CHEE 

221: Chemical Processes and Systems

Module 3. 
Material Balances with Reaction 

Part a: Stoichiometry and Methodologies

(Felder & Rousseau Ch 4.6‐4.8
not 4.6c )
Material Balances on Reactive Processes

What does a reaction do to the general balance equation?

Accumulation = In – Out + Generation – Consumption

For a reactive process at steady‐state, the general balance equation becomes:  

0 = In – Out + Generation – Consumption

Accounts for material produced or 
consumed within the system

The stoichiometric equation of the reaction imposes constraints on the 
relative amounts of reactants and products in the input and output streams.

CHEE 221 2
Material Balances on Reactive Processes

What quantities are conserved?
Type of Balance Without Rxn With Rxn

Total mass
 
Total moles
 
Mass of a chemical compound
 
Moles of a chemical compound
 
Mass of an atomic species
 
Moles of an atomic species
 
CHEE 221 3
Stoichiometry Basics
Stoichiometry – theory of the proportions in which chemical species combine
with one another in a reaction
2 SO2 + O2  2 SO3
Stoichiometric Equation – an equation that relates the relative number of
molecules or moles of reactants and products (but not mass!) that participate
in a chemical reaction. To be valid, the equation must be balanced.
For example, are the following stoichiometric equations balanced?

C2H5OH + O2  CO2 + H2O

(NH4)2Cr2O7  Cr2O3 + N2 + H2O

Stoichiometry imposes additional constraints to balances
 Defines relationship between generation of products and consumption of 
reactants
 Always in terms of molar units (not mass)
CHEE 221 4
Stoichiometry Basics… cont’d

Stoichiometric Coefficients (i) – values preceding each molecular species (i)

in a balanced stoichiometric equation. Values are defined to be positive for
products and negative for reactants. For the reaction,
2 SO2 + O2  2 SO3 
 SO2  2;  O2  1;  SO3  2

Stoichiometric Ratio – ratio of stoichiometric coefficients in a balanced

stoichiometric equation. For the above reaction for example,
2 mol SO 3 generated
1 mol O 2 consumed

Two reactants, A and B, are in stoichiometric proportion if the ratio (moles

of A present)/(moles of B present) equals their stoichiometric ratio
determined from the balanced stoichiometric equation.

CHEE 221 F&R Ch 4.6a 5

Limiting and Excess Reactants

If the reactants are not present in stoichiometric proportions, the reactant

that would be completely consumed if a reaction went to completion is
known as the limiting reactant (LR). The other reactant(s) are termed
excess reactant(s).

The fractional excess of the reactant is the ratio of the excess to the 
stoichiometric requirement:
( nA ) feed - ( nA )stoich  ( n ) - ( n A )stoich 
fractional excess of A  or   A feed 

(nA ) stoich  (n A ) stoich 

where (nA)feed is the number of moles of an excess reactant, A, present in 
the feed to a reactor and (nA)stoich is the stoichiometric requirement of A, or 
the amount needed to react completely with the limiting reactant, even if 
the reaction does not go to completion.
Percentage excess is 100 times the fractional excess.
CHEE 221 F&R Ch 4.6b 6
Fractional Conversion

Chemical reactions do not occur instantaneously, but often proceed quite slowly.
Therefore, it is often not practical to design a reactor for complete conversion of the
limiting reactant. Instead, the reactant is separated from the reactor outlet stream
and recycled back to the reactor inlet. The fractional conversion of a reactant is the
ratio of the amount reacted to the amount fed:

nA reacted n A reacted

fA  or fA 
nA fed n A fed
 If no reactant is specified, then fractional conversion refers to the limiting reactant
(LR). This is usually the case.
 Fractional conversion is unitless. The percentage conversion is 100 × fA.    
 The fraction unreacted (i.e., in exit stream) is 1 – fA.  

“Fractional Conversion” can be considered as a process constraint (extra equation), as

it describes how the process is operating (i.e. how much rxn did take place?).
CHEE 221 7
Identifying the Limiting Reactant

1. Balance the stoichiometric equation
2. Compare the ratios 

 nx   nx 
  versus  
 ny   ny 
  feed   stoich

 nx   nx 
If,  

 
 ny 
, reactant x is not the limiting reactant
 ny  feed   stoich
 nx   nx 
    , reactant x is the limiting reactant
If,    ny 
 ny  feed   stoich

CHEE 221 8
Example 1: Butane Combustion

The complete combustion of butane can be described as:
C4H10 +  O2             CO2 +  H2O
For a continuous flow process at steady state with a feed of 100 moles of
butane per second, and 1000 moles of oxygen per second, determine the
overall flowrate (mol/s) and molar composition of the outlet stream, if the
fractional conversion of the limiting reactant in the burner is 70%

Always make sure that the stoichiometric equation is balanced!

CHEE 221 9
Extent of Reaction‐How to Handle Different Stoichiometric Ratios

The extent of reaction ( or )is a quantity that characterizes the reaction and
can significantly simplify calculations.

For a continuous process at steady‐state:    ni  ni 0   i

where ni 0 and ni are the molar flow rates of species i in the feed and outlet
streams, respectively (out = in +/‐ conversion).

ni  ni 0   i
For a batch process:   How do these equations arise
from the general M.B.?

where       and     are the initial and final molar amounts of species i, 
ni 0 ni
respectively.   
( or )
The extent of reaction                        has the same units as n n
(or   ).  
Every reaction has a single, unique value of .

CHEE 221 F&R Ch 4.6b 10

Reactor Types
F&R Encyclopedia of Chemical 
Engineering Equipment
(textbook website)

Wk 5 pre‐tutorial exercise: CSTRs (continuous stirred tank reactors) and

PFRs (plug flow reactors) are two of the more common continuous reactor
configurations.

