ERT 208

REACTION ENGINEERING
MOLE BALANCE
MISMISURAYA MEOR AHMAD
School of bioprocess engineering
Unimap

Course Outcome No.1:

Ability to solve the rate of reaction
and their kinetics.

objectives
DESCRIBE and DEFINE the rate
of reaction,
DERIVE the general balance
equation,
APPLY the general mole balance
to the three most common types
of industrial reactors.

Definition

Chemical Reaction Engineering (CRE):

Combines the study of chemical
kinetics with the reactors in which the
reaction occur.
Chemical kinetics:
the study of chemical reaction rates
& reaction mechanisms.
Chemical kinetics & reactor design
are important things in chemical industrial

CHEMICAL ENGINEER
Distinguishes between other engineers is:

a knowledge of
Chemical Kinetics & Reactor Design
Aim
Select reaction system that operates in the safest
and most efficient manner key to economic
success or failure of a chemical plant.

Chemical Reaction Engineering

principle can be applied in:
Waste treatment
Microelectronics
Nanoparticles
pharmaceutical
living system of chemical manufactures

Points of view
Before discuss the conditions that effect chemical
reaction rate mechanisms & reactor design

it is necessary to account for the various chemical

species entering & leaving a reaction system.

Achieved through overall mole balances on

individual species in the reacting system.

So that, we will develop a general mole balance that

can be applied to any species entering, leaving or
remaining within the reaction system volume
After that, used general mole balance equation to
develop a preliminary form of the design equations
of the most common industrial reactor:

Batch Reactor (BR), Continuous-Stirred Tank

Reactor (CSTR), Plug Flow Reactor/ Tubular
(PFR) & Packed Bed Reactor (PBR)

THE RATE OF Reaction (-rA)

The Rate of Reaction show how fast a
number of moles of one chemical
species are being consumed to form
another chemical species. (The rate at
which a species loses its chemical
identity per unit volume)

Chemical identity

A chemical species is said to have

reacted when it has lost its
chemical identity.
The identity of a chemical species is
determined by the kind, number,
and configuration of that species'
atoms.

Three ways a
chemical species
can lose its
chemical identity

1) Decomposition

3) Isomerization

2) Combination

 The rate of a reaction can be expressed in several

ways:
1) The rate of disappearance of a reactant,

-rj

rj is the number of moles j reacting

(disappering) per unit time per unit volume
(mol/dm3.s)
The numerical value rj is positive number

2) The rate of appearance of species j, j

rj is the rate of formation (generation) of species j.

If species j is reactant The numerical value of

rj will be a negative number.
(i.e: rA = - 4 mole A/dm3.s)
If species j is product The numerical value of
rj will be a positive number.
(i.e: rB = 4 mole A/dm3.s)
The relation between the rate of formation of one species
and the rate of disapperance of another species in chemical
reaction will be discuss in Chapter 3

Example:

A + 2B

C+D

 2 types of reaction systems:

1) Homogeneous system (one phase)- rate of
reaction measure in volume
2) Haterogeneous system (more than one phase)rate of reaction measure in reaction surface
area or catalyst weight

A
B
For a catalytic reaction, we refer to -rA',
which is the rate of disappearance of
species A on a per mass of catalyst basis.

THE RATE Equation (rate law) for -rj

Is an algebraic equation that is solely

function of the properties of the reacting
materials & reaction condition [i.e: species
concentration, temperature, pressure and
the type of catalyst].
The rate equation is independent of the type
of reactor (batch, plug flow,cstr etc.) in
which the reaction is carried out.

THE RATE Equation (rate law) for -rj

However, because the properties & reaction
conditions of the reacting materials may vary
with position in chemical reactor, rj can turn be
function of position & can vary from point to
point in the systems.
Rate law is essentially an algebraic equation
involving concentartion (is not a differential
equation)

 Example, the algebraic form of the rate

law for rA for the reaction:

A products
may be a linear function
of concentration:
may be a quadratic function
of concentration:

determined
from
experimental
observation

 The rate of disappearance of A is equal to a

rate constant K (which is a function of
temperature) times the square of the
concentration of A.

