Lecture 3

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 3

Lecture 3
Review of Lectures 1 and 2
Building Block 1
Mole Balances (Review)
Size CSTRs and PFRs given rA= f(X)
Conversion for Reactors in Series
Building Block 2
Rate Laws
Reaction Orders
Arrhenius Equation
Activation Energy
Effect of Temperature

2
 Review Chapter 1

Building Block 1: Mole Balance

The GMBE applied to the four major reactor
types (and the general reaction AB)
Reactor Differential Algebraic Integral
NA
NA
dN A
Batch dN A
rAV t rAV
dt N A0
t
CSTR FA 0 FA
V
rA FA
FA
dFA dFA
PFR
dV
rA V
FA 0
drA
V

FA FA
dFA dFA
PBR
dW
rA W
FA 0
rA
3
W
 Review Chapter 2

a A bB
c C d D
Choose limiting reactant A as basis of calculation

b c d
A B
C D
a a a

moles A reacted
X
moles A fed

4
 Review Chapter 2

Building Block 1: Mole Balance

In terms of Conversion
Reactor Differential Algebraic Integral
X
X
dX
Batch N A0
dX
r AV t N A0
dt 0
rAV
t
FA0 X
CSTR V
rA
X
dX dX
PFR FA0 rA V FA0
dV 0
rA
X
X
dX
PBR FA0
dX
rA W FA0
5 dW rA
0
W
 Review Chapter 2

Levenspiel Plots

6
 Review Chapter 2

Reactors in Series

moles of A reacted up to point i

Xi
moles of A fed to first reactor

Only valid if there are no side streams

7
 Review Chapter 2

Reactors in Series

8
 Chapter 3

Building Block 2: Rate Laws

Power Law Model:

order in A
rA kCA CB
order in B
Overall Rection Order

9
 Chapter 3

Building Block 2: Rate Laws

2A B 3C

A reactor follows an elementary rate law if the

reaction orders just happens to agree with the
stoichiometric coefficients for the reaction as written.
e.g. If the above reaction follows an elementary rate
law
rA k AC ACB
2

2nd order in A, 1st order in B, overall third order

10
 Chapter 3

Building Block 2: Rate Laws

Rate Laws are found from Experiments
2A+B3C
Rate Laws could be non-elementary. For
example, reaction could be:
Second Order in A
Zero Order in B
Overall Second Order
rA k AC A2
rB k B C 2
A

11
rC kC C A2
 Chapter 3

Relative Rates of Reaction

aA bB cC dD
b c d
A B C D
a a a
rA rB rC rD

a b c d

12
 Chapter 3

Relative Rates of Reaction

2A B 3C
mol
Given rA 10
dm s
3

rA rB rC
Then
2 1 3
rA mol
rB 5
2 dm s
3

3 mol
rC rA 15
2 dm s
3

13
 Chapter 3

Reversible Elementary Reaction

kA
A+2B 3C
k-A

C 3

rA k AC AC B k ACC k A C A C B
2 3 2 C

k A k A
2 CC3
k A C A C B
Ke

14
 Chapter 3

Reversible Elementary Reaction

kA
A+2B 3C Reaction is: First Order in A
k-A Second Order in B
Overall third Order

moles
rA 3
moles
CA
dm s dm3

rA mole dm3 s dm6

k 2
A B
C C mole dm 3

mole dm 3

2
mole2 s
15
 Chapter 3

16
 Chapter 3

Algorithm
How to find rA f X

Step 1: Rate Law rA g Ci

Step 2: Stoichiometry Ci h X

Step 3: Combine to get rA f X

17
 Chapter 3

Arrhenius Equation
k is the specific reaction rate (constant) and is
given by the Arrhenius Equation.
where:
E RT
k Ae

T k A
k T 0 k 0
A 10 13

T
18
 Chapter 3

Arrhenius Equation
where:
E = Activation energy (cal/mol)
R = Gas constant (cal/mol*K)
T = Temperature (K)
A = Frequency factor (same units as rate constant k)
(units of A, and k, depend on overall reaction order)

19
 Chapter 3

Activation Energy
Concept 1. Law of Mass Action
The rate of reaction increases with increasing concentration of reactants
owing to the corresponding increase in the number of molecular collisions.

