ACRE2a Non Elementary Reaction Kinetics Rev

Advanced
Chemical Reaction Engineering

Topic 2
Non-Elementary
Reaction Kinetics
(Chapter 9 Fogler’s Essentials)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L10-2
Topic Learning Outcomes

After completing this topic, students will be able to:
• Discuss the pseudo-steady-state-hypothesis and
explain how it can be used to solve reaction
engineering problems.
• Write reaction pathways for complex reactions.
• Explain what an enzyme is and how it acts as a
catalyst.
• Describe the Michaelis-Menten enzyme kinetics and
rate law along with its temperature dependence.
• Discuss how to distinguish the different types of
enzyme inhibition.
• Discuss the stages of cell growth and the rate laws
used to describe growth.
• Write material balances on cells, substrates, and
products in bioreactors to size chemostats and plot
concentration-time trajectories in batch reactors.
L10-3
L10: Nonelementary Reaction Kinetics

In practice, knowledge of the reaction mechanism helps us to design better
catalyst and aid in troubleshooting poor reactor performance
• Rate law is typically determined from experimental data
• Goal: Use the experimental rate law to postulate a reaction mechanism
• Elementary: the reaction orders and stoichiometric coefficients are
identical
• Nonelementary reaction kinetics: no direct correspondence between

reaction order and stoichiometry
– Nonelementary kinetics
– Pseudo-steady-state hypothesis (PSSH)
– Chain reactions: cracking ethane or polymerizations
– Enzymatic reactions (covered in the next part)
– Bioreactors (covered in in the next part)
L10-4
Review (L4): Reversible Reactions

kA
aA  b B cC  dD
kA
a b a b
Rate of disappearance of A (forward rxn): rfA  k ACACB  rfA  k ACACB
c d
Rate of generation of A (reverse reaction): rbA  k  A CCCD
rA,net  rA  rfA  rbA
rA  k A CaA CB
b c d
 k  A CCCD
consumed generated
At equilibrium, the reaction rate is zero, rA=0
rA  0  k ACaACB
b c d
 k  ACCCD
 k ACaACB
b c d
 k  ACCCD
kA CcCCD
d
Thermodynamic equilibrium relationship
  a b  KC
k  A CA CB KC: concentration equilibrium constant (capital K)
L10-5
Determining Mechanism to Describe

Nonelementary Reaction Kinetics
Overall Reaction: 2NO  O2  2NO2
• If the reaction were elementary, the reaction kinetics would follow:
rNO  k1CO2 CNO2
• Instead experiments show that the kinetics are:
kiCNO2CO2
rNO  Nonelementary
1  kiiCNO
• Nonelementary kinetics are the result of multiple elementary reaction
steps and reactive intermediates (an intermediate that is so reactive it is
consumed as fast as it is formed)
How do we determine the mechanism?
• Postulate a reaction mechanism that is a series of elementary reactions
• Derive a rate equation for the postulated mechanism
• Is the rate equation for the postulated mechanism consistent with the
experimental results?
For example…
L10-6
Postulating a Reaction Mechanism

1. If CB appears in the denominator of the rate law, then one elementary rxn
step is probably:
B  A *  Collision products A* is a reactive intermediate
2. If the denominator contains a constant that is not multiplied by a
concentration, then one rxn step is probably:
A *  Decomposition products
3. If the numerator contains a species concentration, then one step is probably:
Cspecies   other species?   A *   other products? 
Apply: kiCNO2CO2 Experimentally observed rate equation for

rNO 
1  kiiCNO  overall reaction : 2NO  O2  2NO2
CNO in denominator: NO collides with reactive intermediate, NO3
NO3  NO  2NO2
CNO & CO2 in numerator: NO and O2 produce NO3 in one reaction step
NO  O2  NO3
Constant in denominator: NO3 produces NO and O2 (reverse of previous?)
NO3  NO  O2
L10-7
A Reaction Mechanism for

