CHEMICAL REACTION ENGINEERING 1

RPKPS

Main reference:
Fogler, H.S., 2006, ”Elements of Chemical
Reaction Engineering”, 4th Ed., Pearson
Education, Inc., Prentice Hall Professional
Technical Reference, New Jersey.

Community:
elisa.ugm.ac.id
Teknik Reaksi Kimia 1_TK_Budhijanto

1. MOLE BALANCES
Objectives:
After completing Chapter 1, you will be able to:
 Define the rate of chemical reaction.

 Apply the mole balance equations to a batch

reactor, CSTR, and PFR.

 Describe photos of real reactors.

Chemical kinetics:
the study of chemical reaction rates and reaction
mechanisms.

Reactor:
an equipment in which reactions occur

Chemical Reaction Engineering (CRE):

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combines the study of chemical kinetics with the
reactors.

How is a chemical engineer different from

other engineers?
It is primarily a knowledge of chemical kinetics
and reactor design that distinguishes the
chemical engineer from other engineers.

Why do we have to study CRE?

The selection of a reaction system that operates
in the safest and most efficient manner can be
the key to the economic success or failure of a
chemical plant.
For example, if a reaction system produces a
large amount of undesirable product, subsequent
purification and separation of the desired
product could make the entire process
economically unfeasible
Specific example: production of maleic
anhydride (raw material for various industries,
e.g. polyester resins, paint, etc)
Main reaction:
O

+ 4,5O2 O + 2CO2 + 2H2O

Side reactions:
+ 7,5O2 6CO2 + 3H2O

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 O

O + 3O 4CO2 + 3H2O
2

Reaction condition: 2 – 5 bar, 400 - 450°C,

vanadium catalyst

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

H3C CH3 H2 + H2C CH2

2. Combination

N2 + O 2 2NO

3. Isomerization
CH3
H3C
H2C
CH2
CH3

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Reaction Rate:
the rate at which a species looses its chemical
identity per unit volume.
It can be expressed as the rate of disappearance
of a reactant or as the rate of appearance of a
product. Consider species A:
AB
rA = the rate of formation of species A per unit
volume
−rA = the rate of a disappearance of species A
per unit volume
rB = the rate of formation of species B per unit
volume
If B is being created at a rate of 0.2 moles per
decimeter cubed per second, ie, the rate of
formation of B is,
rB = 0.2 mole/(dm3∙s)
Then A is disappearing at the same rate:
−rA = 0.2 mole/(dm3∙s)
The rate of formation of A is
rA = −0.2 mole/(dm3∙s)
For a catalytic reaction, we refer to −rA’, which
is the rate of disappearance of species A on a per
mass of catalyst basis.
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NOTE: dCA/dt is not the rate of reaction

Example: Is sodium hydroxide reacting?

Sodium hydroxide and ethyl acetate are
continuously fed to a rapidly stirred tank in
which they react to form sodium acetate and
ethanol:
NaOH + CH3COOC2H5  CH3COONa + C2H5OH

The product stream, containing sodium acetate

and ethanol, together with the unreacted sodium
hydroxide and ethyl acetate, is continuously
withdrawn from the tank at a rate equal to the
total feed rate. The contents of the tank in which
this reaction is taking place may be considered
to be perfectly mixed. Because the system is
operated at steady state, if we were to withdraw
liquid samples at some location in the tank at
various times and analyze them chemically, we
would find that the concentrations of the
individual species in the different samples were
identical. Because the species concentrations are
constant and therefore do not change with time,
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 𝑑𝐶𝐴
=0
𝑑𝑡

where A is NaOH. If we defined

𝑑𝐶𝐴
𝑟𝐴 =
𝑑𝑡
then
𝑟𝐴 = 0
which is incorrect because C2H5OH and
CH3COONa are being formed from NaOH and
CH3COOC2H5 at a finite rate. Consequently, the
rate of reaction as defined by
𝑑𝐶𝐴
𝑟𝐴 =
𝑑𝑡
cannot apply to a flow system and is incorrrect if
it is defined in this manner.
rA is an algebraic law!
𝑑𝐶𝐴
𝑟𝐴 =
𝑑𝑡
is simply a mole balance that is only valid for a
constant volume batch system.
Consider species j:

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  rj is the rate of formation of species j per
unit volume [e.g. mol/(dm3∙s)]
 rj is a function of concentration,
temperature, pressure, and the type of
catalyst (if any)
 rj is independent of the type of reaction
system (batch, plug flow, etc.)
 rj is an algebraic equation, not a differential
equation
We use an algebraic equation to relate the rate of
reaction, −rA, to the concentration of reacting
species (e.g. CA) and to the temperature (T) at
which the reaction occurs. Example:
A  product
−𝑟𝐴 = 𝑘 (𝑇)𝐶𝐴
−𝑟𝐴 = 𝑘 (𝑇)𝐶𝐴2
𝑘1 (𝑇)𝐶𝐴
−𝑟𝐴 =
1 + 𝑘2 (𝑇)𝐶𝐴
Which one is the correct one?
It must be determined from experimental
observation.

