Lecture 3- Rate Laws

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.

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

Reactor Mole Balances

Summary
The GMBE applied to the four major reactor types
(and the general reaction AB)
Reactor
Batch

Differential

PBR
3

dN A
t
rV
N A0 A
V

dFA
rA
dV

dFA
rA
dW

Integral
NA

dN A
rAV
dt

CSTR
PFR

Algebraic

FA 0 FA
rA

FA

FA 0

FA

FA 0

dFA
drA
dFA
rA

NA
t
FA
V
FA
W

a A bB cCd D
Choose limiting reactant A as basis of calculatio n
b
c
d
A B C D
a
a
a
moles A reacted
X
moles A fed

Reactor Mole Balances

Summary
In terms of Conversion
Reactor

Batch

Differential

N A0

dX
t N A0
rAV
0
V

dX
FA0
rA
dV

Integral
X

dX
r AV
dt

CSTR

PFR

Algebraic

FA0 X
rA
X

dX
V FA0
rA
0

X
PBR
5

dX
FA0
rA
dW

W FA0
0

dX
rA

Levenspiel Plots

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

Reactors in Series

Reaction Kinetics 1- Topics

Introduction, Reaction Kinetics & Rate Law
Rate of Reaction - Concentration dependence
Rate Law Elementary Reactions
Molecularity vs. Order

Rate of Reaction Temperature dependence

Rate of Reaction Pressure dependence
Elementary Vs.Non-elementary Reaction Kinetics
Reaction Rates for Reversible Reactions

Chemical Reaction Engineering

Reaction Kinetics Introduction1

Kinetics is natures way of preventing
everything from happening all at once
-S.E. LeBlanc
What do ants and bees have in
common (besides being insects) ?
Are concentrations affecting kinetics?

Chemical Reaction Engineering

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Reaction Kinetics Introduction 2

What must happen for two molecules
to react?

Reactants have to collide to react.

Chemical Reaction Engineering

2010

11

Reaction Kinetics & Rate Law

Factors affecting rate of reaction
Concentrations
Temperature
Pressure

Rate law is an algebraic expression of the

rate of a reaction.
Rate law is a function of concentration and
temperature (through the rate constant, k)
-rA= [k(T)] [f(CA, CB, ...)]
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Rate of Reaction Concentration dependence

Recap: Order of Reaction
If aA+bB cC + dD
-rA=kACAaCBb
a order with respect to A
b order with respect to B
n = a + b overall order

Some more Examples:

AR
2A R

Chemical Reaction Engineering

-rA= kCA
-rA= kCA2,

I order
II order

13

Rate Law Elementary Reactions

A reaction follows an elementary rate law if and
only if the stoichiometric coefficients are the
same as the individual reaction order of each
species.
For example, if aA+bB cC + dD, the rate law
would be: -rA=kACAaCBb
a order with respect to A
b order with respect to B

If 2NO+O2 2NO2
then -rNO = kNO C 2 NO CO2 if it is elementary!
f(CA) is determined by experimental observation.
Chemical Reaction Engineering

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Molecularity
The molecularity of an elementary reaction is
the number of atoms, molecules, or ions
coming together to react.
Reactions can be termed as unimolecular,
bimolecular or termolecular, depending on one,
two, or three atoms, molecules, or ions collide.
Elementary reactions may be
unimolecular, in which a single molecule shakes
itself apart or into a new arrangement of its atoms
bimolecular, in which two molecules collide and
undergo some change.

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Molecularity vs. Order

The order of a reaction is an empirical quantity
which follows from an experimentally
determined rate law.
The molecularity of a reaction refers to a particular elementary reaction which is postulated as
part of a proposed mechanism.
For an elementary reaction, the rate law can be
written down from its chemical equation.

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Writing Rate Laws for

Elementary Reactions
The reaction H2 + Br2 2HBr is bimolecular.
Its rate law is r = k [H2][Br2]
Bimolecular reactions are second order.
But, reverse is not necessarily true. That is, all the
second-order reactions are not necessarily
bimolecular, unless they are elementary reactions.
Unimolecular reactions are first order.
For a reaction such as
ka
kb
.

