L10-1

Review: Multiple Rxns & Selectivity

1) Parallel / competing rxns k1 k2
2) Series rxns A B C
k1 B Desired product
A
k1 k2
3) Complex rxns A+B C+D A+C E
k2 C
instantaneous rate selectivity, SD/U instantaneous yield, YD
rate of formation of D rD (at any point or time in reactor)
SD U rate of formation of D r
rate of formation of U rU YD D
rate of consumption of A rA
overall rate selectivity,S% DU
%
overall yield, Y
ND Final moles of desired product D
S%D U FD at
%
NU Final moles of undesired product flow YD F F exit
A0 A
F Exit molar flow rate of desired product
S%D U D ND at
FU Exit molar flow rate of undesired product batch Y%
D tfinal
NA0 NA
Maximize selectivity / yield to maximize production of desired product
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 Review: Maximizing SD/U for L10-2

Parallel Rxns
ED EU

CA CB
AD 1 2 1 2 What reactor conditions and
SD U e RT configuration maximize selectivity?
AU
Specific rate of desired reaction kD increases:
a) If ED > EU b) If ED < EU
more rapidly with increasing T less rapidly with increasing T
Use lower temperature(not so low
Use higher temperature
that the reaction rate is tiny)
To favor production of the desired product
Now evaluate concentration:
a) 1 2 1 2 0 b) 1 2 1 2 0

Use large CA Use small CA

c) 1 2 1 2 0 d) 1 2 1 2 0
Use large CB Use small CB
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 kD L10-3
D High C favors desired High CA favors undesired
A+B A
product formation product formation
kU
U (keep CA low)
Batch reactor
PFR/PBR
Side streams feed low CA
High CB CA
When CA & CB are low (end time Semi-batch
favors or position), all rxns will be slow reactor slowly feed High CB
desired A to large amt of B
product PFR/PBR CA CA CA
formation High P for gas-phase rxn, do not CSTRs in
add inert gas (dilutes reactants) series
CA00 CA0
CB00 CB
CSTR
PFR/PBR w/ side streams feeding
High CB low CB CB
favors Semi-batch
undesired reactor, slowly High CA PFR/PBR
product feed B to large amount of A PFR/PBR w/ high
formation CB CB CB recycle
CSTRs in Dilute feed with inerts that are
(keep CB series
easily separated from product
low) B consumed
Slides courtesy of Prof before&leaving
M L Kraft, Chemical CSTR
Biomolecular Engr Low P if gas phaseUrbana-Champaign.
n Dept, University of Illinois,
 L10-4

Review: Reactions in Series: Cj & Yield

Time is the key factor here!!!
k1 k2
A D U Spacetime for a flow reactor
(desired) (undesired)
Real time t for a batch reactor
To maximize the production of D, optimize the time (batch) or spacetime (flow)

B CA CA0ek1
A C
ek1 ek 2
CB k1C A0
k k
2 1

CC CA0 CA CB
opt
The reactor V (for a given 0) and that maximizes CB occurs when dCB/dt=0
dCB k1CA0
d

k 2 k1

k1e k1
k 2 e k 2
0
1 k V
opt ln 1 so Vopt 0 opt
k1 k 2 k 2 0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-5

L10: Nonelementary Reaction Kinetics

In practice, knowledge of the reaction mechanism helps use to design better
catalyst, trouble shoot, 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 CHBE 471)
Bioreactors (covered in CHBE 471)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-6

Review (L4): Reversible

k
Reactions
aA b B A
c C d D
kA
a b a b
Rate of disappearance of A (forward rxn): rfA k A CA CB rfA k A CA CB
c d
Rate of generation of A (reverse reaction): rbA k A CC CD
rA,net rA rfA rbA

rA k A CaA CB
b c d
k A CC CD
consumed generated
At equilibrium, the reaction rate is zero, rA=0

rA 0 k A CaA CB
b c d
k A CCCD

k A CaA CB
b c d
k A CC CD

kA CcCCD
d
Thermodynamic equilibrium relationship
KC
k A CaA CB
b
KC: concentration equilibrium constant (capital K)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-7

