Chemical Reaction Engineering

(CRE) is the field that studies the

rates and mechanisms of chemical
reactions and the design of the
reactors in which they take place.

Chapter Four: Stoichiometry

1
STOICHIOMETRY
If rate law depends on more than
one species, we must relate
concentrations of different species
to each other.
This relationship is most easily
established with aid of a
stoichiometric table.
2
This table presents stoichiometric
relationships between reacting
molecules for a single reaction.

It tells us how many molecules of

one species will be formed during a
chemical reaction when a given
number of molecules of another
species disappears.
3
These relationships will be developed for general
reaction

already used stoichiometry to relate

relative rates of reaction for Eq. (2-1):

In formulating our stoichiometric table, take species A as

our basis of calculation (i.e., limiting reactant) & then
divide through by stoichiometric coefficient of A,
4
in order to put everything on a basis
of per mole of A.
Next, develop stoichiometric
relationships for reacting species
that give change in number of
moles of each species (i.e., A, B, C,
& D ).
5
4.1 Batch Systems
Batch reactors are primarily used
for production of specialty
chemicals & to obtain reaction
rate data in order to determine
reaction rate laws & rate law
parameters such as k, specific
reaction rate. 6
Fig. (4-1) shows batch system in
which we will carry out reaction
given by Eq. (2-2).

At time t = 0, open reactor & place a

number of moles of species A, B, C,
D, & I (NA0, NB0, NC0 , ND0, & NI0 ,
respectively) into reactor.
7
Figure 4-1

8
Species A is our basis of
calculation, & NA0 is number of
moles of A initially present in
reactor.
Of these, NA0X moles of A are
consumed in system as a result of
chemical reaction, leaving (NA0-
NA0 X) moles of A in system.
9
Number of moles of A
remaining in reactor after a
X has been achieved is

10
To determine number of moles of
each species remaining after
NA0X moles of A have reacted,
form stoichiometric table (Table
4-1).

This stoichiometric table presents

following information:
11
Table 4-1

12
Column 1: particular species
Column 2: number of moles of
each species initially present
Column 3: change in number of
moles brought about by reaction
Column 4: number of moles
remaining in system at time t
13
Lets take a look at totals in last
column of Table 4-1.

Stoichiometric coefficients in
parentheses (d/a+c/ab/a-1)
represent increase in total number
of moles per mole of A reacted.

14
 (4-1)

Parameter tells us change in total number of

moles per mole of A reacted.

Total number of moles:

15
4.1.1 Equations for Batch Concentrations

Concentration of A is number of moles of A per

unit volume:

After writing similar equations for B, C,

& D, we use stoichiometric table to
express concentration of each
component in terms of conversion X:
16
 (4-2)-(4-5)

We further simplify these equations by

defining parameter i

17
 (4-3)-(4-5)

Now need only to find volume as a

function of X to obtain species
concentration as a function of X.
18
Constant-Volume Batch Reaction
Systems
Some significant simplifications in
reactor design equations are
possible when reacting system
undergoes no change in volume as
reaction progresses. These systems
are called constant-volume, or
constant-density. 19
This situation may arise from
several causes. In gas -phase
batch systems, reactor is
usually a sealed constant-
volume vessel with appropriate
instruments to measure
pressure & temperature within
reactor. 20
Volume within this vessel is
fixed & will not change, & is
therefore a constant-volume
system (V=V0).
Laboratory bomb calorimeter
reactor is a typical example of
this type of reactor.
21
Another example of a
constant-volume gas-phase
isothermal reaction occurs
when number of moles of
products equals number of
moles of reactants.
22
For constant-volume systems described
earlier, Eqs. (4-2)-(4-5) can be simplified to
give (relating concentration & conversion):

(4-6)

(4-7)-(4-9)

23
To summarize for liquid-phase reactions, use a
rate law for reaction (2-2) such as rA= kACACB to
obtain rA= f(X), that is,

Substituting for given parameters k.