I P

d[A]/dt = -ka[A]
d[I]/dt = ka[A] - kb[I]
d[P]/dt = kb[I]
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Units of rate constant

(rA) = k x [conc. terms]
units of k
= units of (r )/units of [conc. terms]
Zero-order reaction
(rA) = k
k in mol/m3 s
First order reaction
(rA) = kCA
k in s-1
Second-order reaction
(rA) = kCA2
k in m3/mol s
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Rate of Reaction
Temperature dependence
Arrhenius law
k A (T ) Ae

RT

Arrhenius law describes the effect of temperature on k

A = frequency factor, E = activation energy, R = gas constant

If we increase T, reaction goes faster, because at

higher temperatures molecules have more energy
Is it possible to change E?
A Catalyst can lower E

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There is still hope Biography of

Svante August Arrhenius (1859-1927)
Arrhenius was born in Vik, Sweden in 1859. At age 25 he
turned in his PhD thesis at the University of Uppsala, Sweden.
His PhD examining committee did not think very highly of his
thesis and rated it 4th class. His oral thesis defense did not fair
much better as they rated it as only 3rd class.
Arrhenius left Sweden for five years to work with Oswald,
Boltzmann and van't Hoff. In 1889 his interpretation of
temperature-dependent equation by van't Hoff led to the
universally accepted Arrhenius equation for kinetic rate laws in
chemistry.
He received the Nobel Prize in 1903. From 1905 until his death
in 1927 he was director of Physical Chemistry at the Nobel
Institute.
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How can we determine E, A?

The equation

k A (T ) Ae

E
RT

Take logarithms on both sides

ln k A (T ) ln A ln e

E
RT

ln A E / RT

ln k

Then, ln kA(T) is plotted against 1/T.

1/T (1/K)

21
Chemical Reaction Engineering

ln k

How can we determine E, A?

1/T (1/K)

Slope = -E/R
Intercept = ln A
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Temperature-dependent Term of a Rate Equation

Temperature Dependency from Arrhenius' Law
For many reactions, and particularly elementary
reactions, the rate expression can be written as a
product of a temperature-dependent term and a
composition dependent term, or
[33]
For such reactions the temperature-dependent term, the
reaction rate constant, has been found in practically all
cases to be well represented by Arrhenius' law:

[34]
where
k, is the frequency or pre-exponential factor and
E is the activation energy of the reaction.
At the same concentration, but at two different
temperatures, Arrhenius' law indicates that
[35]

Comparison of Theories with Arrhenius' Law

The below expression summarizes the predictions of the
simpler versions of the collision and transition state theories
for the temperature dependency of the rate constant.
[35]
For more complicated versions m can be as great as 3 or 4.
Now, because the exponential term is so much more
temperature-sensitive than the pre-exponential term, the
variation of the latter with temperature is effectively
masked, and we have in effect
[36]
This shows that Arrhenius' law is a good approximation to the
temperature dependency of both collision and transition-state theories

Activation Energy and Temperature Dependency

The temperature dependency of reactions is determined
by the activation energy and temperature level of the
reaction, as illustrated in Fig. 2.2 and Table 2.1.

These findings are summarized as follows:

1. From Arrhenius' law a plot of ln k vs 1/T gives a
straight line, with large slope for large E and small
slope for small E (slope = E/R).
2. Reactions with high activation energies are very
temperature-sensitive; reactions with low activation
energies are relatively temperature-insensitive.
3. k0 does not affect the temperature sensitivity.

EXAMPLE 2.3
Milk is pasteurized if it is heated to 63 oC for 30
min, but if it is heated to 74C it only needs 15 s
for the same result. Find the activation energy of
this sterilization process.

t1 = 30 min
at T1 = 336 K
t2 = 15 s
at T2 = 347 K
Using Eq. 25:

E = 422,000 J/mol = 422 kJ/mol

Rate of Reaction
Pressure dependence
Think about pressure. What causes pressure?
For an ideal gas, how does it affect the reaction
rate?
pV = nRT

How to increase pressure without changing volume,

or number of moles?
one must increase T,
which changes k

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Effect of Pressure
Increasing pressure without changing number of
moles or temperature, changes volume.

Increasing pressure without changing temperature or

volume, changes number of moles:

BOTH CHANGE CONCENTRATION!