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:
k iCNO2CO2
rNO Nonelementary
1 k iiCNO
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-8

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?
k iCNO2CO2 Experimentally observed rate equation for
Apply: rNO
1 k iiCNO 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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-9

A Reaction Mechanism for

Observed Kinetics?
k iCNO2CO2 Experimentally observed rate equation for
Apply: rNO
1 k iiCNO 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
k
Postulated mechanism: NO O2 1
NO3
k 1 Does this add up to
+ NO3 NO

k2
2NO2
the overall reaction?

2NO O2 2NO2 yes

Now derive a rate equation for the postulated mechanism and check if
it describes the experimentally observed rate equation
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-10

Postulated Mechanism for

Nonelementary Reaction Kinetics
k iCNO2CO2
Nonelementary kinetics, result of
rNO multiple elementary rxns & active
1 k iiCNO
intermediates

k1 Reactive
Postulated mechanism: NO O2 NO 3 intermediate
k 1
k2
NO3 NO
2NO2
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-11

Pseudo-Steady State Hypothesis

k1 Reactive intermediate,
Postulated mechanism 1.) NO O2
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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-12

Concentration of Reactive Intermediate

k1 Reactive
Postulated mechanism 1.) NO O2
NO3
intermediate
k 1
k2
2.) NO3 NO
2NO2
k iCNO2CO2 Observed rate equation
rNO
1 k iiCNO (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 k1CNO CO2 CNO
3
k 1 k 2CNO k1CNOCO2
k1CNO CO2
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-13

Rearranging the Postulated Rate Eq.

Postulated mechanism 1.) NO O k1 Reactive
2
NO3
k 1 intermediate
k2
2.) NO3 NO
2NO2
k1CNOCO2
Plug in CNO3 rNO k1CNO CO2 k 2CNO k 1
k 1 k 2CNO
k 2CNO k 1 Common
Factor out r
k1CNOCO2
NO k1CNO CO2 1
k 1 k

C
2 NO
denominator

k k C k C k 1

rNO k1CNOCO2 1 2 NO 2 NO
k 1 k 2CNO k 1 k 2CNO
Add fraction

2
2k 2CNO

rNO k1CNOCO2
k k

1 2 NO C

Multiply
rNO
2k1 2 NO CO2
k C
k 1 k 2CNO
2k1k 2 k 1 CNO2CO2 Conventional to reduce
rNO the additive constant in
1 k 2 k 1 CNO the numerator to 1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-14

Comparison Between Postulated

and Experimental Rate Equation
Postulated mechanism 1.) NO O k1 Reactive
2
NO3
k 1 intermediate
k2
2.) NO3 NO
2NO2
Compare rate eq for postulated mechanism to the experimental rate eq

2k1k 2 k 1 CNO2CO2 k iCNO2CO2

rNO rNO
1 k 2 k 1 CNO 1 k iiCNO
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-15

Chain Reaction

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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-16

Free Radical Polymerizations (4 steps)

M
M M
monomer M M M M-M-M polymer
n
k
0
1. Initiation: I
2 2I Initiator (I) decomposes to 2 free radicals
ki
I M
R1 Radical (1)
kp
2. Propagation: R1 M
R2 Chain elongation, new
kp monomers add to chain
R j M
R j1
km
3. Chain transfer: R j M
j
P R1
Live polymer chain transfers radical to monomer.
Polymer chain is no longer reactive (dead). Can also
transfer to solvent or other species
k add
4a. Termination by addition: R j Rk
R j k
k dis
4b. Termination by disproportionation: R j Rk
Rj Rk
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-17

