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 Building Blocks

types (and the general reaction AB)

Reactor Differential Algebraic Integral
NA NA
dN A
Batch dN A
 rAV t 
dt rV
N A0 A
t
CSTR FA 0  FA
V
rA FA
FA
dFA dFA
PFR
dV
 rA V 
FA 0
drA
V

FA
dFA FA
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 Building Blocks

Reactor Differential Algebraic Integral

X
X
dX
Batch N A0
dX
  r AV t  N A0 
dt 0
 rAV
F X t
CSTR V  A0
 rA
X
dX dX
PFR FA0  rA V  FA0 
dV 0
 rA

X
X
dX dX
PBR FA0   rA W  FA0 
dW 0
 rA
5 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: Building Blocks

  α order in A
 rA  kC C
A B
β order in B
Overall Rection Order  α  β

9
 Chapter 3

Building Block 2: Rate Laws

2A  B  3C Building Blocks

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 AC B
2

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

10
 Chapter 3

Building Block 2: Rate Laws

2A+B3C Building Blocks

If  rA  kC 2
A

›Second Order in A
›Zero Order in B
›Overall Second Order
- rA =kA CA2 CB
- rB =k B CA2 CB
2
rC =kC C CB
A

11
 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
dm3  s
rA rB rC
Then  
 2 1 3
 rA mol
 rB  5
2 dm 3  s
3 mol
rC  rA  15
2 dm 3  s
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  
 K e 

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 moles
  rA   3 CA 
dm s dm 3

  rA  mole dm 3 s dm 6
k   2   
 A B   mole dm  mole dm 
2 2
C C 3 3 mole s
15
 Chapter 3

16
 Chapter 3

The 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 ® 0k® 0

A » 1013 s  and in appropriate

                  concentration units
18 T
 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 =éëk A ( T ) ùûé
ëfn ( CA ,CB …) ù
û (3-2)

For example for the elementary reaction

AB +C ®
¬ A + BC
- rAB =k ABCABCC =AAB e- E RT
CABCC

E = Activation Energy, (kJ/mol)

20
 Chapter 3

Collision Theory
AB +C ®
¬ A + BC
C

AB
A C
B
AB
C

UR

- rAB =kCABCC
21
 Why is there an Activation Chapter 3

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

æ m ö3 2 é- mU2 ù
( )
f U,T =4p çç ÷ exp ê úU2
÷ ê
è2pkBT ø ë 2kBT ú
û
Where
kB = Boltzmann’s constant = 3.29 x 10–24 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

𝑓 ( 𝑈 ,𝑇 )
 

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 BT 

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
æ 1 ö3 2 1 2 é- E ù
( )
f E,T =2p ç ÷ E exp ê ú
è pRT ø ëRT û
(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.

æ 1 ö3 2 é- E ù
1 2
( )
f E,T dE=2p çç ÷ E exp ê údE
÷
è pkBT ø ê
ëkBT ú
û
(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
æ kcal ö 0.35
çFraction with energies between (0.25) and 0.35) ÷= ò f E,T dE
( )
è mol ø 0.25
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 æ kcal kcal ö
( ) ( )
f E,T dE=f 0.3, 300K D E=
kcal è
ç0.35
mol
- 0.25
mol ø
÷=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 = ò f E,T dE
) ( ) ( ) (3-22)
EA

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
æFraction of collision with ö 2 æE ö æ E ö
(
çenergies greater than E ÷=F E> EA ,T @ ç ÷ exp ç- A ÷
A
)
ç ÷ ç RT ÷ (3-23)
è Aø p èRT ø è ø

Equation (3-23) is plotted in Figure 4-4(b) as a function of activation energy, E A,

32 as shown in the next slide.
 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 10–14 while at 600 K, the fraction increases to 2.39 x 10–7, 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  
rAB rBC A BC AB C

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 figure:
36
 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:

r1 r* r2
37
 Chapter 3 Professional
Reference Shelf

Supplementary Material
Reference
AB
S2
S1
BC
Energy
(
Ea =S1 r* - r1 )
[See PRS Ch3]
E*

Ea
E1P
E2P r1 r* r2 ∆HRx=E2P-E1P

38 r