32

Chemical Reaction Engineering

Elementary Vs.Non-elementary
Reaction Kinetics
Reaction: A + B
-rA = k CAa CBb

cC + dD

(Power Law Model)

a = reaction order with respect to species A

b= reaction order with respect to species B
n = a + b = overall order of reaction
If, a = and b = , the reaction is considered to
follow elementary rate law.
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Non-Elementary Rate Law

If the rate law for the reaction
A+B C + D is
-rA=kACA2 CB
Then, it is non-elementary.
The reaction is said to be
2nd order in A,
1st order in B, and
3rd order overall.
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Non-elementary Reactions
Why do some reactions have nonelementary rate laws?
e.g. 2NO+F2 2ONF
-rNO = k CNOCF

Answer: Reaction is actually a series of

elementary steps!
First: NO+F2 ONF + F
Second NO+F ONF
Examples:
free radicals (CH3, CCl3)
molecular intermediates
chain reactions

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Rate Determining Step

One reaction is the slowest
Reaction proceeds at this rate
This is a bottleneck for the
reaction
This step is known as the
rate determining step

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Example: reaction of two noxious

automobile products
Exhaust products:
CO + NO CO2 + 0.5 N2
CO + S CO S
Rapid
NO + S NO S
NO S + CO S CO2 + N S + S Rate-limiting
N S + N S N2 S
N2 S N2 + S
Chemical Reaction Engineering

Rapid

37

More complicated Kinetics

Remember that steps can be reversible
Also, some rate laws are really funky...
H2 + Br2 2HBr
Same

rHBr

k1C H 2 C

12
Br2

k 2 C HBr C Br2

idea
Series of elementary steps
BUT sometimes contains intermediates,and their
concentration cant be measured
Example:
2 NO (g) + O (g) 2NO
2
2
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Summary
Reactants have to collide to react.
-rA= [k(T)][f(CA, CB, etc.)]
Pressure can affect either T, or concentration

k(T) = Ae-E/RT
A and E can be found graphically, or by solving 2
equations

Rate laws can be described using reaction

order and molecularity
Elementary and non-elementary reaction Rate
laws are different.
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Assignment #3
1. Order of Reaction: Write rate laws including
relative rates and determine the order of reaction
for the following reactions:
Elementary: H2 + I2 2HI
3Fe + 4H2O Fe3O4 +4H2
N2 + 3H2 2NH3
Non-Elementary: H2 + I2 2HI

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Assignment #3
2. Arrhenius (rate constant)
2.1 Use the data below to get the activation
energy E in [KJ/mol] and the frequency
factor A.
k [s-1]
T [K]

0.00043
313.0

0.00103
319.0

2.2 A reaction with high activation energy is

more or less sensitive to changes in
temperature?
[Ans: E = 120.8 KJ/mol , A = 6.4 * 10-16 s-1]
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Assignment #3
3. Arrhenius (rate constant): The following data is
given:
k [L2.mol-2.min-1]

0.03

0.20

1.04

T [C]

10

120

240

3.1 What is the overall order of the reaction?

3.2 Determine the activation energy for this reaction in
KJ.mol-1
3.3 Calculate the frequency factor
3.4 What would be the rate constant be at 350C
Ans:
3.2 E = 18.6 KJ/mol
3.3 A = 81.6 L2.mol-2.min-1
3.4 k = 2.25 L2.mol-2.min-1
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Building Block 2: Rate

Laws
Power Law Model:

rA kC C

order in A
order in B
Overall Rection Order

43

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
2

rA k AC AC B

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

44

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 BC A2
45

rC kC C A2

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

46

Relative Rates of Reaction

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

rA
rB rC

2 1 3
rA
mol
rB
5
2
dm 3 s

47

3
mol
rC
rA 15
2
dm 3 s

Reaction Rates for Reversible

k
Reactions Reaction: aA + bB
cC + dD
for

krev

Rate of consumption of A by forward reaction

(-rA_forward) = kfor CAa CBb
Rate of formation of A by forward reaction
(rA_forward) = kfor CAa CBb
Rate of formation of A by reverse reaction
(rA_reverse) = krev CCc CDd
Net rate of formation of A = (rA_reverse) + (rA_forward)
48

Concentration

Equilibrium - Reversible Reactions

Reactants
Products

Reaction Rate

Time
Forward
Reverse

Time

49

Thermodynamic relationship at
equilibrium:
Reaction aA+bB cC+dD
c
d
CCe
C De
KC a b
C AeC Be

(KC concentration equilibrium constant)

c
Ce
a
Ae

d
De
b
Be

p p
Kp
p p

(Kp pressure equilibrium constant)