Observed Kinetics?
Apply: kiCNO2CO2 Experimentally observed rate equation for
rNO 
1  kiiCNO  overall reaction : 2NO  O2  2NO2
CNO in denominator: NO3  NO  2NO2
Reactive
CNO & CO2 in numerator: NO  O2  NO3 intermediate
Constant in numerator: NO3  NO  O2
k1
Postulated mechanism: NO  O2 NO3
k 1 Does this add up to
+ NO3  NO 
2  2NO k the overall reaction?
2
2NO  O2  2NO2 yes
Now derive a rate equation for the postulated mechanism and check if
it describes the experimentally observed rate equation
L10-8
Postulated Mechanism for

kiCNO2CO2
Nonelementary kinetics, result of
rNO  multiple elementary rxns & active
1  kiiCNO intermediates

k1
 Reactive
Postulated mechanism: NO  O2   NO 3 intermediate
k 1
k
NO3  NO 
2  2NO
2
Write –rNO for the postulated reaction mechanism
rNO   rxns that form NO  - rxns that consume NO 
rNO  k 1CNO3  k1CNOCO2  k 2CNO3 CNO
Consumption of NO: rNO  k1CNOCO2  k 1CNO3  k 2CNO3 CNO

(change signs)
• -rNO is in terms of CNO3, which is not measurable species because it is a
reactive intermediate (so reactive it is consumed as fast as it is formed)
• Need to get CNO3 in terms of measurable species and plug into -rNO
L10-9
Pseudo-Steady State Hypothesis

k1 Reactive intermediate,

Postulated mechanism 1.) NO  O 
2
 NO3

k 1 must replace CNO3 in
k2 the rate equation
2.) NO3  NO 
 2NO2
rNO  k1CNOCO2  k 1CNO3  k 2CNO3 CNO Factor out to simplify
 rNO  k1CNOCO2  k 2CNO  k 1  CNO3
1) Write rNO3
2) Rearrange to get CNO3 in terms of measurable species
3) plug eq for CNO3 back into -rNO
rNO3  k1CNOCO2  k 1CNO3  k 2CNO3 CNO
CNO3 is very small, and NO3 is assumed to be so reactive that it is consumed
as fast as it is formed, so rNO3  0
Pseudo-Steady State Hypothesis: Net formation of reactive intermediate ≈0
rNO3  0  k1CNOCO2  k 1CNO3  k 2CNO3 CNO
Solve for concentration of reactive intermediate NO3 in terms of other species

L10-10
Concentration of Reactive Intermediate

k1
  Reactive
Postulated mechanism 1.) NO  O2   NO3 intermediate
k 1
k
2.) NO3  NO 
2  2NO
2
kiCNO2CO2 Observed rate equation
rNO 
1  kiiCNO (nonelementary)
rNO  k1CNOCO2  k 2CNO  k 1  CNO3
rNO3  0  k1CNOCO2  k 1CNO3  k 2CNO3 CNO Solve for CNO3 in

terms of other species
 k 1CNO3  k 2CNO3 CNO  k1CNOCO2  CNO
3
k 1  k2CNO   k1CNOCO2
k1CNOCO2
 CNO3  Plug CNO3 into -rNO
k 1  k 2CNO
k1CNOCO2
 rNO  k1CNOCO2   k 2CNO  k 1 
k 1  k 2CNO
Now we will rearrange and simplify to see if it matches the experimental data
L10-11
Rearranging the Postulated Rate Eq.

Postulated mechanism 1.) NO  O k1
 Reactive
2   NO3 intermediate
k 1
k
2.) NO3  NO 
2  2NO
2
k1CNOCO2
Plug in CNO3  rNO  k1CNOCO2   k 2CNO  k 1 
k 1  k 2CNO
 k 2CNO  k 1  Common
Factor out  r  k C C
k1CNOCO2 NO


1 NO O2  1 
k 1  k

 denominator
2 NO 
C
k k C k C  k 1 
 
 rNO  k1CNOCO2  1 2 NO  2 NO  Add fraction
 k 1  k 2CNO k 1  k 2CNO 
 2k 2CNO  Multiply 2k1k 2CNO2CO2

 rNO  k1CNOCO2 
k 
 1 2 NO 
k C
   rNO 
k 1  k 2CNO
 2k1k 2 k 1  CNO2CO2 Conventional to reduce
 rNO  the additive constant in
1   k 2 k 1  CNO the denominator to 1
L10-12
Comparison Between Postulated

and Experimental Rate Equation
Postulated mechanism 1.) NO  O k1
 Reactive
2   NO3 intermediate
k 1
k
2.) NO3  NO 
2  2NO
2
Compare rate eq for postulated mechanism to the experimental rate eq
 2k1k 2 k 1  CNO2CO2 kiCNO2CO2

 rNO  rNO 
1   k 2 k 1  CNO 1  kiiCNO
Rate equation for Experimentally observed
postulated mechanism rate equation
Clicker Q: Are these rate equations the same?
a) Yes 2k1k 2 k2
b) No  ki  kii
k 1 k 1
Yes, these are the same → postulated rate law explains the experimental data
Active Intermediates and PSSH
An active intermediate is a molecule that is in a
highly energetic and reactive state It is short lived
as it disappears virtually as fast as it is formed.
That is, the net rate of reaction of an active
intermediate, A*, is zero.
The assumption that the net rate of reaction is zero is

