+

BKF2343
MATERIAL AND
ENERGY BALANCE

Dr. Suriyati Saleh

2017/2018

Chapter 2c: Material

Balance – Reactive
Processes (part 1)
1
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Contents for Material Balance
 Process classification
 Balances
 Material Balance Calculations on Single Unit Process
(Nonreactive process)
 Balance on Multiple Unit Processes (Nonreactive process)

Balances on Reactive Processes

 Combustion Reaction
 Recycle and Bypass
+ 3

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.
+
Chemical Reaction Stoichiometry

Limiting and Excess Multiple Reaction,

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

Balance on Reactive System

+ 5

Balance on Reactive Systems

Material balance no longer takes the form:

INPUT = OUTPUT
Must account for the disappearance of
reactants and appearance of products
through stoichiometry.

Input Generation Output Consumption

+
Stoichiometry

 Stoichiometry – theory of quantities in which

chemical species combine with one another.
 Stoichiometric equation of chemical reaction:
 statement of the relative amounts of reactants and
products that participate in the reaction.
 valid only if the number of atoms of each atomic
species is balanced
4O+2O→6O
? N2 + ? H2  ? NH3
? SO2 + ? O2  ? SO3
+ 7

2B+1C 1S

Membrane Technology @ FKKSA, UMP SMS2011

+
Stoichiometric Ratio
 Ratioof stoichiometric coefficients (species) in the
balanced reaction equation.
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?

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

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

 If 100 mol/min of SO2 is to be fed into a reactor, producing 50

mol/min SO3, how many SO2 left leaving at the reactor outlet?
+ 10

Example
2 SO2 + O2 ---> 2 SO3

 What is the amount of oxygen required if 1600

kg/h of SO3 is to be produced?
+
Test Yourself
C4H8 + 6 O2 --------> 4 CO2 + 4 H2O

1. Is the stochiometric equation balance?

 Yes
2. What is stochiometric coefficient for CO2
 4
3. What is stochiometric ratio of H2O to O2 including it
unit
 4 mol H2O generated/ 6 mol O2 consumed

4. How many moles of O2 reacted to form 400 moles CO2

 600 moles O2 reacted
+ 12

Stoichiometric proportion
 Two reactants are said to be in stoichiometric proportion if the
ratio of feed (moles A present/moles B present) equals the
stoichiometric ratio from the balanced reaction equation.
2 SO2 + O2 ---> 2 SO3
 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 stoichiometric proportion, and the
reaction proceeds to completion, all reactants are consumed.
 If 200 mol of SO2 and 100 mol of O2 are initially present and
reaction proceed to completion, SO2 and O2 would disappear
at the same instant.
+
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.
+ 14

6 2

Membrane Technology @ FKKSA, UMP SMS2011

+ 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

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

Inlet condition: 20 kmol/h C2H2 and 20 kmol/h H2.

What is limiting reactant?

Feed vs. Stoich. Ratio

+ Fractional Excess and Percentage
Excess
 fractionalexcess (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

n = number
of moles
+ 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

+
Fractional Conversion
fractional conversion (f) – ratio of the amount
of a reactant reacted, to the amount fed.

Moles Reacted Moles Feed – Mole Out

Fractional
= Moles Fed = Moles Feed
conversion, f

If 100 moles of reactant are fed, and 90 moles reacted, f

= 0.9 and percentage conversion is 90%

moles reacted
Percentage conversion = x 100%
moles fed
+ 20

Example
200 moles of SO2 and 100 moles O2 are fed to a reactor.
Only 100 moles of SO2 react according to
2SO2+O2→2SO3.
Find fractional conversion of SO2, percentage conversion
and fraction unreacted?
+ 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
ni  nio  vi  Batch
or
n  n  v 
i io i
Continuous

ξ = extent of reaction

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

nio = moles of species i in the feed

vi = stoichiometric 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?
+
Exercise
Acrylonitrile is produced in the reaction of propylene,
ammonia, and oxygen:

