MATERIAL AND

ENERGY BALANCE

Mass Balance
Balance on Reactive
Processes
1

Contents for Material Balance

Process classification
Balances
Material Balance Calculations on Single Unit
Process
Balance on Multiple Unit Processes

Balances on Reactive Processes

and Systems
Combustion Reaction
Recycle and Bypass

Chemical Reaction Stoichiometry

Stoichiometr
y

Limiting and Excess

Reactant, Fractional
Conversion and
Extent of Reaction

Chemical
Equilibriu
m

Multiple
Reaction,
Yield and
Selectivity

Balance on Reactive System

Atomic
Species
Balance

Extent of
Reaction

Molecula
r Species
Balance

Stoichiometry

Stoichiometry theory of proportions in

chemical species combine with one another.
Stoichiometric equation of chemical reaction

which

statement of the relative number of molecules or moles

of reactants and products that participate in the
reaction.
must be BALANCE

2 SO2 + O2 ---> 2 SO3

Stoichiometric ratio
ratio of species stoichiometry coefficients in the
balanced reaction equation
can be used as a conversion factor to calculate the
amount of particular reactant (or product) that
was consumed
(produced).
2 mol SO2
2 mol SO
3

generated

consumed

2 mol SO2

1 mol O2 consumed

Test Yourself
C4H8 + 6 O2 --------> 4 CO2 + 4 H2O
1. Is the stochiometric equation balance?

Yes

2. What is stochiometric coefficient for CO 2

3. What is stochiometric ratio of H 2O to O2 including it unit

4 mol H2O generated/ 6 mol O2 consumed

4. How many lb-moles of O2 reacted to form 400lb-moles

CO2

600 lb-moles O2 reacted

5. 100 mol/min C4H8 fed into reactor and 50% is reacted.

At what rate water is formed?

200 mol/min water generated

Limiting and Excess 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.
A reactant is limiting if it is present in less than its
stoichiometric proportion relative to every other
reactant.
If all reactants are present in stoichiometric
proportion, then no reactant is limiting.
Fractional Excess

Percentage Excess

feed

n
n

-n

stoich

stoich

feed

-n

stoich

stoich

100%

Example
C2H2 + 2H2 ------> C2H6
Inlet condition: 20 kmol/h C2H2 and 50 kmol/h H2
What is limiting reactant and fractional excess?
Feed
vs. Stoich. Ratio
(20 kmol/h C2H2: 50 kmol/h H2)
(1 mol C2H2: 2 mol H2)
( 1 kmol/h C2H2: 2.5 kmol/h H2)
Therefore C2H2 is limiting reactant since H2 is excess
Fractional excess of H2 = (50-40)/40 = 0.25

Fractional Conversion
Moles Reacted
Fractional
conversion,
f

Moles Feed

Percentage
conversion =

Moles Feed Mole

Out
=

Moles Feed

moles reacted
moles fed

x
100%

Extent of Reaction
ni nio vi
or
n i n io vi
= extent of 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
N2 + 3H2 ------------> 2NH3
Reactor inlet: 100 mol N2/s; 300 mol H2/s; 1 mol Ar/s
If fractional conversion of H2 0.6, calculate extent of
reaction and the outlet composition.

n H 2 300 3
n N 2 100
n Ar 1
n NH 3 2
Unreacted H2 or H2 outlet= (1-0.6) 300 = 120 mol H 2/s
Solve for extent of reaction : 60 mol/s

Exercise
2 C2H4 + O2 ------->2 C2H4O
The feed to a reactors contains 100kmol C2H4 and 100kmol O2.
a) which is limiting reactant?
C2H4
b) Percentage of excess?
{(100-50)/50 }x100%=100%
c) O2 out?
C2H4O formed?
Extent of reaction?
50kmol
100kmol C2H4O
50kmol
d) if fractional conversion for limiting reactant is 50%, what is outlet
composition and extent of reaction?
50kmol C2H4; extent of reaction = 25 kmol; 75 kmol O2
50 kmol C2H4O
e) if reaction proceed to a point where 60kmol O2 left, what is fractional
conversion for C2H4? Fractional conversion of O2 and extent of reaction?
fC2H4=0.8 fO2=0.4
extent of rxn=40 kmol

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.