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

k1
2CH3 r1,C2H6 k1CC2H6

k2 r2,C2H6 k 2CCH3 CC2H6

Propagation: CH3 C2H
6 CH4 C2H5
k3 r3,C2H4 k 3 CC2H5
C2H5
C2H4 H

H C2H
k4 r4,C2H6 k 4CHCC2H6
6 2H5 H2
C

k5 2
Termination: 2C2H5
C4H10 r5,C2H5 k 5 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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-18
The rate of formation of ethylene rC2H4 k 3 CC2H5 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:
rC2H5 r2,C2H6 r3,C2H4 r4,C2H6 r5,C2H5 r k C C 2,C2H6 2 CH3 C2H6
CH3 was formed in rxn 1 and consumed in rxn 2:
-r3,C -k 3 C C
rCH 2r1,C H r2,C H 2H4 2H5
3 2 6 2 6
r4,C2H6 k 4CHCC2H6
H was formed in rxn 3 and consumed in rxn 4:

2
rH r3,C2H4 r4,C2H6 r5,C2H5 k 5 CC2H5
Plug rate eqs into eq above, assume rate = 0 (PSSH) & solve for reactive species

2
rC k 2CCH CC k3CC k 4CHCC k5 CC 0
2H5 3 2H6 2H5 2H6 2H5
Need to replace CCH3 and CH
rCH 0 2k1CC k 2CCH CC 2k1CC k 2CCH CC
3 2H6 3 2H6 2H6 3 2H6

k1CC2H6 2k k3CC
2H5
CCH CCH
3
1 Do the same for CH CH
k 2CC2H6 3 k2 k 4CC
2H6

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-19
The rate of formation of ethylene rC2H4 k 3 CC2H5 Goal: replace CC2H5
The net rates of reaction of active intermediates C2H5, CH3, H are (PSSH):
C2H5 was formed in rxns 2 & 4, and consumed in r1,C2H6 k1CC2H6
rxns 3 & 5:
rC2H5 r2,C2H6 r3,C2H4 r4,C2H6 r5,C2H5 r k C C 2,C2H6 2 CH3 C2H6
CH3 was formed in rxn 1 and consumed in rxn 2:
-r3,C -k 3 C C
rCH 2r1,C H r2,C H 2H4 2H5
3 2 6 2 6
r4,C2H6 k 4CHCC2H6
H was formed in rxn 3 and consumed in rxn 4:

2
rH r3,C2H4 r4,C2H6 r5,C2H5 k 5 CC2H5
Plug rate eqs into eq above, assume rate=0 (PSSH) & solve for reactive species

2
rC k 2CCH CC k3CC k 4CHCC k5 CC 0
2H5 3 2H6 2H5 2H6 2H5

Plug in expressions for CCH3 and CH into 2k1 C k3CC2H5

C2H5 rate eq for C2H5 & solve for C2H5 CCH3 k H
k 4CC H
2 2 6
assuming rate = 0 (PSSH)
k3CC H
2k1

2 5 C 2
rC H k 2 CC H k3CC H k 4 C2H6 k 5 C C2H5 0
2 5 k2 2 6 2 5 k 4CC H
2 6

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-20
The rate of formation of ethylene rC2H4 k 3 CC2H5 Goal: replace CC2H5
The net rates of reaction of active intermediates C2H5, CH3, H are (PSSH):
C2H5 was formed in rxns 2 & 4, and consumed in r1,C2H6 k1CC2H6
rxns 3 & 5:
rC2H5 r2,C2H6 r3,C2H4 r4,C2H6 r5,C2H5 r k C C 2,C2H6 2 CH3 C2H6
CH3 was formed in rxn 1 and consumed in rxn 2:
-r3,C -k 3 C C
rCH 2r1,C H r2,C H 2H4 2H5
3 2 6 2 6
r4,C2H6 k 4CHCC2H6
H was formed in rxn 3 and consumed in rxn 4:

2
rH r3,C2H4 r4,C2H6 r5,C2H5 k 5 CC2H5
Plug rate eqs into eq above, assume rate=0 (PSSH) & solve for reactive species
2k k3CC H

2
rC k 2CCH CC k3CC k 4CHCC k 5 CC 0 CCH3 1 CH 2 5
2H5 3 2H6 2H5 2H6 2H5 k2 k 4CC H
2 6
k3CC H
2k1

