Atomic Species Balance  Degree-of-freedom analysis

No. of unknowns variables 2 unknowns variables (n1, n2)

- No. of independent reactive atomic species balance
- No. of molecular balance on indep. nonreactive species
- No. of other equation relating the variable
=============================
No. of degree of freedom
=============================
- 2 independent atomic species balance (C, H)
- 0 molecular balance on indep. nonreactive species
- 0 other equation relating the variable
=============================
0 No. of degree of freedom
=============================
+ 38

Problem 4.49 (pg 174)

+ 39

Problem 4.50 (pg 174)

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Problem 4.51 (pg 175)