called the Pseudo Steady State Hypothesis (PSSH)
13
Active Intermediates and PSSH
14
Example
The rate law for the reaction
A  B C
is found from experiment to be
2
kC
 rA  A
1  k C A
How did this rate law come about? Suggest a

mechanism consistent with the rate law.
15
Example
For reactions with active intermediates, the reaction
coordinate now has trough in it and the active
intermediate, A*, sits in this trough
16
Active Intermediates/Free Radicals
and PSSH
Hall of Fame Reaction
The reaction: 2NO +O2 2NO2

If an elementary rate law is assumed
rNO2  kCNO
2
CO2
However… Look what happens to the rate as the
temperature increases:
-rNO2
17
T
Why does the rate law decrease with increasing
temperature?
Mechanism:
NO  O2 
k1
NO3* (1)
NO3* 
k2
NO  O2 (2)
NO3*  NO 
k3
2 NO2 (3)
Write rate of formation of product rNO2

Note: k3 is defined w.r.t. NO3*
18
Define k with respect to NO3*
Assume that all reactions are elementary
reactions, such that:
r1NO3 = k1CNOCO2 = k1 [ NO][O2 ]

r2 NO* = -k2CNO* = k2 éë NO ùû
*
3
3 3
r3NO* = -k3CNO* CNO = k3 éë NO3* ùû [ NO]

3 3
rNO = 2 é -r3NO* ù
2 ë 3 û
19
The net reaction rate for NO3* is the sum of the
individual reaction rates for NO3*:
r1NO* = r1 Þ r1NO* = k1[ NO] [O2 ]

3 3
-r2NO* = r2 Þ r2NO * = -k2 [ NO *

3 ]
3 3
r3 NO*  r3  r3 NO*  k3  NO3*   NO 

3 3
rNO* = r1NO* + r2NO* + r3NO*

3 3 3 3
rNO*  k1  NO  O2   k2  NO3*   k3  NO3*   NO 

3
20
Pseudo Steady State Hypothesis (PSSH)
The PSSH assumes that the net rate of species A*
(in this case NO3*) is zero.
rNO *  0
3
0  k1  NO  O2   k2  NO3*   k3  NO3*   NO 
0 = k1 [ NO] [O2 ] - éë NO3* ùû ( k2 + [ NO])
k1 [ NO ][O2 ]
éë NO ùû =
*
k2 + k3 [ NO ]
3
21
𝑘1 𝑁𝑂 𝑂2
[𝑁𝑂3∗ ] =
𝑘2 + 𝑘3 𝑁𝑂
 
rNO2  2r3 NO*  2 NO3* NO 
3
k1 k 3 NO 2 O2
𝑟𝑁𝑂2 =2
k 2 + k 3 NO
22
k2 >> k3 [ NO]
E2   E1  E3 
rNO2 2
k1k3
NO O2   2
2 A1 A3
e RT
NO O2 
2
k2 A2
E2  E1  E3 
This result shows why the -rNO2

