1.

REACTION KINETICS

Main reference:
Fogler, H.S., 2016, ”Elements of Chemical
Reaction Engineering”, 5th Ed., Pearson
Education, Inc., Prentice Hall International
Series in the Physical and Chemical Engineering
Sciences, New Jersey.

Community:
elisa.ugm.ac.id
Kinetika_Reaksi_S2_Budhijanto

1.MOLE BALANCES

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

Reactor:
an equipment in which reactions occur

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.
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Three ways a chemical species can lose its
chemical identity:
1. Decomposition

H3C CH3 H2 + H2C CH2

2. Combination

N2 + O2 2NO

3. Isomerization
CH3
H3C
H2C
CH2
CH3

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
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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.
rA is an algebraic law.
Consider species j:
 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

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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
−r A=k (T ) C A
2
−r A=k (T ) C A
k (T ) CA
−r A= 1
1+k 2 ( T ) C A

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
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

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A mole balance on species j at any instant in
time, t:

V
dNj
F j 0−F j +G j =F j 0−F j +∫ r j dV =
❑ dt
Where
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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 F j 0=F j=0
V
dN
∫ r j dV = dt j
❑

Assumption: the reaction is perfectly mixed.

dNj
=r j V
dt
Or
Nj
dNj
t=∫
N j0
r jV

There are two types of batch reactor for gas

phase reactions.
1.Constant volume batch reactors
dCj
=r j
dt
2.Constant pressure batch reactors
1 d N j 1 d ( C j V ) d C j C j dV d C j d ( ln V )
r j= = = + = +C j
V dt V dt dt V dt dt dt

Continuous Stirred Tank Reactor (CSTR =

Vat = Backmix Reactor)

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Assumption: the reaction is perfectly mixed.
Thus:
V

1. ∫ r dV =r V
❑
j j

2. The conditions in the exit stream (e.g.

concentration, temperature) are identical to
those in the tank.
dNj
F j 0−F j +r j V =
dt
At steady state:
dNj
=0
dt
We get:
F j 0−F j +r j V =0

Or
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 F j 0−F j
V=
−r j

Because:
F j=C j v

Where
v = the volumetric flow rate (volume/time)
C j 0 v 0−C j v
V=
−r j

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

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The differential volume, ΔV, is sufficiently small
such that there are no spatial variations in
reaction rate within its volume.
At steady state:
ΔV
F j|V +∫ r j dV −F j|V + ΔV =0
F j|V +r j ΔV −F j|V + ΔV =0
F j|V + ΔV −F j|V
=r j
ΔV
limit ∆V→0:
dF j
=r j
dV
Or
Fj dF j
V =∫F
j0 rj

Summary:
General Mole Balance Equation:
V dN j
F j0 +∫ r j dV −F j=
dt

Reactor Mole Balance Remark

Batch dN j Perfectly mixed
=r j V
dt
CSTR F j0 −F j Perfectly mixed;
V= Steady State
−r j
PFR dF j Steady State
=r j
dV
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Problem 1.2.: How Large Is It?
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 ( −r =k C ¿ reaction is carried out
A A

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 227°C.

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