Problem 1.1.: The Convention for Rates of

Reaction
Consider the reaction
A + 2B  3C

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in which the rate of disappearance of A is 5
moles of A per dm3 per second at the start of the
reaction.
At the start of the reaction
(a) What is −rA?
(b) What is the rate of formation of B?
(c) What is the rate of formation of C?
(d) What is the rate of disappearance of C?
(e) What is the rate of formation of A, rA?
(f) What is –rB?

General Mole Balance Equation

A mole balance on species j at any instant in

time, t:

𝑉 𝑑𝑁𝑗
𝐹𝑗0 − 𝐹𝑗 + 𝐺𝑗 = 𝐹𝑗0 − 𝐹𝑗 + ∫ 𝑟𝑗 𝑑𝑉 =
𝑑𝑡
Where

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Nj represents the number of moles of species j in
the system at time t.
V is the reaction volume.

Batch Reactors

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10
 𝐹𝑗0 = 𝐹𝑗 = 0
𝑉 𝑑𝑁𝑗
∫ 𝑟𝑗 𝑑𝑉 =
𝑑𝑡

Assumption: the reaction is perfectly mixed.

𝑑𝑁𝑗
= 𝑟𝑗 𝑉
𝑑𝑡
Or
𝑁𝑗 𝑑𝑁
𝑗
𝑡=∫
𝑁𝑗0 𝑟𝑗 𝑉
There are two types of batch reactor for gas
phase reactions.
1. Constant volume batch reactors
𝑑𝐶𝑗
= 𝑟𝑗
𝑑𝑡
2. Constant pressure batch reactors
1 𝑑𝑁𝑗 1 𝑑(𝐶𝑗 𝑉) 𝑑𝐶𝑗 𝐶𝑗 𝑑𝑉
𝑟𝑗 = = = +
𝑉 𝑑𝑡 𝑉 𝑑𝑡 𝑑𝑡 𝑉 𝑑𝑡
𝑑𝐶𝑗 𝑑 (ln 𝑉 )
= + 𝐶𝑗
𝑑𝑡 𝑑𝑡

Continuous Stirred Tank Reactor (CSTR =

Vat = Backmix Reactor)

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Assumption: the reaction is perfectly mixed.
Thus:
𝑉
1. ∫ 𝑟𝑗 𝑑𝑉 = 𝑟𝑗 𝑉
2. The conditions in the exit stream (e.g.
concentration, temperature) are identical to
those in the tank.
𝑑𝑁𝑗
𝐹𝑗0 − 𝐹𝑗 + 𝑟𝑗 𝑉 =
𝑑𝑡
At steady state:
𝑑𝑁𝑗
=0
𝑑𝑡
We get:
𝐹𝑗0 − 𝐹𝑗 + 𝑟𝑗 𝑉 = 0
Or
𝐹𝑗0 − 𝐹𝑗
𝑉=
−𝑟𝑗
Because:
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 𝐹𝑗 = 𝐶𝑗 𝑣
Where
v = the volumetric flow rate (volume/time)
𝐶𝑗0 𝑣0 − 𝐶𝑗 𝑣
𝑉=
−𝑟𝑗
Tubular Reactor

Assumption: plug flow  no radial variation in

reaction rate  the reactor is referred to as a
Plug Flow Reactor (PFR).

Fj0 Fj,exit

Fj│V ∆V Fj│V+∆V
) volume, ΔV, is sufficiently
The differential
small such that there are no spatial variations in
reaction rate within its volume.
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At steady state:
Fj V   V rj dV  Fj V  V  0
Fj V  rj V  Fj V  V  0
Fj V  V  Fj V
 rj
V
limit ∆V→0:
dFj
 rj
dV
Or
dFj
V F
F jj0
rj

Summary:
General Mole Balance Equation:
dN j
F j 0   rj dV  F j 
V

dt

Reactor Mole Balance Remark

Batch dN j Perfectly mixed
 rjV
dt
CSTR Fj0  Fj Perfectly mixed;
V Steady State
 rj
PFR dFj Steady State
 rj
dV
Akhir Kuliah 1
Problem 1.2.: How Large Is It?

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Consider the liquid phase cis-trans isomerization
of 2-butene.
H H H CH3

H3C CH3 H3C H

which we will write symbolically as
A → B
The first order (−𝑟𝐴 = 𝑘𝐶𝐴 ) reaction is carried
out isothermally in a tubular reactor in which the
volumetric flow rate, v, is constant = 10 L/min.
The exiting concentration of A is 10% of its
entering concentration. k = 0,23/min.
a. Sketch the concentration profile inside the
PFR
b. Determine the reactor volume

Problem 1.3.:
The same as Problem 2b, but instead of using a
PFR, the reaction occured in an isothermal
CSTR.

Problem 1.4.:
A 200 L constant-volume batch reactor is
pressurized to 20 atm with a mixture of 75% A
and 25% inert. The gas-phase reaction is carried
out isothermally at 227 C.

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 V = 200 L
P = 20 atm
T = 227°C
a. Assuming that the ideal gas law is valid, how
many moles of A are in the reactor initially?
What is the initial concentration of A?
b. If the reaction is first order:

Calculate the time necessary to consume 99%

of A.
c. If the reaction is second order:

Calculate the time to consume 80% of A. Also

calculate the pressure in the reactor at this
time if the temperature is 127°C.

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