rate decreases as
temperature increases.
T
23
Development of Rate Laws by Reaction
Mechanism and Experimental Means
 To illustrate how rate laws of this type are formed, we shall first
consider the gas-phase decomposition of azomethane, AZO, to
give ethane and nitrogen:
 Experimental observations show that the rate of formation of
ethane is first order with respect to AZO at pressures greater
than 1 atm (relatively high concentrations)
 and second order at pressures below 50 mmHg (low
concentrations):
 We could combine these two observations to postulate a rate
law of the form
24
To find a mechanism that is consistent with the experimental
observations, we use the following steps.
TABLE 9-1 STEPS TO DEDUCE A RATE LAW
1. Propose an active intermediate(s).
2. Propose a mechanism, utilizing the rate law obtained from experimental
data, if possible.
3. Model each reaction in the mechanism sequence as an elementary
reaction.
4. After writing rate laws for the rate of formation of desired product, write
the rate laws for each of the active intermediate
5. Write the net rate of reaction for the active intermediate & use the PSSH.
6. Eliminate the concentrations of the intermediate species in the rate laws
by solving the simultaneous equations developed in Steps 4 and 5.
7. If the derived rate law does not agree with experimental observation,
assume a new mechanism and/or intermediates and go to Step 3.
A strong background in organic and inorganic chemistry is helpful in
predicting the activated intermediate for the reaction under consideration.
25
 Step 1. Propose an active intermediate. We will choose as an
active intermediate an azomethane molecule that has been excited
through molecular collisions, to form AZO*,
 Step 2. Propose a mechanism.
 In reaction 1, two AZO molecules collide and the kinetic energy of one
AZO molecule is transferred to internal rotational and vibrational
energies of the other AZO molecule, and it becomes activated and
highly reactive (i.e., AZO*).
 In reaction 2, the activated molecule (AZO*) is deactivated through
collision with another AZO by transferring its internal energy to
increase the kinetic energy of the molecules with which AZO* collides.
 In reaction 3, this highly activated AZO* molecule, which is wildly
vibrating, spontaneously decomposes into ethane and nitrogen.
26
Step 3. Write rate laws.
 Because each of the reaction steps is elementary, the
corresponding rate laws for the active intermediate AZO* in
reactions (1), (2), and (3) are
 These rate laws [Equations (9-3) through (9-5)] are pretty much
useless in the design of any reaction system because the
concentration of the active intermediate AZO* is not readily
measurable.
 Consequently, we will use the Pseudo-Steady-State-Hypothesis
(PSSH) to obtain a rate law in terms of measurable concentrations.
27
 Step 4. Write rate of formation of product.
 Step 5. Write net rate of formation of the active

intermediate and use the PSSH.
 To find the concentration of the active intermediate AZO*,
we set the net rate of formation of AZO* equal to zero,
28
 Step 6. Eliminate the concentration of the active intermediate species
in the rate laws by solving the simultaneous equations developed in Steps 4
and 5. Substituting Equation (9-8) into Equation (9-6)
 Step 7. Compare with experimental data.

 At low AZO concentrations,
 for which case we obtain the following second-order rate law:
 At high concentrations
 in which case the rate expression follows
 first-order kinetics,
 Apparent Reaction Orders: In describing reaction orders for this equation,

one would say that the reaction is apparent first order at high azomethane
concentrations and apparent second order at low azomethane
concentrations.
29
L10-30
Chain Reactions
• A chain reaction consists of the following sequence:
– Initiation
• formation of an active intermediate (radicals)
– Propagation or chain transfer
• interaction of an active intermediate with the
reactant or product to produce another active
intermediate (a radical species)
– Termination
• deactivation of the active intermediate
Common in radical polymerizations and cracking of ethane
L10-31
Free Radical Polymerizations (4 steps)

M
monomer M M M M-M-M polymer
M M n
k0
1. Initiation: I2   2I  Initiator (I) decomposes to 2 free radicals
k
I  M 
i R 
1
Radical (1)
kp
2. Propagation: R1  M 
 R2  Chain elongation, new
kp monomers add to chain
R j  M 
 R j1 
km
3. Chain transfer: R j  M   Pj  R1 
“Live” polymer chain transfers radical to monomer.
Polymer chain is no longer reactive (dead). Can also
transfer to solvent or other species
k
4a. Termination by addition: R j  Rk  
add R j k
k
4b. Termination by disproportionation: R j  Rk  
dis  R  R
j k
L10-32
PSSH Applied to Thermal Cracking

of Ethane
The thermal decomposition of ethane to ethylene, methane, butane and
hydrogen is believed to proceed in the following sequence:
Initiation: C2H6 

1 2CH • k r1,C2H6  k1CC2H6
3
Propagation: CH3   C2H6 

2  CH  C H k r2,C2H6  k 2CCH3 CC2H6
4 2 5
C2H5 • 
k
3 C H  H • r3,C2H4  k3CC2H5 
2 4
H • C2H6 
k
4  C H • H r4,C2H6  k 4CHCC2H6
2 5 2
 
k 2
Termination: 2C2H5  
5 C H
4 10 r5,C2H5   k5 CC2H5 
(a) Use the PSSH to derive a rate law for the rate of formation of ethylene
(b) Compare the PSSH solution in Part (a) to that obtained by solving the complete set
of ODE mole balance
The rate of formation of ethylene rC2H4  k 3 CC2H5 
L10-33
Goal: replace CC2H5•
The net rates of reaction of reactive intermediates C2H5•, CH3•, H• are:
C2H5• was formed in rxns 2 & 4, and consumed in r1,C2H6  k1CC2H6
rxns 3 & 5:
rC H   r2,C H  r3,C H  r4,C H  r5,C H  r k C C
2 5 2 6 2 4 2 6 2 5 2,C2H6 2 CH3  C2H6
CH3• was formed in rxn 1 and consumed in rxn 2:
-r3,C2H4  -k 3 C C 2H5
rCH3   2r1,C2H6  r2,C2H6
•
r4,C2H6  k 4CHCC2H6
H• was formed in rxn 3 and consumed in rxn 4:
 