50

Equilibrium - Le Chateliers principle

51

"When a system at equilibrium is subjected to a

stress, the system will react so as to relieve the
stress."
Change of concentration: H 2 I 2 2 HI
Increase hydrogen => more HI to decrease
hydrogen
Change of pressure
2SO2 O2 2SO3
increase P => more SO3
N 2 3H 2 2 NH 3
Change of temperature
increase T => less NH3 !
(because the forward reaction is exothermic)

Practice (I)

2 NO + O2 2 NO2

A 2-step reaction mechanism has been proposed

for this reaction
Step 1 (Fast, equilibrium)
NO + NO N O
2 2
Step 2 (Slow, rate determining)
N O + O 2NO
2 2
2
2
Check
Do these steps give the correct overall reaction?
Is this mechanism consistent with the observed
rate law?
What is the r
Net for reversible part of the overall
reaction?

52

-rA = k CN2O2 CO2

Practice (II)

For a reversible reaction, A B, what is the value

of KC if kA= 5 L.mol-1.min-1 and k-A=3 min-1?
d
CcCeCDe
k forward k A
KC a b

5 / 3 1.67
C Ae CBe k reverse k A

How to size a reactor in case of a reversible

reaction? E.g. CSTR
FA 0 X FA 0 X e

53

rA

Where -rA is the net rate, -rA-net .

-rA-net = kA CA k-A C B

rAnet

Reversible Elementary Reaction

A+2B

kA
k-A

3C

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

k
k
A
A

C
2
C
k A C A CB

K
e

54

Reversible Elementary Reaction

A+2B

kA
k-A

3C

Reaction is: First Order in A

Second Order in B
Overall third Order
moles
CA
dm 3

moles
rA 3
dm s

rA
mole dm 3 s
k

2
3
3
C
C
mole
dm
mole
dm
A B

55

dm 6

mole 2 s

56

Assignment #3
4. For the reversible reaction, A B, kA=0.04min-1 &
k-A=0.08 min-1, Calculate the following:
1.1 KC
1.2 the equilibrium conversion XE
1.3 The volume of a PFR necessary to achieve a
conversion of 20%, if volumetric flow rate= 600L.hr-1
Ans: 1.1 KC = 0.5
1.2 XE = 0.33
1.3 V = 25.3 L
57

Assignment #3
5. For the reversible reaction, 2A B, with
kA=0.04 L.mol-1.min-1 , k-A=0.06 min-1, CA0 = 5
mol.L-1 , Calculate the following:
2.1 KC
2.2 the equilibrium conversion XE
2.3 The volume of a CSTR necessary to achieve a
conversion of 50%, if FA0 = 500mol.hr-1
Ans: 2.1 KC = 0.67
2.2 XE = 0.68
2.3 V = 23.8 L
58

Algorithm
How to find r

fX

Step 1: Rate Law rA g Ci

Step 2: Stoichiometry

Ci h X

Step 3: Combine to get rA f X

59

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

k Ae

E RT

T k A
T 0 k 0

A 1013
T
60

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)

61

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:

62

63

Collision Theory

64

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.
65

Distribution of Velocities
We will use the Maxwell-Boltzmann Distribution of
Molecular Velocities. For a species af mass m,
the Maxwell distribution of velocities (relative
velocities) is:

m
f U , T dU 4

2 k BT

32

mU 2 2 k BT

U 2 dU

f(U,T)dU represents the fraction of velocities

between U and (U+dU).
66

Distribution of Velocities
A plot of the distribution function, f(U,T), is shown
as a function of U:
T1
T2

T2>T1

67

U
Maxwell-Boltzmann Distribution of velocities.

Distribution of Velocities

m
Given f U , T dU 4

2 k BT

32

mU 2 2 k BT

U 2 dU

1
2
E

mU
Let
2

f E , T dE

E
1 2 k BT

2 kBT

32

E e

dE

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

have energy between E and (E+dE)
68

f(E,T)dE=fraction of molecules with energies between E+dE

One such distribution of energies is in the following figure:

69

Supplementary Material
AB

BC
VBC

VAB

kJ/
Molecule

kJ/
Molecule

r0

rBC
rAB

Potentials (Morse or Lennard-Jones)

70

r0

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

l
A B C
rAB

71

l
A
BC

l
AB
C

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
figure:

Supplementary Material
Reference

S2
BC

Energy

AB
S1

E*

E1P
E2P
72

Ea
r

HRx=E2P-E1P