Faculty of

Institute of Chemical and Food

Technology Engineering

Course: Advanced Reaction Engineering

(ChEg,xxxx)

Lecture II: Stoichiometry and Reaction Rate Laws

Stoichiometry

Rate Laws

Mole Balance

2012 E.C Nigus Gabbiye Habtu (PhD)

Lecture II: Content

• Rate Laws and Stoichiometry

• Reaction Orders
• Arrhenius Equation
• Activation Energy
• Effect of Temperature

2
Introduction: Reaction Rate Laws

Reaction Rate Laws

Power Law Model: 2A  B  3C

  α order in A
 rA  kCA CB
β order in B
Overall Rection Order  α  β

 A reaction follows an elementary rate law if the reaction

orders just happens to agree with the stoichiometric
coefficients for the reaction as written.

3
Introduction: Reaction Rate Laws

Example: If the reaction presented below follows an

elementary rate law

2A+B3C
 The rate will be
-rA = kA C CB
2
A

-rB = kB C CB
2
A A reaction follows
rC = kC C CB
2
A an elementary rate law

• Second Order in A
 rA  kC 2
A When?
• Zero Order in B
B In excess
• Overall Second Order 4
Relative Rates of Reaction

Reversible Elementary Reaction

kA
A + 2B 3C
k-A

 CC 
3
 rA  k AC AC B  k  ACC  k A C A C B 
2 3 2

 k A k A 
 2 CC 
3
 k A C A C B  
 Ke  Reaction is:
• First Order in A
• Second Order in B
• Overall third Order
5
Relative Rates of Reaction

 When do you expect?

 In Heterogeneous catalysis

6
Relative Rates of Reaction

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

7
Reaction rate constant: Arrhenius Equation

• k is the specific reaction rate (constant) and is given

by the Arrhenius Equation.

where:
Gas phase reaction
 Partial pressure
 E RT
k  Ae  Catalyst type
Liquid phase reaction
 Total pressure
 Ionic strength, types of solvent
T ®¥k ® A
k  Temperature effect
T ®0k®0
is more pronounced!
A » 10 s  and in appropriate
13
T                   concentration units

 Rule of thump: the rate of reaction doubles for every 10 OC

8
increase temperature
Reaction rate constant: 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)

9
Activation Energy

Concept one: Law of Mass Action

1. The rate of reaction increases with increasing concentration of
reactants owing to the corresponding increase in the number
of molecular collisions.

2. 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 = éëkA (T )ùûéë fn (CA,CB …)ùû

For example for the elementary reaction

AB + C ®
¬ A + BC
-E RT
-rAB = kABCABCC = AABe CABCC E = Activation Energy, (kJ/mol)
10
Activation Energy

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.

11
Activation Energy

Concept Two: 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 below.

12
Concept 2. Potential Energy Surfaces and Energy Barriers

13
Activation Energy

Concept Three. 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 -mU 2 ù
( )
f U ,T = 4p ç
ç 2pk T
÷
÷ expê
ê
úU 2
è B ø ë 2kBT úû

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
f(U,T) = Fraction of relative velocities between U and U + dU 14
Activation Energy
Concept Three. 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
Maxwell-Boltzmann Distribution of velocities.

15
Activation Energy
Concept Three. Fraction of Molecular Collisions That Have Sufficient
Energy to React

Distribution of Velocities
3 2
 m 
f U , T  dU  4   e  mU 2 2 k BT 2
U dU
 2 k BT 

1
Given E  mU 2
2

E
2
Let f  E , T  dE  E1 2e k BT
dE
 2 k BT 
3 2

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

between E and (E+dE)
16
Activation Energy

In terms of energy per mole, E, instead of energy per molecule, e, we have

32
æ 1 ö é -E ù
( )
f E ,T = 2p ç ÷
è pRT ø
E 12
expê ú
ë RT û

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.

32
æ 1 ö é -E ù
( )
f E ,T dE = 2p çç ÷
÷
è pkBT ø
E expê údE
12
êë kBT úû

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

slide.

17
Activation Energy

Concept Three: Fraction of Molecular Collisions That Have

Sufficient Energy to React

æ kcal ö 0.35
çFraction with energies between (0.25) and 0.35)
è
÷= ò
mol ø 0.25
( )
f E ,T dE

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 ö

( ) ( )
f E ,T dE = f 0.3, 300K DE =
kcal è
ç 0.35
kcal
mol
-0.25
mol ø
÷ = 0.081

We see 8.1% of the collisions have energies between 0.25 and 0.35 kcal/mol 18
Activation Energy

Concept Three: 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 ) = òE f (E ,T ) dE

¥

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
æFraction of collision with ö æ ö æ ö
( ) 2 A E E
çenergies greater than E ÷ = F E > E ,T @ ç ÷ exp ç - A÷
è ç ÷ ç ÷
Aø
A
p è RT ø è RT ø
Equation (3-23) is plotted in Figure 4-4(b) as a function of activation energy, EA,
as shown in the next slide.

19
Activation Energy

Concept Three. 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.