2
rH  r3,C2H4  r4,C2H6 r5,C2H5   k5 CC2H5 
Plug rate eqs into eq above, assume rate = 0 (PSSH) & solve for reactive species
 
2
rC H   k 2CCH CC H  k3CC H   k 4CHCC H  k5 CC H  0
2 5 3 2 6 2 5 2 6 2 5
Need to replace CCH3• and CH•
rCH3   0  2k1CC2H6  k 2CCH3 CC2H6  2k1CC2H6  k 2CCH3 CC2H6
k1CC2H6 k3CC
2k 2H5 
  CCH3   CCH   1 Do the same for CH• CH 
k 2CC2H6 3 k2 k 4CC
2H6
L10-34
The net rates of reaction of active intermediates C2H5•, CH3•, H• are (PSSH):
rxns 3 & 5:
2 5 2 6 2 4 2 6 2 5 2,C2H6 2 CH3  C2H6
-r3,C2H4  -k 3 C C 2H5
rCH3   2r1,C2H6  r2,C2H6
•
 
2
Plug rate eqs into eq above, assume rate=0 (PSSH) & solve for reactive species
 
2
rC H   k 2CCH CC H  k3CC H   k 4CHCC H  k5 CC H  0
2 5 3 2 6 2 5 2 6 2 5
Plug in expressions for CCH3• and CH• into k3CC
2k 2H5 
C2H5• rate eq for C2H5• & solve for C2H5• CCH3 •  1 CH 
k2 k 4CC
assuming rate = 0 (PSSH) 2H6
 
2k1 k3CC H  2
rC  k2 CC H  k3CC H   k 4 2 5 C
C2H6  k 5 CC2H5  0
2H5  k2 2 6 2 5 k 4CC H
2 6
L10-35
rxns 3 & 5:
2 5 2 6 2 4 2 6 2 5 2,C2H6 2 CH3  C2H6
-r3,C2H4  -k 3 C C 2H5
rCH3   2r1,C2H6  r2,C2H6
•
 
2
Plug rate eqs into eq above, assume rate=0 (PSSH) & solve for reactive species
k3CC H 
 
2 2k1
rC H   k 2CCH CC H  k3CC H   k 4CHCC H  k5 CC H   0 CCH3 •  CH  2 5
2 5 3 2 6 2 5 2 6 2 5 k2 k 4CC H
2 6
 
2k1 k3CC H  2
 k2 CC H  k3CC H   k 4 2 5 C
C2H6  k 5 CC2H5  0
k2 2 6 2 5 k 4CC H
2 6
   
2 2
 2k1CC H  k3CC H   k3CC H   k5 CC H   0  2k1CC2H6  k5 CC2H5 
2 6 2 5 2 5 2 5
2k1CC 2k1CC H
 2H6  CC 2
2H5   2 6 C
C2H5 
k5 k5
L10-36
rxns 3 & 5:
2 5 2 6 2 4 2 6 2 5 2,C2H6 2 CH3  C2H6
-r3,C2H4  -k 3 C C 2H5
rCH3   2r1,C2H6  r2,C2H6
•
 
2
k3CC Plug expressions for

2k1CC H 2k 2H5 
2 6 C
C2H5 
CCH3 •  1 CH  reactive species into eq
k5 k2 k 4CC
2H6 for rC2H4 above
0.5 The CC2H4 depends on CC2H6.

 2k1 
rC2H4  k 3 CC2H5   rC2H4 = k 3  CC2H6  How does CC2H6 change with
 5
k  time?
-rC2H6 = k1CC2H6 + k 2CCH3 •CC2H6 + k 4 CH•CC2H6 Need to eliminate the

reactive species
L10-37
Rate of disappearance
of ethane: -rC2H6 = k1CC2H6 + k 2CCH3 • CC2H6 + k 4 CH• CC2H6
Purpose: replace [CH3•] and [H•]