Membrane Technology @ FKKSA, UMP

13
SMS2011

Problem 4.40
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
Answer: b)175 kmol O2, c) O2 LR, 17.6% excess NH3, EoR = 0.625 kmol, 75 kg NO

Chemical Equilibrium
Irreversible reaction
reaction proceeds only in a single
direction (from reactants to products)
the concentration of the limiting
reactant eventually approaches zero.

Reversible reaction

reactants form products for forward reaction and products

undergo the reverse reactions to reform the reactants.
Equilibrium point is a rate of forward reaction and reverse
reaction are equal

A full discussion of the relations that can be used to determine

equilibrium compositions of reactive mixtures is beyond the
scope during this course. The equilibrium relationship are
normally given in this course

Exercise
If the water-gas shift reaction,
CO (g) + H2O (g) CO2(g) + H2(g)
proceeds to equilibrium at a temperature T (K), the mole
fraction of the four reactive species satisfy the relation
yCO2yH2

yCOyH2O

K(T)

where K(T) is the reaction equilibrium constant. At T=

1105K, K= 1.00.
Suppose the feed to a reactor contains 1.00 mol of
CO, 2.00 mol of H2O, and no CO2 or H2 and the
reaction mixture comes to a equilibrium at 1105K.
Calculate the equilibrium composition and the
fractional conversion of the limiting reactant.
Answer: EoR = 0.667 mol

Multiples Reaction
Some of the chemical reaction has a side
reaction which is formed undesired productmultiple 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.

Concept of extent of reaction can also be

applied for multiple reaction
only now each independent reaction has its
own extent.

ni nio vi j
j

ij

Yield and Selectivity

Yield definition is different depending on the
process specification
Moles of desired product formed
Yield

Yield

Yield

selectivity

Moles that would have been formed if there were no side

reaction and the limiting reactant had reacted completely

Moles of desired product formed

Moles of reactant fed

Moles of desired product formed

Moles of reactant consumed

moles of desired product

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 the
fractional yield of ethylene is 0.471. Calculate
the molar composition of the product gas and
the selectivity of ethylene to methane
production.
EoR1= 40 mol, EoR2= 2.6 mol

Three (3) Methods to Solve

Material Balance of Reactive
Processes

Different methods have different approach of

degree-of-freedom analysis
We must understand the concept of
independent equations, independent species
and independent chemical reactions

Independent Equations
Algebraic equations are independent if you
CANNOT obtain any one of them by
ADDING and SUBTRACTING multiples of
any of the others
x + 2y = 4 [1]
3x + 6y= 12 [2]
only one independent equation because [2] = 3 x [1]

x + 2y = 4 [1]
2x z = 2 [2]
4y + z = 6 [3]
only 2 independent equation because [3]= 2 x [1] [2]

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).

Independent Molecular Species

n3 mol O2
3.76 n3 mol N2

n1 mol O2

n4 mol CCl4(v)

3.76 n1 mol N2

n2 mol CCl4(l)

Process
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).

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

Independent Atomic Species

n3 mol O2
3.76 n3 mol N2

n1 mol O2

n4 mol CCl4(v)

3.76 n1 mol N2
n2 mol CCl4(l)

Process
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).