General mole balance equation

(gmbE)

To perform a mole balance on any

system, the system boundary
must be specified.
The volume enclosed by these
boundaries is referred as system
volume, V.

 We shall perform a mole balance on a

particluar chemical species, j in a
system volume, V.

 So that, mole balance on species j at any instance in

time,t produces the following equation:

How to derive?

Step 1:
Understand the meaning of all the
terms!
(Fj0,Fj, Gj and Nj)

 Fj0= rate of flow of j into the system

Fj = rate of flow of j out of the system
Nj =the no of moles of species j in the
system at time,t

Gj = reaction volume x rate of formation of

species j,

If all the system variable [temp., catalytic

activity, conc. of the chemical species] are
uniform throughout the system volume, the
Rate of Generation of species j, Gj is just the
product of the reaction volume, V & the
rate of formation of species j, rj.

The rate of formation of species j for the

reaction varies with the position in the
system volume. So that, it has rj1 at location
1, which is surrounded by a small volume,
V1, within which the rate is uniform.
Suppose, rj1 is surrounded by V1 and so
on, therefore:

 The total rate of generation within the

system volume is the sum of all the rates
of generation in each of the
subvolumes.
If the total system volume is divided into
M subvolumes, the total rate of
generation is:

 Appropriate limit ( let

the equation becomes:

Now, replace Gj with this equation.

 Therefore, the GMBE for any chemical species j which

is entering, leaving, reacting, and/or accumulating
within any system volume V.

From this GMBE, we can develop the design

equations for the various types of industrial
reactors.
Evaluation of GMBE can determine the time
(batch) or reactor volume (continuous flow)
necessary to convert a specified amount of the
reactants into products.

Mole balance equation on different

reactor types

The GMBE applied to the major reactor

types and the general reaction:

1) Batch Reactor (BR)

BR used for small scale operation:
For testing new processes.
For manufacture expensive products.
For processes that are difficult to
convert to continuous operations.

BR advantage:
High conversions (can be obtained by leaving
the reactant in the reactor for long period of
time).

BR disadvantage:
High labor cost per batch
The variability of products from batch to
batch
The difficulty of large-scale production

1) Batch Reactor

Batch derivation
General Mole Balance on System Volume, V

No inflow or outflow while reaction is carried out:

From GMBE:
Mole Balance Equation for Batch reactor become:

Assumption (BR):

Perfect mixing,therefore no variation in

reaction rate throughout the reactor
volume (Same rate of reaction). So, rj is
removed, integrate, rewrite the MBE:

Now, lets think about isomerization of

species A in a BR.

As the reaction proceeds:

no of moles of A, NA decreases &
no of moles of B, NB increases.

 Question: what time, t1 is necessary to

reduce the initial no of moles from NA0
to final desired number, NA1.
Step1: Apply the equation:

Step 2: Rearranging, so that we get t:

 Step 3: Integrate with limits,

at t=0, then NA=NA0
at t= t1, then NA=NA1

Obtain:
This is integral form of
mole balance on a BR.
It gives the time, t1 necessary to reduce the
number of moles from NAO to NA1 and also to form NB1
moles of B

2) Continous flow reactors

Operate at steady state (conditions do not
change with times).
Consider 3 types:
i) Continous Stirred Tank Reactors(CSTR)
ii) Plug Flow Reactors(PFR)/Tubular Reactor
iii) Packed Bed Reactors(PBR)

i) Continous Stirred Tank reactor

(CSTR)
Used commonly in industrial processing
the stirred tank operated continuously.
Also referred as vat or backmix reactor.
Used primarily for liquid phase reactions.
Operate at steady-state.
Is assumed to be perfect mixed/ ideal mixing [no
time & no position depends with the temp., conc.
or reaction rate inside the CSTR- means every
variable is the same at every point inside the
reactor ].

 View of CSTR

 GMBE on System Volume V.