The net rates of reaction of active intermediates CH3•, C2H5•, H• are (PSSH):
rC2H5   r2,C2H6  r3,C2H4  r4,C2H6  r5,C2H5   0
rCH3   2r1,C2H6  r2,C2H6  0 rH  r3,C2H4  r4,C2H6  0
From the previous slide:

k3CC 1
CCH3 •  2k1 k 2 2H5   2k  2
CH  CC2H5 •   1 CC2H6 
k 4CC
1
2H6  k5 
k 3  2k1 2 1
CH•   
k 4  k5  CC2H6 0.5
2k -rC2H6 = k1CC2H6 + k 2CCH3 •CC2H6 + k 4 CH•CC2H6
CCH3 •  1
k2 0.5
2k k  2k  CC2H6
 -rC2H6 = k1CC2H6 + k 2 1 CC2H6 + k 4 3  1 
k2 k 4  k5  CC2H6 0.5
0.5 0.5
 2k   2k 
 -rC2H6 = k1CC2H6 + 2k1CC2H6 + k 3  1 CC2H6   -rC2H6 = 3k1CC2H6 + k 3  1 CC2H6 
 k5   k5 
L10-38
1 1
 2k  2  2k  2
rC2H4 = k 3  1 CC2H6  -rC2H6 = 3k1CC2H6 + k 3  1 CC2H6 
 k5   k5 
For a constant-volume batch reactor :
1 1
dCC2H4  2k1  2 dCC2H6  2k1  2
= k3  CC2H6  - = 3k1CC2H6 + k 3  CC2H6 
dt  k5  dt  k5 
For given initial concentration of C2H6

and temperature, these two equation
can be solved simultaneously ( i.e.,
use Polymath)
Providing the concentration - time relationship using the PSSH
Other methods can also be used - solve the complete set of ODE mole balances
L10-39
C2H6 
k1
 2CH3 •
H • C2H6 
k4
C2H5 • H2
CH3 • C2H6 
k2
CH4  C2H5 •
2C2H5 • 
k5
C4H10
C2H5 • 
k3
C2H4  H •
1. Mole balances: 2. Rate laws for each species:
(Batch)
dC1
= r1 r1 = -k1C1 - k 2C1C2 - k 4C1C6
C2H6 dt
dC2
CH3• dt = r2 r2 = 2k1C1 - k 2C2C1 All these O.D.Es can be
dC3 r3  k 2C1C2 solved simultaneously
CH4 dt = r3
dC4
C2H5• = r4 r4 = k 2C1C2 - k3C4 + k 4C1C6 - k5C42
dt
dC5
C2H4 dt = r5 r5 = k3C4 The comparisons of the results
dC6
r6 = k3C4 - k 4C1C6 obtained from the two methods are
H• = r6
dt shown on Fig.E7.2 of textbook 3rd Ed.
dC7 The two results are identical,
H2 = r7 r7 = k 4C1C6
dt indicating the validity of the PSSH
C4H10 dC8 = r8 1
r8 = k 5C42 under these conditions
dt 2
L10-40
Fig.E7.2 of textbook 3rd Ed- Comparison of
Concentration-time Trajectories
L10-41
Fig.E7.2 of textbook 3rd Ed- Comparison of
Temperature-time Trajectories for Ethylene
L10-42
L10-43
Ozone (O3 ) Example Problem

Overall Reaction for Ozone Decomposition: 2O3  3O2
When ozone decomposes in the presence of an inert gas, M, the
following kinetics are observed:
kCO3 2CM
rO3 
CO2 CM  k 'CO3
Postulate a reaction mechanism that is consistent with this rate law
This is provided as an extra example that can be skipped if

there isn’t enough time to cover it in class.
Postulating Mechanism for O3 L10-44
Decomposition (Step 1)
step is probably: reactive intermediate
B  A *  Collision products
2. If the denominator contains a constant term, then one rxn step is probably:
3. If the numerator contains a species concentration, then one rxn step is
probably:
kCO3 2CM Experimentally observed rate equation for

Apply: r 
O3
CO2 CM  k 'CO3  overall reaction  : 2O3  3O2
CO2, CM & CO3 in denominator, so O2, M, and O3 must each collide a with
reactive intermediate. What is the reactive intermediate?
Since one oxygen atom is lost from the ozone molecule (O3), oxygen
radicals (O•) are likely the reactive intermediate:
O2  O  O3 (Possible Rxn 1) O3  O  2O2 (PR2) M  O  M  ? (PR3)
L10-45
Postulating Mechanism for O3
Decomposition (Step 1 continued)

Apply: r 
O3
CO2, CM & CO3 in denominator; they must collide with reactive intermediate O•
O2  O  O3 (possible rxn 1) O3  O  2O2 (PR2) M  O  M  ? (PR3)
Wait, M is inert, so it cannot react with O• to create a new chemical species