C3H6 + NH3 + 3/2 O2  C3H3N + 3H2O

The feed contains 10.0 mole% propylene, 12.0% ammonia,

and 78.0% air. A fractional conversion of 30.0% of the
limiting reactant is achieved. Taking 100 mol of feed as a
basis, determine which reactant is limiting, the percentage
by which each of the other reactants is in excess, and the
molar amounts of all product gas constituents for a 30%
conversion of the limiting reactant.
+
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.
+
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 =
 Selectivity Moles of reactant consumed

Moles of desired product

Selectivity =
Moles of undesired product
+ Extent for multiple reactions 28

 Concept of extent of reaction can also be applied for multiple

reaction
 Each independent reaction has its own extent.

ni  nio   vi j
j ij i-component/species
j-reaction 1,2,3…
+ 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 the fractional yield of ethylene is 0.471. Derive
the extent of reaction equations.
+ 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
is 0.471. Calculate the molar composition of the product gas
and the selectivity of ethylene to methane production.
+
Exercise
Ammonia is burned to form nitric oxide in the following reaction:

4NH3 + 5O2 -> 4NO + 6H2O

a) calculate the ratio (lb-mole O2 react/lb-mol NO formed)
b) if ammonia is fed to a continuous reactor at a rate of 100 kmol
NH3/h, what O2 feed rate (kmol/h) would correspond to 40%
excess O2.
c) if 50 kg of NH3 and 100 kg O2 are fed to batch reactor, determine
the limiting reactant, the percentage by which the other reactant is
in excess and the extent of reaction and mass of NO produced (kg)
if the reaction proceeds to completion (MW: NH3 = 17, O2 = 32,
NO = 30)

Answer: b)175 kmol O2, c) O2 LR, 17.6% excess NH3, EoR = 0.625 kmol, 75 kg NO
+ 32

BALANCES ON
REACTIVE
PROCESSES
+Three Methods to Solve Material Balance
of Reactive Processes

Atomic Species Balance

Extent of Molecular
Reaction Species Balance
+
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
+ 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
+
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

+
Molecular Species Balance
GMBE: INPUT + GENERATION = OUTPUT + CONSUMPTION

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 C2H6 cons/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 material balance
39

Atomic Species Balance Extent of Reaction Molecular Species Balance

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
==========================
Write a balance on atom;
e.g. atom C, atom H, atom O
Balance always equal to ( IN=OUT)
No. of unknowns variables
+ No. of independent chemical reaction
- No. of independent reactive species
- No. of independent nonreactive species
- No. of other equation relating the variable
==========================
No. of degree of freedom
==========================
Write an extent of reaction equation
We need to determine the EoR
No. of unknowns variables
+ No. of independent chemical reaction
- No. of independent reactive species
- No. of independent molecular species
balances
- No. of other equation relating the
variable
==========================
No. of degree of freedom
==========================
Write a balance on molecules:
e.g. balance of water, balance on O2,
balance on CH4, etc..
Balance depend whether is a reactant or
product (need to consider gen. or
consm.)

• 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
+
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).
+
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.

n unknown =3
n independent equation =2
+
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. Do the degree-of-freedom analysis for 3
different methods in solving balance for reactive process.
 + 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

DOF: Molecular Species Balance

 Degree-of-freedom analysis
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:
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
=============================
+ 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,
- No. of independent reactive species
H2 )
- No. of independent nonreactive species
- 0 independent nonreactive species
- No. of other equation relating the variable
- 0 other equation relating the variable
=============================
============================
No. of degree of freedom
0 Degree of freedom
=============================
============================
+
Exercise
Methane is burned with air in a continuous steady-state
combustion reactor to yield a mixture of CO, CO2 and
water. The reactions taking place are:

CH4 + 3/2 O2  CO + 2H2O

CH4 + 2O2  CO2 + 2H2O
The feed to the reactor contains 7.80% mole CH4, 19.4%
O2 and 72.8% N2. The conversion percentage of methane is
90% and the gas leaving the reactor contains 8 mol
CO2/mol CO. Calculate the molar composition of the
product stream by using 3 different methods.
+ Exercise
49
+ 50

Problem 4.50 (pg 174)

+ 51

Problem 4.51 (pg 175)