Applying on CSTR(Steady State i.e condition dont
change with time):

Also, Perfect Mixing (no variation in rate of reaction):

So, it becomes a design equation of a CSTR:

 The design equation gives the reactor volume, V

necessary to reduce the entering flow rate of
species j, Fjo to the exit flow rate, Fj when species j
is disappering at a rate rj.
CSTR is modeled based on conditions in the exit
stream [conc., temp.] are identical to those in the
tank. So that, the molar flow rate, Fj is just the
product of the conc. of species j & volumetric flow
rate, V
Fj = concentration of species j x the volumetric flow
rate:

 Replace Fj and combine, we can write a

balance on species A in CSTR as:

ii) Tubular Reactors

Consists of a cylindrical pipe.
Operate at steady-state.
Used for gas-phase reaction.

Tubular Reactor Schematic

 In the tubular reactor, the reactants are continually

consumed as they flow down the lenght of the
reactor.
In modeling the tubular reactor, we assume the
concentration varies continously in axial direction
through the reactor.
Therefore, the reaction rate (function of conc.) will
also varies axially.
We consider systems in which the flow field
modeled by Plug Flow Profile (uniform velocity
as in turbulent flow, no radial variation in reaction
rate & the reactor referred to as a Plug Flow
Reactor (PFR))

PLUG-FLOW REACTOR (PFR)

There are two ways to developed the design equation

of PFR at steady state:
1) Directly from GMBE by differentiating with
respect to volume, V

Or
2) From mole balance on species j in a differential
segment of the reactor volume V.

 Lets choose the 2nd ways to arrive at the differential

form of the PFR mole balance

The differential volume, V will be chosen sufficiently small

(there are no spatial variation in reaction rate within this
volume). Thus the generation Gj is

We obtain the differential form of steady state

mole balance on a PFR:

To derive MB on PFR:

At steady state: Accumulation = 0

Dividing by V and rearranging

The term in brackets resembles the definition of the derivative:

 Taking the limit as V approaches zero, we

get the differential form of steady state
mole balance on a PFR.

MBE of tubular reactors of

variable & constant crosssectional area

Pablo Picasso design the reactor for an

irregular shape reactor [Pablo Picassos
reactor]

The conclusion from the application of the design

equation Picassos Reactor:

The degree of completion of a

reaction achieved in ideal PFR does
not depends on its shape, only on its
total volume

 Consider isomerization of A B in PFR.

As reactants proceed down the reactor, A
is consumed by chemical reaction and B is
produced.
Consequently, the molar flow rate of A
decreases and molar flow rate of B
increases.
Profile of Molar
Flow Rate in a
PFR

 Question: What is the reactor volume, V1

necessary to reducethe entering molar flow rate
of A from FA0 to FA1.

Rearrange equation to become:

Integrate with limits:
at V=0,FA=FA0
at V=V1, FA=FA1
V1 is the volume necessary
to reduce the entering
molar flow rate FA0 to FA1
& also the volume
necessary to produce a
molar flow rate of B, FB1

iii) Packed-bed reactor (PBR)

The principle difference between

rector design calculation which is
the reaction occur in the surface of
the catalyst (heterogeneous system).
So that, the reaction is based on
mass of solid catalyst, W rather than
reactor volume, V.
The differential form of mole
balance for PBR:

 The mass solid catalyst, W used

because the amount of the catalyst
is important to the rate of product
formation.
The reactor volume that contain
catalyst is of secondary significance.
Shows a schematic of an industrial
catalytic reactor with vertical tubes
packed with catalyst.

For heterogeneous system, the rate of

reaction of a substance A is define as:

Derivation of mole balance on PBR

The derivation of the design equation for PBR will
be carried out in a manner analogous to the
development of the tubular design equation.
To do this, we replace the volume, V coordinate in
MB of PFR (Tubular) with the catalyst weight, W.

 The MB on species A over catalyst weight W

produces this equation:

The dimensions of generation terms in the equation

are:

The differential form of MB for a PBR:

When pressure drop through the reactor &

catalyst decay are neglected, the integral
form of PBR design equation can be used
to calculate the catalyst weight:

Example 1.1: How Large is it?

Question?

Solution

SUMMARY
In the BR, PFR & CSTR, the design equation (mole balances)
were developed based on reactor volume, V. While design
equation of PBR based on mass solid catalyst, W.

Industrial Reactors
British Petroleum Reactor Photos
Fixed Bed Reactor

3 Stage Converter used to convert H2S to SO2

Fluidized Bed Reactor

Hydrogen Plant

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