2 5 C 2
k2 CC H k3CC H k 4 C2H6 k 5 CC2H5 0
k2 2 6 2 5 k 4CC H
2 6

2 2
2k1CC H k 3CC H k 3CC H k5 CC H 0 2k1CC2H6 k5 CC2H5
2 6 2 5 2 5 2 5
2k1CC H 2 2k1CC H
2 6 CC H 2 6 C
2 5 C2H5
k5 k5
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-21
The rate of formation of ethylene rC2H4 k 3 CC2H5 Goal: replace CC2H5
The net rates of reaction of active intermediates C2H5, CH3, H are (PSSH):
C2H5 was formed in rxns 2 & 4, and consumed in r1,C2H6 k1CC2H6
rxns 3 & 5:
rC2H5 r2,C2H6 r3,C2H4 r4,C2H6 r5,C2H5 r k C C 2,C2H6 2 CH3 C2H6
CH3 was formed in rxn 1 and consumed in rxn 2:
-r3,C -k 3 C C
rCH 2r1,C H r2,C H 2H4 2H5
3 2 6 2 6
r4,C2H6 k 4CHCC2H6
H was formed in rxn 3 and consumed in rxn 4:

2
rH r3,C2H4 r4,C2H6 r5,C2H5 k 5 CC2H5

2k1CC 2k k3CC Plug expressions for

2H6 2H5
CC CCH3 1 CH reactive species into eq
k5 2H5 k2 k 4CC
2H6 for rC2H4 above
0.5 The CC2H4 depends on CC2H6.
2k1
rC k 3 CC rC2H4 = k3 CC2H6
2H4 2H5 How does CC2H6 change with
k
5 time?

-rC2H6 = k1CC2H6 + k 2CCH3 CC2H6 + k 4 CHCC2H6 Need to eliminate the

reactive species
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-22
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 2k1 2
CH CC2H5 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 CHCC2H6
CCH3 1
k2 0.5
2k k 2k1 CC2H6
-rC2H6 = k1CC2H6 + k 2 1 CC2H6 + k 4 3
k2 k 4 k5 CC2H6 0.5
0.5 0.5
2k1 2k1
-rC2H6 = k1CC2H6 + 2k1CC2H6 + k3 CC2H6 -rC2H6 = 3k1CC2H6 + k3 CC2H6
k5 k5
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-23
1 1
2k1 2 2k1 2
rC2H4 = k 3 CC2H6 -rC2H6 = 3k1CC2H6 + k 3 CC2H6
k5 k5
For a constant-volume batch reactor :
1 1
dCC2H4 2k1 2 dCC2H6 2k1 2
= k3 CC2H6 - = 3k1CC2H6 + k3 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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-24
C2H6
k1
2CH3
H C2H6
k4 C2H5 H2
CH3 C2H6
k2
4
CH C2H5
2C2H5
k5 C4H10
C2H5
k3
C2H4 H
1. Mole balances: 2. Rate laws for each species:
(Batch)
dC1
C2H6 dt
= r1 r1 = -k1C1 - k 2C1C2 - k 4C1C6
dC2
CH3 dt = r2 r2 = 2k1C1 - k 2C2C1 All these O.D.Es can be
dC3
CH4 dt = r3
r3 k 2C1C2 solved simultaneously

C2H5
dC4
= r4 r4 = k 2C1C2 - k 3 C4 + k 4C1C6 - k 5C4 2
dt
dC5
C2H4 dt = r5 r5 = k 3 C4
The comparisons of the results
dC6
r6 = k 3C4 - k 4 C1C6 obtained from the two methods are
H = r6
dt shown on page 391 of textbook.
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-25

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 isnt enough time to cover it in class.