Explain the basic differences (simple diagrams may help), and state the
application advantages of each.
CHEE 221 11
Example 2

The biological removal of nitrogen (in the form of nitrate) from wastewater is
accomplished by anaerobic bacteria in which methanol is added as a carbon
(energy) source for the cells according to the reaction shown below:

6 NO3 + 5 CH3OH 5 CO2 + 3N2 + 7 H2O + 6 OH

If 100 g methanol is added to a water source containing 50 g of nitrate,

determine which is the limiting reactant and the % excess of the non‐limiting
reactant. For a fractional conversion of 30% of the limiting reactant,
determine the composition of the molecular species at the end of the
reaction.

CHEE 221 12
Example 3: F&R Ex 4.6‐1 (Acrylonitrile Production)

Acrylonitrile is produced in the reaction of propylene, ammonia, and oxygen:

3
C 3H6  NH3  O 2  C 3H 3N  3 H 2 O
2

The feed contains 10.0 mole% propylene, 12.0 mole% ammonia, and 78.0
mole% 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.

Try this on your own , then see the textbook for the solution!  

CHEE 221 13
Multiple Reactions
Generally, the synthesis of chemical products do not involve a single reaction
but rather multiple reactions. The goal is to maximize the production of the
desirable product and minimize the production of unwanted byproducts. For
example, ethylene is produced by the dehydrogenation of ethane:
C2H6  C2H4 + H2
C2H6 + H2  2CH4 undesirable side 
C2H4 + C2H6  C3H6 + CH4 reactions

This leads to the following definitions:  
mols of desired product formed
Yield 
maximum mols of product formed (if there were
no side rxns and limiting reactant reacted completely)

mols of desired product formed

Selectivity 
mols of undesired product formed

CHEE 221 F&R Ch 4.6d 14

Multiple Reactions – Extent of Reaction

The extent of reaction method can also be applied to multiple reactions, with
each reaction having its own extent.

For a single reaction: (ni )out  (ni ) fed


 (ni )out  (ni ) fed  i
i

If a set of reactions takes place in a batch or continuous steady‐state reactor,

we can write:
N rxn
(ni )out  (ni ) fed   ij j
j 1

where, ij is the stoichiometric coefficient of substance i in reaction j

j  is the extent of reaction for reaction j.

CHEE 221 15
Balances on Reactive Species

Systems that involve chemical reactions can be analyzed using one of three 
possible methods:

(a) Molecular species balances – the approach always used for

nonreactive systems, but approach is more cumbersome for reactive
processes. Balances must include generation and consumption
terms for each species.

(b) Atomic species (C, H, O, etc.) balances – straightforward method.

Balances are of the form input=output since atomic species cannot
be created or destroyed.

(c) Extents of reaction (Molecular balances)

Each approach provides the same results, but one method may
be more convenient than the other for a given calculation, so
you should be comfortable with both methods.
CHEE 221 F&R Ch 4.7 16
Example 4: Ethylene Oxide

The ethylene oxide reactant used in the production of ethylene glycol is made
by the partial oxidation of ethylene with excess oxygen over a silver catalyst.
The primary reaction is:
C2H4 + O2 C2H4O

Unfortunately some of the ethylene also undergoes complete oxidation to CO2

and water according to:
C2H4 + O2 CO2 + H2O

For a feed flow of 1000 moles/h containing 10% (mole basis) ethylene, and an
ethylene conversion of 25%, a yield of 8% ethylene oxide is obtained.
Determine the flowrates of the species leaving the reactor.

Solve using both “extents of reaction” and “atom balance” methodology

CHEE 221 17
DFA for Reactive Processes
Molecular Species Balances and Extent of Reaction:  
ndf = nunknowns + n independent chemical reactions  – nindependent molecular species balances      
– n other equations relating variables

Atomic Species Balances:
ndf = nunknowns – nindependent atomic species balances 
– nmolecular balances on independent nonreactive species  – nother equations relating variables

Note: F&R develops a separate DFA equation for molecular species balances
and extent of reaction technique, but they are the same.

F&R gives several good examples of these methods in sections 4.7 a‐e; 
READ THESE SECTIONS CAREFULLY.
CHEE 221 18
Notes on Independent Chemical Reactions

Chemical reactions are independent if the stoichiometric equation of any one

of them cannot be obtained by adding and subtracting multiples of the
stoichiometric equations of others.

Consider the following equations:

A  2B (1)
BC (2)
A  2C (3)

These three reactions are not all independent, since (3) = (1) + 2 x (2)

CHEE 221 19
Remember about Independent Species Balances!

Generally, there are n balances for n independent species.  

BUT…

If 2 species are in the same ratio to each other wherever they appear in the
process, balances on these species will not be independent equations.

Example: Air is 3.76 mol N2/mol O2, but only if neither one reacts (e.g. when
evaporating a volatile compound in Air). If one of them does participate in a
reaction (e.g. O2 in a combustion reaction), then these compounds will not be
in the same proportion in different streams.

CHEE 221 20
MB and Reactive Processes: Solution Methodology

What quantities are conserved?
Type of Balance Without Rxn With Rxn

Total mass
 
Total moles
 
Mass of a chemical compound
 
Moles of a chemical compound
 
Mass of an atomic species
 
Moles of an atomic species
 
CHEE 221 21
Example 5: F&R Ex 4.6‐3

The reactions
C2H6  C2H4 + H2
C2H6 + H2  CH4

take place in a continuous reactor at steady‐state. The feed contains 85.0

mole% ethane (C2H6) and the balance inerts (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.

Try this on your own, then see the textbook for the solution!  

CHEE 221 22