Topic 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.

Topic 3
Building Block 1 (completed)
Mole Balances (Review)
Size CSTRs and PFRs given rA= f(X)
Conversion for Reactors in Series
Building Block 2- Rate Laws
Single and Multiple Reactions
Rate Laws-Reaction Orders
Arrhenius Equation
Activation Energy
Effect of Temperature
Reversible Reactions
2

Reaction Kinetics - 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

Single and Multiple Reactions

When a single stoichiometric equation and single
rate equation can represent the progress of the
reaction, we have a single reaction.
When more than one stoichiometric equation is
necessary to represent the observed changes, then
more than one kinetic expression is needed to
follow the changing composition of all the reaction
components, and we have multiple reactions.
Single Reactions can be Irreversible or Reversible.

Chemical Reaction Engineering

Multiple reactions may be classified as:

Series reactions,

Parallel reactions,

and more complicated schemes, an example of which is

Reaction Kinetics Introduction 2

What must happen for two molecules
to react?

Reactants have to collide to react.

Chemical Reaction Engineering

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, ...)]
Chemical Reaction Engineering

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

Building Block 2: Rate Laws

Power Law Model:

rA kC C

order in A
order in B
Overall Rection Order

Building Block 2: Rate Laws

2A B 3C
A reaction 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

10

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

rC kC C A2

11

L4-12

Elementary Reactions & Rate Laws

Dependence of reaction rate rA on concentration of chemical species in
the reaction is experimentally determined
Elementary reaction: involves 1 step (only)
Stoichiometric coefficients in an elementary reaction are identical to the
powers in the rate law:

A B C

rA k A C A CB

Reaction order:
order with respect to A
order with respect to B
Overall reaction order n =
Zero order: -rA = kA k is in units mol/(volumetime)
1st order: -rA = kACA k is in units time-1
2nd order: -rA = kACA2
3rd order: -rA = kACA3

k is in units volume/(moltime)
k is in units volume2/(mol2time)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

L4-13

Non-Elementary Reactions
Overall equations describe the overall reaction stoichiometry
Reaction order cannot be deduced from overall equations
Examples:
2

k
C
2NO O2 2NO2
NO
NO NO CO2
This reaction is not elementary, but under some conditions it
follows an elementary rate law
Forward reaction is 2nd order with respect to NO and 1st order
with respect to O2 (3nd order overall)

Compare the above reaction with the nonelementary reaction

between CO and Cl2
rCO kCCOCCl2 3 2
CO Cl2 COCl2
Forward reaction is 1st order with respect to CO and 3/2 order with
respect to Cl2 (5/2 order overall)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

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

14

Relative Rates of Reaction

2A B 3C
Given
Then

mol
rA 10
dm 3 s

rA
rB rC

2 1 3
rA
mol
rB
5
2
dm 3 s
3
mol
rC
rA 15
2
dm 3 s

15

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.

Chemical Reaction Engineering

16

Molecularity of a reaction refers to the min.

no. of molecules which must combine
Law of mass action: The rate of a reaction is
proportional to the product of active masses
of the reactants, where the active masses are
raised to the power of their respective
stoichiometric coefficients.
aA + bB rR + sS

rA ka a kC C
a b
A B

a
A

b
B

The second part is true for ideal solution behavior.

17

Elementary reaction ??
Order & Molecularity for Elementary reactions

Unimolecular

A Pr od .

Bimolecular

2 A Pr od .

rA kC A

rA kC

2
A

Bimolecular

A B Pr od .

rA kC AC B

Trimolecular

3 A Pr od .

Trimolecular

2 A B Pr od . rA kC A2C B

rA kC A3

Trimolecular A B C Pr od . rA kC AC B CC
Order & Molecularity of the forward reaction can be
18
different from those of the reverse reaction

Elementary reaction
obeys the law of mass action
proceeds in one step
Non-Elementary reaction
does not obey the law of mass action
proceeds in more than one step
involves the appearance of intermediates
Example: H2 + Br2 2HBr
1/ 2

k1[ H 2 ][ Br2 ]
rA
k 2 [ HBr ] /[ Br2 ]
What is the order & molecularity ??

19

Non-Elementary reaction
Non-Elementary reactions involve more than one
step
Involve the formation of intermediates
Intermediates cannot be observed as they are
highly reactive and present in minute quantities
Intermediates could be:
Free radicals: CH3*, C2H5* etc.
Ions & Polar substances: Na+, OH-,NH4+
Highly reactive molecules: A R S
Transition State Complexes
20

Rate constant (Specific reaction rate):

The term reaction rate constant is actually a misnomer,
since k may vary with temperature, the solvent for the
reaction, and the concentrations of any catalysts that may
be present in the reaction system.
The term is in universal use, however, because it implies
that the parameter k is independent of the concentrations of
reactant and product species.

1 dN A
rA
k (concentration) n
V dt

k (concentration)1 n (time) 1

Example: A + 2B 2C
Write the rate laws for each species ??
Are the rate constants in each case same ?
What is the relation between them??

kC A

kC B kC R kC S

a
b
r
s

21

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
Chemical Reaction Engineering

22

Lec, Stanislaw
Some like to understand what they believe in. Others like to believe in
23
what they understand.

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
Chemical Reaction Engineering

24

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
25

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)

26

SVANTE AUGUST ARRHENIUS

Svante August 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 universal
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

k A (T ) Ae

E
RT

1859 -1927

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.
Chemical Reaction Engineering

28

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:

29

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.
30

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)

31
Chemical Reaction Engineering

ln k

How can we determine E, A?

1/T (1/K)

Slope = -E/R,
Intercept = ln A
Chemical Reaction Engineering

32

[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]

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

Chemical Reaction Engineering

39

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!

40

Chemical Reaction Engineering

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)
41

Concentration

Equilibrium - Reversible Reactions

Reactants
Products

Reaction Rate

Time
Forward
Reverse

Time

42

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)

43

Equilibrium - Le Chateliers principle

44

"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

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?
b
k forward
CBe
kA
KC a

5 / 3 1.67
C Ae k reverse k A

How to size a reactor in case of a reversible

reaction? E.g. CSTR
FA0 X FA0 X

45

rA

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

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

rAnet

Kinetic view of equilibrium for Elementary reactions

A + B C

Forward reaction rate = k1CACB

Backward reaction rate = k2CC
At equilibrium: Forward rate = Backward rate

k1CACB = k2CC

CC
k1
KC

k 2 C AC B
46

Reversible Elementary Reaction

2A+B

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

47

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

48

dm 6

mole 2 s

L4-49

Reversible Reactions
k

aA b B A
c C d D
kA

a
b
a
b
Rate of disappearance of A (forward rxn): rfA k A C A CB rfA k A C A CB
c
d
Rate of generation of A (reverse reaction): rbA k A CC CD

rA,net rA rfA rbA rA k A CA a CBb k A CCc CDd

At equilibrium, the reaction rate is zero, rA=0
rA 0 k A CA a CBb k A CCc CDd k A CA a CBb k A CCc CDd
CCc CDd
kA
Thermodynamic equilibrium relationship

KC
k A CA a CBb
KC: concentration equilibrium constant (capital K)
KC is temperature dependent K (T) K (T )exp HRX 1 1

C
C 1
T T
R
(no change in moles or CP):
1

HRX: heat of reaction

If KC is known for temperature T1, KC for temperature T can be calculated

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

50

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

51

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.
52

Chemical Reaction Engineering