CA0, & B , now use techniques in
Chapter 2 to size CSTRs & PFRs
for liquid-phase reactions. 24
(4-1)

25
26
(4-2)

27
28
4.2 Flow Systems
Form of stoichiometric table for a
continuous-flow system (see Fig.
4-2) is virtually identical to that
for a batch system (Table 4-1)
except that we replace Nj0 by Fj0
& Nj by Fj (Table 4-2).
29
(4-2)

30
(4-2)

31
Taking A as basis, divide Eq. (2-
1) through by stoichiometric
coefficient of A to obtain

32
4.2.1 Equations for Concentrations
in Flow
For Systems
a flow system, concentration C at a
A
given point can be determined from molar
flow rate FA & volumetric flow rate at
that point:
(4-10)

33
Now, write concentrations of A, B,
C, & D for general reaction given
by Eq. (2-2) in terms of their
respective entering molar flow rates
(FA0, FB0, FC0, FD0), conversion X, &
volumetric flow rate , .
(4-11)

34
4.2.2 Liquid-Phase Concentrations
For liquids, volume change with
reaction is negligible when no phase
changes are taking place.
Consequently, we can take

(4-12)

(4-13)
35
Consequently, using
any one of rate laws in
chapter 3, we can now
find rA = f(X) for
liquid-phase reactions.
36
However, for gas-phase
reactions, volumetric flow
rate most often changes
during course of reaction
because of a change in total
number of moles or in
temperature or pressure.
37
Hence, one cannot
always use Eq. (4-13) to
express concentration as
a function of conversion
for gas-phase reactions.
38
4.2.3 Gas Phase Concentrations

In our previous discussions, we

considered primarily systems in
which reaction volume or
volumetric flow rate did not vary
as the reaction progressed.
Most batch & liquid-phase & some
gas-phase systems fall into this
category. 39
There are other systems, though, in
which either V or do vary, & these
will now be considered.
A situation where one encounters a
varying flow rate occurs quite
frequently in gas-phase reactions that do
not have an equal number of product &
reactant moles.
For example, in synthesis of ammonia,
40
4 mol of reactants gives 2 mol of
product. In flow systems where this type
of reaction occurs, molar flow rate will
be changing as reaction progresses.

Because equal numbers of moles occupy

equal volumes in gas phase at same
temperature & pressure, volumetric flow
rate will also change.
41
In stoichiometric tables
presented on preceding
pages, it was not necessary
to make assumptions
concerning a volume
change in first four
columns of table 42
(i.e., species,
initial number of moles or
molar feed rate,
change within the reactor, &
remaining number of moles
or molar effluent rate).

43
All of these columns of stoichiometric
table are independent of volume or
density, & they are identical for
constant-volume (constant-density) &
varying-volume (varying-density)
situations.

Only when concentration is expressed

as a function of conversion does
variable density enter picture.
44
Flow Reactors with Variable Volumetric Flow Rate

To derive concentrations of
each species in terms of
conversion for a variable-
volume flow system, use
relationships for total
concentration.
45
Total concentration, CT,
at any point in reactor is
total molar flow rate, FT
divided by volumetric
flow rate .
46
In gas phase, total
concentration is also found
from gas law, CT = P/ZRT.
Equating these two
relationships gives
(4-14)

47
 At entrance to reactor,
(4-15)

Ratio of Eq. (4-15) to Eq. (4-14) & assuming

negligible changes in compressibility factor,

(4-16)

48
express concentration of species j for a flow
system in terms of its flow rate, Fj,
temperature, T, & total pressure, P.

(4-17)

total molar flow rate is just sum of molar

flaw rates of each of species:
(4-18)

49
Now lets express concentration in terms of
conversion for gas flow systems. From Table
4-2 total molar flow rate can be written in
terms of conversion: (4-19)

50
51
Flow System

(4-23)

52
 (4-25)

(4-21)

(4-3)

53
(4-3)

54
One of major objectives of this
chapter is to learn how to express
any given rate law -rA as a
function of conversion.

Schematic diagram in Fig. 4-3

helps to summarize our
discussion on this point.
55
(4-3)
56
Concentration of key
reactant, A, is expressed as
a function of conversion in
both flow & batch systems,
for various conditions of T,
P, & V.
57
(4-3)

58
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(4-5)

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