L10 Nonelementary Rxns

L10-1
Review: Multiple Rxns & Selectivity

1) Parallel / competing rxns
A
k1
k2
k1
A
Desired product
2) Series rxns
3) Complex rxns
instantaneous rate selectivity, SD/U

rate of formation of D rD
SD U
rate of formation of U rU
overall rate selectivity,S%
DU
S%D U
A+B
k1
k2
C+D A+C
k2
instantaneous yield, YD
(at any point or time in reactor)

r
rate of formation of D
YD
D
rate of consumption of A rA
ND
Final moles of desired product
NU Final moles of undesired product
F
Exit molar flow rate of desired product
S%D U D
FU Exit molar flow rate of undesired product
overall yield, Y
%
FD
%
flow YD F F
A0
A
at
exit
ND
batch Y%
D
NA0 NA
at
tfinal
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

Parallel Rxns
SD U
ED EU
AD
e RT
AU
CA
1 2
CB
1 2
L10-2
What reactor conditions and

configuration maximize selectivity?
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
kD
A+B
kU
High CA favors undesired

High
C
favors
desired
A
product formation
product formation
U
(keep CA low)
High CB
favors
desired
product
formation
L10-3
Batch reactor
When CA & CB are low (end time
or position), all rxns will be slow
PFR/PBR
High P for gas-phase rxn, do not
add inert gas (dilutes reactants)
PFR/PBR
Side streams feed low CA
CA
Semi-batch
reactor slowly feed
High CB
A to large amt of B
CA
CA
CA
CSTRs in
series
CA00
CB00
CA0
CB
CSTR
PFR/PBR w/ side streams feeding

High CB
low CB
CB
favors
Semi-batch
High CA
PFR/PBR
undesired reactor, slowly
PFR/PBR
w/ high
feed B to large amount of A
product
recycle
CB
CB
CB
formation
CSTRs in
Dilute feed with inerts that are
(keep CB series
easily separated from product
low)
B consumed
before&leaving
CSTR
Low
P if gas
phaseUrbana-Champaign.
Slides courtesy of Prof
M L Kraft, Chemical
Biomolecular
Engr
University
of Illinois,
n Dept,
L10-4
Review: Reactions in Series: Cj & Yield

A
k1
Time is the key factor here!!!
k2
U
D
(desired) (undesired)
Spacetime for a flow reactor

Real time t for a batch reactor
To maximize the production of D, optimize the time (batch) or spacetime (flow)
CA CA0ek1
B
A
ek1 ek 2
CB k1C A0
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
k1
k 2
k
e
k
e
0
1
2
d
k 2 k1
opt
k
1
ln 1
k1 k 2 k 2
V
so Vopt 0 opt
0
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)
L10-6
Review (L4): 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 CA CB rfA k A CA CB
c d
CD
Rate of generation of A (reverse reaction): rbA k A CC
rA,net rA rfA rbA

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

KC: concentration equilibrium constant (capital K)
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
Nonelementary
rNO
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
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?
Apply:
rNO
k iCNO2CO2
1 k iiCNO
Experimentally observed rate equation for

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
L10-9
A Reaction Mechanism for

Observed Kinetics?
Apply:
rNO
k iCNO2CO2
1 k iiCNO

overall reaction : 2NO O2 2NO2
NO3 NO 2NO2
CNO in denominator:
NO O2 NO3
CNO & CO2 in numerator:
NO3 NO O2
Constant in numerator:
Postulated mechanism:
Reactive
intermediate
NO3
NO O2 1
k 1
NO3 NO

k2
2NO2
2NO O2 2NO2
Does this add up to

the overall reaction?
yes
Now derive a rate equation for the postulated mechanism and check if
it describes the experimentally observed rate equation
L10-10
Postulated Mechanism for

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
NO3 NO

k2
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
L10-11
Pseudo-Steady State Hypothesis

Postulated mechanism 1.) NO O2
2.) NO3 NO

k1
k 1
k2
NO3
2NO2
Reactive intermediate,
must replace CNO3 in
the rate equation
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
rNO3 0
as fast as it is formed, so
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
L10-12
Concentration of Reactive Intermediate

k1

Postulated mechanism 1.) NO O2
k 1
2.) NO3 NO

rNO
k iCNO2CO2
1 k iiCNO
k2
NO3
Reactive
intermediate
2NO2
Observed rate equation