The rate of disappearance of A, rA, depends on temperature and

concentration. For many irreversible reactions, it can be written as the
product of a reaction rate constant, kA, and a function of the concentrations
(activities) of the various species involved in the reaction:

-rA = kA (T ) fn (CA,CB ) (3-2)

For example for the elementary reaction

AB + C
A + BC
-rAB = kABCABCC = AABe-E RT
CABCC
E = Activation Energy, (kJ/mol)
20
 Chapter 3

Collision Theory

21
 Chapter 3

Why is there an Activation Energy?

We see that for the reaction to occur, the reactants
must overcome an energy barrier or activation
energy EA. The energy to overcome their barrier
comes from the transfer of the kinetic energy from
molecular collisions to internal energy (e.g.
Vibrational Energy).
1. The molecules need energy to disort or stretch
their bonds in order to break them and thus form
new bonds
2. As the reacting molecules come close together
they must overcome both stearic and electron
repulsion forces in order to react.
22
 Chapter 3

Activation Energy
Concept 2. Potential Energy Surfaces and Energy Barriers

AB + C
A\B\C A + BC
As two molecules, say AB and C, approach each other, the potential
energy of the system (AB, C) increases owing repulsion of the molecules.
The reaction coordinate is a measure of progress of the reaction as we go
form AB and C to A and BC as shown in Figure 3-2 below.

23
 Chapter 3

Activation Energy
Concept 2. Potential Energy Surfaces and Energy Barriers
The figure below shows a 3-dimensional energy surface and barrier over
which the reaction must pass

24
 Chapter 3

Activation Energy
Concept 2. Potential Energy Surfaces and Energy Barriers

25
 Chapter 3

Activation Energy
Concept 3. Fraction of Molecular Collisions That Have Sufficient Energy
to React
The kinetic energy of the molecule must be transferred to potential energy to
distort bonds and overcome steric forces in order for the reacting molecules to
pass over the energy barrier.
The distribution of velocities of the reacting molecules relative to one another is
given by the Boltzmann distribution

m 3 2 -mU2
( )
f U ,T = 4p exp

2pkBT
U2
2kBT
Where
kB = Boltzmanns constant = 3.29 x 1024 cal/molecule/K
m = Reduced mass, g
U = Relative velocity, m/s
T = Absolute Temperature, K
e = Energy = mU2, kcal/molecule
E = Kinetic energy, kcal/mol
26 f(U,T) = Fraction of relative velocities between U and U + dU
 Chapter 3

Activation Energy
Concept 3. Fraction of Molecular Collisions That Have Sufficient
Energy to React
Distribution of Velocities
We will use the Maxwell-Boltzmann Distribution of Molecular Velocities.
For a species of mass m, the Maxwell distribution of velocities (relative
velocities) is:
32
m
f U , T dU 4 e mU 2 2 k BT
U 2 dU
2 k BT
f(U,T)dU represents the fraction of velocities between U and (U+dU).

27
 Chapter 3

Activation Energy
Concept 3. Fraction of Molecular Collisions That Have Sufficient
Energy to React
Distribution of Velocities
A plot of the distribution function, f(U,T), is shown as a function of U:
T1
T2 T2>T1

U
28 Maxwell-Boltzmann Distribution of velocities.
 Chapter 3

Activation Energy
Concept 3. Fraction of Molecular Collisions That Have Sufficient
Energy to React
Distribution of Velocities
32
m
Given f U , T dU 4 e mU 2 2 k BT
U 2 dU
2 k B T

1
Let E mU 2
2
E
2
f E , T dE 1 2 k BT
E e dE
2 k BT
32

f(E,T)dE represents the fraction of collisions that have energy between

E and (E+dE)
29
 Chapter 3

Activation Energy
Concept 3. Fraction of Molecular Collisions That Have Sufficient Energy
to React
In terms of energy per mole, E, instead of energy per molecule, e, we have

1 3 2 1 2 -E
( )
f E ,T = 2p E exp
pRT RT
(3-20)

where E is in (cal/mol) or (J/mole), R is in (cal/mol/K), and f(E,T) is in mol/cal.