• An inert molecule can provide kinetic energy in another reaction
→ M must participate in one of the other reactions Which one?
CM is multiplied by CO2 in the denominator, so combine PR3 with PR1
M  O2  O  O3  M (PR1b)
Postulating Mechanism for O3 L10-46
Decomposition (Steps 2 & 3)

2. If the denominator contains a constant term, then one rxn step is probably:
3. If the numerator contains a species concentration, then one rxn step is
probably:

Apply: r 
O3
M  O2  O  O3  M (PR1b) O3  O  2O2 (PR2)
Denominator doesn’t contain a constant, so step 2 isn’t in our mechanism
Both CO3 and CM appear in the numerator, so one reaction step may be:
O3  M  M  O2  O  (PR4)
Note that PR4 is the reverse of PR1
L10-47

Ozone Decomposition
Apply: r 
O3
CM and CO2 in denominator: M  O2  O  O3  M

CO3 in denominator: O3  O  2O2 Reactive
CO3 and CM in numerator: O3  M  M  O2  O  intermediate
k1
Postulated mechanism: O3  M M  O2  O 
k 1 Does this add up to
+ O3  O  
2  2Ok the overall reaction?
2
2O3  3O2 yes!
Now derive a rate equation for the postulated mechanism and check if
it describes the experimentally observed rate equation
L10-48

kCO3 2CM
Nonelementary kinetics, result of
rO3  multiple elementary rxns & active
CO2 CM  k 'CO3
intermediates
k1 Reactive
Postulated mechanism: O3  M M  O2  O 
k 1 intermediate
k
O3  O  
2  2O
2
Write –rO3 for the postulated reaction mechanism
rO3  rxns that consume O3  - rxns that form O3 
rO3  k1CO3 CM  k 1CMCO2 CO  k 2CO3 CO
• -rO3 is in terms of CO•, which is not measurable species because it is a

reactive intermediate (so reactive it is consumed as fast as it is formed)
• Need to get CO• in terms of measurable species and plug into –rO3
L10-49
Pseudo-Steady State Hypothesis

k1 Reactive intermediate,
Postulated mechanism: 1.) O3  M M  O2  O  must replace CO• in the
k 1
k2 rate equation
2.) O3  O  
 2O2
rO3  k1CO3 CM  k 1CMCO2 CO  k 2CO3 CO Factor out to simplify

 rO3  k1CO3 CM  k 2CO3  k 1CMCO2 CO 
1) Write rO•
2) Rearrange to get CO• in terms of measurable species
3) plug eq for CO• back into –rO3
rO  k1CO3 CM  k 1CMCO2 CO  k 2CO3 CO
CO• is very small, and O• is so reactive that it is consumed as fast as it is
formed, so apply pseudo-steady state hypothesis: rO  0

rO  0  k1CO3 CM  CO k 1CMCO2  k 2CO3 
Put concentration of reactive intermediate O• in terms of other species
L10-50
Concentration of Reactive O•
Postulated mechanism: 1.) O  M k1 Reactive intermediate,
3 M  O2  O  must replace CO• in the
k 1
k2 rate equation
2.) O3  O  
 2O2
kCO3 2CM Observed rate equation
rO3 
CO2 CM  k 'CO3 (nonelementary)

rO3  k1CO3 CM  k 2CO3  k 1CMCO2 CO 

rO  0  k1CO3 CM  CO k 1CMCO2  k 2CO3  Solve for CO• in terms
of other species
 
 k 1CMCO2  k 2CO3 CO  k1CO3 CM
k1CO3 CM
 CO  Plug CO• into –rO3
k 1CMCO2  k 2CO3
 
k1CO3 CM
 rO3  k1CO3 CM  k 2CO3  k 1CMCO2
Now we will rearrange and simplify to see if it matches the experimental data
L10-51
Rearranging the Postulated Rate Eq.