Three (3) Methods for Solving Material

Balance for Reactive Process
Atomic
Species
Balance

Extent of
Reaction

Molecula
r Species
Balance

DOF Analysis for Reactive

System:
Atomic 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
=============================

DOF Analysis for Reactive

System:
Extent of Reaction

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
=============================

DOF Analysis for Reactive

System:
Molecular Species Balance
same as extent of reaction

No. of unknowns variables

+ No. of independent chemical reaction
No. of independent molecular species* balance
No. of other equation relating the variable
=============================
No. of degree of freedom
=============================
*for reactive and nonreactive molecular species

Three (3) Methods for Solving

Material Balance for Reactive
Process
Atomic 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)

Extent of Reaction
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
=====================
=====

Molecular Species Balance

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

Write a balance on molecules:

e.g. balance of water, balance on
O2, balance on CH4, etc..

We need to determine the EoR

Balance depend whether is a
reactant or product (need to
consider gen. or consm.)

Example 4.7.1
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 unknown 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

M1: Atomic Species Balance

All atomic balance is INPUT=OUTPUT
Degree-of-freedom analysis
2 unknowns variables (n1, n2)
- 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
=============================

 Balance on atomic C (input= output)

100 kmol C2H6

2 knol C
1 kmol C2H6

n1 kmol C2H6
=

2 kmol C
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

n2(2)

M2: Extent of Reaction

Degree-of-freedom analysis
2 unknowns variables (n1,n2)
+ 1 independent chemical reaction
- 3 independent reactive species (C2H6, C2H4, H2)
- 0 independent nonreactive species
- 0 other equation relating the variable
============================
0 No. of degree of freedom
============================

 Write extent of reaction for each

species
C2H6 : n1 = 100-
C2H4 : n2 =
H2
: 40 =
Solve for n1 and n2 ( =40)
n1= 60 kmol C2H6/min; n2= 40 kmol
C2H4/min

M3: molecular Species Balance

Degree-of-freedom analysis
2
+1
-3

unknowns variables (n1, n2)

independent chemical reaction
independent molecular species balance
(C2H6, C2H4, H2)
-0
other equation relating the variable
=============================
0 No. of degree of freedom
=============================

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

Example 4.7.1
Methane is burned with air in a continuous steadysate 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.

Exercise 4.49
Methane and oxygen react in the presence of a catalyst to form
formaldehyde. In a parallel reaction, methane is oxidized to carbon
dioxide and water:
CH + O2 HCHO
4

+ HO
+ 2H 0
2

CH + 2O2 CO2
The feed to the reactor contains equimolar amounts of methane and
oxygen. Assume a basis of 100 mol feed/so
(a) Draw and label a flowchart. Use a degree-of-freedom analysis
based on extents of reaction to determine how many process variable
values must be specified for the remaining variable values to be
calculated.
(b) Use Equation 4.6-6 to derive expressions for the product stream
component flow rates in terms of the two extents of reaction, 1 and
2.
(c) The fractional conversion of methane is 0.900 and the fractional
yield of formaldehyde is 0.855.
Calculate the molar composition of the reactor output stream and the
selectivity of formaldehyde production relative to carbon dioxide
production.
4

Exercise 4.51
Ethanol is produced commercially by the hydration of ethylene:
C2H4 + H20 ~ C2H5OH
Some of the product is converted to diethyl ether in the side reaction
2 C2H5OH ~ (C2H5)20 + H20
The feed to the reactor contains ethylene, steam, and an inert gas. A sample of the
reactor effluent gas is analyzed and found to contain 43.3 mole% ethylene, 2.5%
ethanol, 0.14% ether, 9.3% inerts,and the balance water.
(a) Take as a basis 100 mol of effluent gas, draw and label a flowchart, and do a
degree-of-freedom analysis based on atomic species to prove that the system has zero
degrees of freedom
(b) Calculate the molar composition of the reactor feed, the percentage
conversion of ethylene, the fractional yield of ethanol, and the selectivity of ethanol
production relative to ether production.
(c) The percentage conversion of ethylene you calculated should be very low.
Why do you think the reactor would be designed to consume so little of the reactant?
(Hint: If the reaction mixture remained in the reactor long enough to use up most of
the ethylene, what would the main product constituent probably be?) What additional
processing steps are likely to take place downstream from the reactor?