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-26
Postulating Mechanism for O3 Decomposition
(Step 1)
1. If CB appears in the denominator of the rate law, then one elementary rxn
step is probably: reactive intermediate
B A *
Collision products
2. If the denominator contains a constant term, then one rxn step is probably:
A *
Decomposition products
3. If the numerator contains a species concentration, then one rxn step is
probably:
Cspecies other species? A * other products?

kCO3 2CM Experimentally observed rate equation for

Apply: rO
3 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
Since one oxygen atom is intermediate?
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)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-27
Postulating Mechanism for O3 Decomposition
(Step 1 continued)
1. If CB appears in the denominator of the rate law, then one elementary rxn
step is probably: reactive intermediate
B A * Collision products

kCO3 2CM Experimentally observed rate equation for

Apply: r
O3
CO2 CM k 'CO3 overall reaction : 2O3 3O2
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)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-28
Postulating Mechanism for O3 Decomposition (Steps 2
& 3)
1. If CB appears in the denominator of the rate law, then one elementary rxn
step is probably: reactive intermediate
B A *
Collision products
2. If the denominator contains a constant term, then one rxn step is probably:
A *
Decomposition products
3. If the numerator contains a species concentration, then one rxn step is
probably:
Cspecies other species? A * other products?

kCO3 2CM Experimentally observed rate equation for

Apply: rO
3 CO2 CM k 'CO3 overall reaction : 2O3 3O2
M O2 O O3 M (PR1b) O3 O 2O2 (PR2)
Denominator doesnt contain a constant, so step 2 isnt 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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-29

Postulated Mechanism for

Ozone Decomposition
kCO3 2CM Experimentally observed rate equation for
Apply: r
O3
CO2 CM k 'CO3 overall reaction : 2O3 3O2

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
k
Postulated mechanism: O3 M 1
M O2 O
k 1 Does this add up to
+ O O
k2
2O
the overall reaction?
3 2

2O3 3O2 yes!

Now derive a rate equation for the postulated mechanism and check if
it describes the experimentally observed rate equation
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-30

Postulated Mechanism for

Nonelementary Reaction Kinetics
kCO3 2CM
Nonelementary kinetics, result of
rO3 multiple elementary rxns & active
CO2 CM k 'CO3
intermediates
M O2 O Reactive
k
Postulated mechanism: O3 M 1
k 1 intermediate
k2
O3 O
2O2
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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-31

Pseudo-Steady State Hypothesis

k Reactive intermediate,
Postulated mechanism: 1.) O3 M M O2 O
1
k 1 must replace CO in the
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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-32

Concentration of Reactive O
Postulated mechanism: 1.) O3 M k1 M O2 O Reactive intermediate,
k 1 must replace CO in the
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
k 1CMCO2 k 2CO3 Plug CO into rO3
k1CO3 CM
rO3
k1CO3 CM k 2CO3 k 1CMCO2
k 1CMCO2 k 2CO3
Now we will rearrange and simplify to see if it matches the experimental data
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-33

Rearranging the Postulated Rate Eq.

Postulated mechanism: 1.) O3 M k1 M O2 O Reactive intermediate,
k 1 must replace CO in the
k2 rate equation
2.) O3 O
2O2
k1CO3 CM

Plug in CO rO3 k1CO3 CM k 2CO3 k 1CMCO2 k 1CMCO
k 2CO3
2
Multiply out k1k 2CO3 2CM k 1k1CM2CO2 CO3 Get common
rO3 k1CO3 CM
brackets k 1CMCO k 2CO 2
denominator
3

rO3

k1CO3 CM k 1CMCO2 k 2CO3 k1k 2CO 2CM k 1k1CM2CO CO
3 2 3
k 1CMCO2 k 2CO3 k 1CMCO2 k 2CO3
k1k 1CM2CO2 CO3 k1k 2CO3 2CM k1k 2CO3 2CM k 1k1CM2CO2 CO3
rO3
k 1CMCO2 k 2CO3
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L10-34

Comparison Between Postulated

and Experimental Rate Equation
Postulated mechanism: 1.) O3 M k1 M O2 O Reactive intermediate,
k 1 cannot appear in the
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

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