CRE-Chapter 4

ENCH3115Chemical
Reaction
Engineering
Chapter 4-
Stoichiometry
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.
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.
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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,
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 ).
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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.
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.
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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.
Number of moles of A remaining in reactor after a X has

been
achieved is
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:
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Table 4-1
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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
Let’s take a look at totals in last column of Table 4-1.
Stoichiometric coefficients in parentheses (d/a+c/a–b/a-1) represent increase in total

number of moles per mole of A reacted.
(4-1)
Parameter δ tells us change in total number of moles per mole of A

reacted.
Total number of moles:
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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:
(4-2)-(4-5)
We further simplify these equations by defining parameter Θi 8

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(4-3)-(4-5)
Now need only to find volume as a function of X to obtain species

concentration as a function of X.
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.
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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.
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.
Another example of a constant-volume gas-phase isothermal reaction
occurs when number of moles of products equals number of moles of
reactants.
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For constant-volume systems described earlier, Eqs. (4-2)-(4-5) can
be simplified to give (relating concentration & conversion):
(4-7)-(4-9)
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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, & ΘB , now use techniques in Chapter
2 to size CSTRs & PFRs for liquid-phase reactions.
(4-1)
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(4-2)
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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).
(4-2)
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(4-2)
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Taking A as basis, divide Eq. (2-1) through by stoichiometric coefficient of A to
obtain
4.2.1 Equations for Concentrations in Flow Systems

For a flow system, concentration CA at a given point can be determined from
molar flow rate FA & volumetric flow rate ν at that point:
(4-10)
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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 , ν.
(4-11)
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
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Consequently, using any one of rate laws in chapter 3, we can now
find –rA = f(X) for liquid-phase reactions.
Problem 4-6 (a) page 134
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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.
Hence, one cannot always use Eq. (4-13) to express concentration as a
function of conversion for gas-phase reactions.
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.
There are other systems, though, in which either V or ν 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 21
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ammonia,
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.
In stoichiometric tables presented on preceding pages, it was not necessary
to
make assumptions concerning a volume change in first four columns of table
(i.e., species, initial number of moles or molar feed rate, change within the
reactor, & remaining number of moles or molar effluent rate).
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.
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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.
Total concentration, CT, at any point in reactor is total molar flow
rate, FT divided by volumetric flow rate υ.
In gas phase, total concentration is also found from gas law, CT =
P/ZRT.
Equating these two relationships gives (4-14)
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At entrance to reactor,
(4-15)
Ratio of Eq. (4-15) to Eq. (4-14) & assuming negligible changes in

compressibility factor,
(4-16)
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 flawUniversity

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species:
(4-18)
Now let’s 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:
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Flow System
(4-23)
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(4-25)
(4-21)
(4-3)
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(4-3)
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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.
(4-3)
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Concentration of key reactant, A, is expressed as a function of conversion in both
flow & batch systems, for various conditions of T, P, & V.
(4-3)
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(4-5)
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‫ة‬-
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CRE-Chapter 4

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ENCH3115Chemical

If rate law depends on more than one species, we must relate

This relationship is most easily established with aid of a

This table presents stoichiometric relationships between reacting

It tells us how many molecules of one species will be formed

already used stoichiometry to relate relative rates of reaction for Eq.

In formulating our stoichiometric table, take species A as our basis

in order to put everything on a basis of “per mole of A.”

Number of moles of A remaining in reactor after a X has

To determine number of moles of each species remaining after

Stoichiometric coefficients in parentheses (d/a+c/a–b/a-1) represent increase in total

Parameter δ tells us change in total number of moles per mole of A

After writing similar equations for B, C, & D, we use stoichiometric table to

We further simplify these equations by defining parameter Θi 8

Now need only to find volume as a function of X to obtain species

Some significant simplifications in reactor design equations are

4.2.1 Equations for Concentrations in Flow Systems

4.2.2 Liquid-Phase Concentrations

For liquids, volume change with reaction is negligible when no

In our previous discussions, we considered primarily systems in which reaction

All of these columns of stoichiometric table are independent of volume

Only when concentration is expressed as a function of conversion does

Equating these two relationships gives (4-14)

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

total molar flow rate is just sum of molar flawUniversity

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