20
 Reaction Rate Laws: Stoichiometry

 We shall set up Stoichiometry Tables using species A as our

basis of calculation in the following reaction. We will use the
stoichiometric tables to express the concentration as a function
of conversion. We will combine Ci = f(X) with the appropriate
rate law to obtain -rA = f(X).

b c d
A  B C  D  A is the limiting reactant
a a a

Definition:
NA  NA0  NA 0 X

Unreacted Initial Reacted

 component reactant component 21
Reaction Rate Laws: Stoichiometry

 For the species, every mole of A that reacts, b/a moles of B react, c/a
mole formed, d/a mole formed Therefore moles of B remaining:

Let define ΘB = NB0/NA0

Then: b æ N B0 b ö
N B = N B0 - N A0 X = N A0 ç - X÷
a è N A0 a ø
 b 
N B  N A0   B  X 
 a 

c  c 
NC  NC 0  N A 0 X  N A 0 C  X 
a  a 


22
Reaction Rate Laws: Stoichiometry

Batch System - Stoichiometry Table

Species Symbol Initial Change Remaining

A A NA0 -NA0X NA=NA0(1-X)

B B NB0=NA0ΘB -b/aNA0X NB=NA0(ΘB-b/aX)

C C NC0=NA0ΘC +c/aNA0X NC=NA0(ΘC+c/aX)

D D ND0=NA0ΘD +d/aNA0X ND=NA0(ΘD+d/aX)

Inert I NI0=NA0ΘI ---------- NI=NA0ΘI

FT0 NT=NT0+δNA0X

Ni0 Ci 0 0 Ci 0 yi 0 d c b
Where: i   
N A0 C A0 0 C A0

y A0
and      1
a a a

δ = change in total number of mol per mol A reacted 23

 Reaction Rate Laws: Stoichiometry

Stoichiometry Constant Volume Batch Reactor

Note: If the reaction occurs in the liquid phase
or
if a gas phase reaction occurs in a rigid (e.g. steel) batch reactor

Then
V V0
N A N A 0 1  X 
CA    CA 0 1  X 
V V0
N B
N A 0  b   b 
CB   B  X  CA 0B  X 
V V0  a   a 

24
Reaction Rate Laws: Stoichiometry

Suppose, the reaction follow

rA  k A C CB 2
A

æ b ö
-rA = kAC (1- X ) ç QB - X ÷
3 2
A0
è a ø

Equimolar feed: B  1

b
Stoichiometric feed: B 
a
1
 rA
and we have  rA  f  X 
X 25
Reaction Rate Laws: Stoichiometry

Flow System – Stoichiometry Table

Species Symbol Reactor Feed Change Reactor Effluent

A A FA0 -FA0X FA=FA0(1-X)

B B FB0=FA0ΘB -b/aFA0X FB=FA0(ΘB-b/aX)
C C FC0=FA0ΘC +c/aFA0X FC=FA0(ΘC+c/aX)
D D FD0=FA0ΘD +d/aFA0X FD=FA0(ΘD+d/aX)
Inert I FI0=A0ΘI ---------- FI=FA0ΘI

FT0 FT=FT0+δFA0X

Where: i  Fi0  Ci0 0  Ci0  y i0 26

FA 0 CA 0 0 CA 0 yA 0
Reaction Rate Laws: Stoichiometry

Fi 0 Ci 0 0 Ci 0 y i 0
Where: i    
FA 0 C A 0 0 C A 0 y A 0

Concentration – Flow System FA d c b

CA 
and
    1
 a a a
Liquid Phase Flow System:   0
FA FA 0 1  X 
CA    CA 0 1  X 
 0
N B N A 0  b   b 
CB   B  X  CA 0B  X 
 0  a   a 


 27
Reaction Rate Laws: Stoichiometry

Liquid Systems

If the rate of reaction were  rA  kCACB

æ b ö
then we would have -rA = kC (1- X ) ç QB - X ÷
2
A0
è a ø
This gives us  rA  f  X 

FA 0
 rA

 28
Reaction Rate Laws: Stoichiometry

Stoichiometry: for Gas Phase Flow Systems

Combining the compressibility factor equation of
state with Z = Z0
P
CT 
ZRT
Stoichiometry: CT 0 
P0
Z 0 R0T0
FT  CT
FT 0  CT 0 0
We obtain:
FT P0 T
  0
FT 0 P T0

29
Reaction Rate Laws: Stoichiometry

FA  P   T0  FT 0 FA  P   T0 
C A  FA         
 FT   P0   T  0 FT  P0   T 
0  
 F0 
Since CT 0  FT 0, 0

FA  P   T0 
C A  FA   CT 0   
FT  P0   T 

Using the same method,

 FB  P  T0 
C B  CT 0    
 FT  P0  T 

The total molar flow rate is: FT  FT 0  FA0X

30
Reaction Rate Laws: Stoichiometry

Substituting FT gives:
 FT 0  FA0 X  T P0  FA0  T P0
  0    0  1  X
 FT 0  T0 P  FT 0  T0 P

T P0 T P0
 0 1  y A0 X   0 1   X 
T0 P T0 P

Where   y A0

   0 1  X 
FA T P0
Concentration Flow System: C A  Gas Phase Flow System:
 T0 P

FA FA0 1  X  C A0 1  X  T0 P
CA   
  1  X  T P0 1  X  T P0
0
T0 P

 b   b 
FA0   B  X  C A0   B  X 
F
CB  B   a 
  a  T0 P
  1  X  T P0 1  X  T P0
0
T0 P
31
Reaction Rate Laws: Stoichiometry

For Gas Phase Flow Systems

If –rA=kCACB

  b  
 1  X    B  a X   P T  2 
 rA  k AC A2 0    0
 

 1  X  1  X   P0 T  
 

This gives us

32
Reaction Rate Laws: Stoichiometry

For Gas Phase Flow Systems

where
d c b
    1
a a a
change in total number of moles

mole of A reacted

 d c b  FA0
      1  y A0
 a a a  FT 0
  y A0

change in total number of moles for complete conversion


total number of moles fed to the reactor

33