The distribution function f(E,T) is most easily interpreted by recognizing that

[f(E,T) dE] is the fraction of collisions with energies between E and E + dE.

1 3 2 -E
( )
f E ,T dE = 2p E exp

pkBT
1 2
dE
kBT
(3-21)

This distribution is shown as a function of E for two temperatures in the next

slide.
30
 Chapter 3

Activation Energy
Concept 3. Fraction of Molecular Collisions That Have Sufficient Energy
to React
kcal
0.25 f (E ,T ) dE
0.35
Fraction with energies between (0.25) and 0.35) =
mol
This fraction is shown by the shaded area in Figure 3-4(a) and is approximated
by the average value of f(E,T) at E = 0.3 kcal/mole is 0.81 mol/kcal.
0.81 mol kcal
( ) ( )
f E ,T dE = f 0.3, 300K DE =
kcal
0.35
kcal
mol
- 0.25
mol
= 0.081

31
We see 8.1% of the collisions have energies between 0.25 and 0.35 kcal/mol
 Chapter 3

Activation Energy
Concept 3. Fraction of Molecular Collisions That Have Sufficient Energy
to React
Fraction of Molecules with Energy Greater than EA
We can also determine the fraction of collision that have energies greater than
a certain value, EA

(Fraction of Molecules with E > EA ) = F (E > EA ,T ) = E f (E ,T ) dE

(3-22)
A

For EA > 3RT, we can obtain an analytical approximation for the fraction of
molecules of collision with energies greater than EA by combining Equations (3-
21) and (3-22) and integrating to get
12
Fraction of collision with E
A
(
energies greater than E = F E > E A ,T @ )
2 EA
exp - A (3-23)

p RT
RT

Equation (3-23) is plotted in Figure 4-4(b) as a function of activation energy,
EA, as shown in the next slide.
32
 Chapter 3

Activation Energy
Concept 3. Fraction of Molecular Collisions That Have Sufficient
Energy to React
Fraction of Molecules with Energy Greater than EA
One observes for an activation energy EA of 20 kcal/mol and a temperature
of 300 K the fraction of collisions with energies greater than 20 kcal/mol is
1.76 x 1014 while at 600 K, the fraction increases to 2.39 x 107, which is
a 7 orders of magnitude difference.

33
 End of Lecture 3

34
 Chapter 3 Professional
Reference Shelf

Supplementary Material
BC AB

VBC VAB
kJ/ kJ/
Molecule Molecule

r0 rBC r0
rAB

Potentials (Morse or Lennard-Jones)

35
 Chapter 3 Professional
Reference Shelf

Supplementary Material
One can also view the reaction coordinate as variation of the BC
distance for a fixed AC distance:

l


l

l


A B C A BC AB C
rAB rBC

For a fixed AC distance as B moves away from C the distance of

separation of B from C, rBC increases as N moves closer to A. As
rBC increases rAB decreases and the AB energy first decreases
then increases as the AB molecules become close. Likewise as B
moves away from A and towards C similar energy relationships
are found. E.g., as B moves towards C from A, the energy first
decreases due to attraction then increases due to repulsion of the
AB molecules as they come closer together. We now
superimpose the potentials for AB and BC to form the following
36 figure:
 Chapter 3 Professional
Reference Shelf

Reaction Coordinate
The activation energy can be thought of as a barrier
to the reaction. One way to view the barrier to a
reaction is through the reaction coordinates. These
coordinates denote the energy of the system as a
function of progress along the reaction path. For the
reaction:
A BC A ::: B ::: C AB C

The reaction coordinate is:

37
 Chapter 3 Professional
Reference Shelf

Supplementary Material
Reference
AB
S2
S1
BC
Energy

E*

Ea
E1P
E2P
HRx=E2P-E1P
38 r