3 M  O2  O  must replace CO• in the
k 1
k2 rate equation
2.) O3  O  
 2O2
 
 
k1CO3 CM
Plug in CO•  rO3  k1CO3 CM  k 2CO3  k 1CMCO2  
 k 1CMCO  k 2CO 
 2 3 
2 2
Multiply out k1k 2 CO CM  k 1k1CM CO2 CO3 Get common
 rO3  k1CO3 CM  3
brackets k 1CMCO  k 2CO 2
denominator
3
 rO3 

k1CO3 CM k 1CMCO2  k 2CO3


k1k 2CO3 2CM  k 1k1CM2CO2 CO3
k 1CMCO2  k 2CO3 k 1CMCO2  k 2CO3
k1k 1CM2CO2 CO3  k1k 2CO3 2CM  k1k 2CO3 2CM  k 1k1CM2CO2 CO3
 rO3 
2k1k 2CO3 2CM Conventional to  2k1k 2 k 1  CO3 2CM
 rO3  remove constant  rO3 
k 1CMCO2  k 2CO3 CMCO2   k 2 k 1  CO3
from 1st term
L10-52
Comparison Between Postulated

and Experimental Rate Equation
3 M  O2  O  cannot appear in the
k 1
k2 rate equation
2.) O3  O  
 2O2
Compare rate eq for postulated mechanism to the experimental rate eq
 2k1k 2 k 1  CO3 2CM kCO3 2CM

rO3  rO3 
CMCO2   k 2 k 1  CO3 CO2 CM  k 'CO3
Rate equation for Experimentally observed

postulated mechanism rate equation
2k1k 2 k2
k  k'
k 1 k 1
These are the same → postulated rate law explains the experimental data
L10-53

ACRE2a Non Elementary Reaction Kinetics Rev

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Advanced

Chemical Reaction Engineering

(Chapter 9 Fogler’s Essentials)

Topic Learning Outcomes

L10: Nonelementary Reaction Kinetics

• Nonelementary reaction kinetics: no direct correspondence between

Review (L4): Reversible Reactions

Determining Mechanism to Describe

Postulating a Reaction Mechanism

Apply: kiCNO2CO2 Experimentally observed rate equation for

A Reaction Mechanism for

2NO  O2  2NO2 yes

Postulated Mechanism for

Consumption of NO: rNO  k1CNOCO2  k 1CNO3  k 2CNO3 CNO

Pseudo-Steady State Hypothesis

Solve for concentration of reactive intermediate NO3 in terms of other species

Concentration of Reactive Intermediate

rNO  k1CNOCO2  k 2CNO  k 1  CNO3

rNO3  0  k1CNOCO2  k 1CNO3  k 2CNO3 CNO Solve for CNO3 in

Rearranging the Postulated Rate Eq.

Comparison Between Postulated

 2k1k 2 k 1  CNO2CO2 kiCNO2CO2

The assumption that the net rate of reaction is zero is

How did this rate law come about? Suggest a

The reaction: 2NO +O2 2NO2

Write rate of formation of product rNO2

r1NO3 = k1CNOCO2 = k1 [ NO][O2 ]

r3NO* = -k3CNO* CNO = k3 éë NO3* ùû [ NO]

r1NO* = r1 Þ r1NO* = k1[ NO] [O2 ]

-r2NO* = r2 Þ r2NO * = -k2 [ NO *

r3 NO*  r3  r3 NO*  k3  NO3*   NO 

rNO* = r1NO* + r2NO* + r3NO*

rNO*  k1  NO  O2   k2  NO3*   k3  NO3*   NO 

0  k1  NO  O2   k2  NO3*   k3  NO3*   NO 

0 = k1 [ NO] [O2 ] - éë NO3* ùû ( k2 + [ NO])

This result shows why the -rNO2

 Step 5. Write net rate of formation of the active

 Step 7. Compare with experimental data.

 Apparent Reaction Orders: In describing reaction orders for this equation,

Free Radical Polymerizations (4 steps)

PSSH Applied to Thermal Cracking

Initiation: C2H6 

Propagation: CH3   C2H6 

k3CC Plug expressions for

0.5 The CC2H4 depends on CC2H6.

-rC2H6 = k1CC2H6 + k 2CCH3 •CC2H6 + k 4 CH•CC2H6 Need to eliminate the

Purpose: replace [CH3•] and [H•]

From the previous slide:

For given initial concentration of C2H6

Providing the concentration - time relationship using the PSSH

Ozone (O3 ) Example Problem

This is provided as an extra example that can be skipped if

kCO3 2CM Experimentally observed rate equation for

kCO3 2CM Experimentally observed rate equation for

Wait, M is inert, so it cannot react with O• to create a new chemical species

Decomposition (Steps 2 & 3)

kCO3 2CM Experimentally observed rate equation for

Postulated Mechanism for

CM and CO2 in denominator: M  O2  O  O3  M

2O3  3O2 yes!

Postulated Mechanism for

• -rO3 is in terms of CO•, which is not measurable species because it is a

Pseudo-Steady State Hypothesis

Rearranging the Postulated Rate Eq.