(nonelementary)
rNO k1CNOCO2 k 2CNO k 1 CNO3

rNO3 0 k1CNOCO2 k 1CNO3 k 2CNO3 CNO
k 1CNO3 k 2CNO3 CNO k1CNO CO2 CNO
CNO3
Solve for CNO3 in

terms of other species
k 1 k 2CNO
k1CNO CO2
k 1 k 2CNO
rNO k1CNOCO2 k 2CNO k 1
k1CNOCO2
Plug CNO3 into -rNO

k1CNOCO2
k 1 k 2CNO
Now we will rearrange and simplify to see if it matches the experimental data
L10-13
Rearranging the Postulated Rate Eq.

Postulated mechanism 1.) NO O

2
2.) NO3 NO

k1
k 1
k2
NO3
Reactive
intermediate
2NO2
Plug in CNO3 rNO k1CNO CO2 k 2CNO k 1
k1CNOCO2
k 1 k 2CNO
k 2CNO k 1 Common
Factor out r
denominator
NO k1CNO CO2 1
k1CNOCO2
k
k
C
1
2 NO
k k C
k C k 1
rNO k1CNOCO2 1 2 NO 2 NO
Add fraction
k 1 k 2CNO k 1 k 2CNO
2
2k 2CNO
2k
k
C
Multiply
1 2 NO CO2
rNO k1CNOCO2
rNO
k
C
k 1 k 2CNO
1 2 NO
2k1k 2 k 1 CNO2CO2
rNO
1 k 2 k 1 CNO
Conventional to reduce
the additive constant in
the numerator to 1
Comparison Between Postulated

and Experimental Rate Equation
Postulated mechanism 1.) NO O

2
2.) NO3 NO

k1
k 1
k2
NO3
L10-14
Reactive
intermediate
2NO2
Compare rate eq for postulated mechanism to the experimental rate eq
2k1k 2 k 1 CNO2CO2
rNO
1 k 2 k 1 CNO
Rate equation for
postulated mechanism
rNO
k iCNO2CO2
1 k iiCNO
Experimentally observed
rate equation
Clicker Q: Are these rate equations the same?

a) Yes
2k1k 2
k2
ki
kii
b) No
k 1
k 1
Yes, these are the same postulated rate law explains the experimental data
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
L10-16
Free Radical Polymerizations (4 steps)

M
monomer
1. Initiation:
M
M
M M M
k
0
I
2
I M
2. Propagation:
M-M-M polymer
n
Initiator (I) decomposes to 2 free radicals
2I
ki
R1 M

R j M

3. Chain transfer: R j M

Radical (1)
R1
kp
kp
R2
R j1
km
P
j
Chain elongation, new

monomers add to chain
R1
Live polymer chain transfers radical to monomer.

Polymer chain is no longer reactive (dead). Can also
transfer to solvent or other species
4a. Termination by addition: R j Rk
k add
R j k
4b. Termination by disproportionation: R j Rk
k dis
Rj
Rk
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:
Propagation:
C2H6
k2
CH3 C2H
6
C2H5

k3
H C2H
6
Termination:
k1
2C2H5

2CH3
r1,C2H6 k1CC2H6
CH4 C2H5
r2,C2H6 k 2CCH3 CC2H6
C2H4 H
k4
k5
C
2H5 H2
C4H10
r3,C2H4 k 3 CC2H5
r4,C2H6 k 4CHCC2H6
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
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 CH3 C2H6
2,C2H6
CH3 was formed in rxn 1 and consumed in rxn 2:

rCH 2r1,C H r2,C H
3
2 6
2 6
-r3,C
2H4
-k 3 C C
2H5
r4,C2H6 k 4CHCC2H6
H was formed in rxn 3 and consumed in rxn 4:

rH r3,C2H4 r4,C2H6
r5,C2H5 k 5 CC2H5
Plug rate eqs into eq above, assume rate = 0 (PSSH) & solve for reactive species
rC
2H5
k 2CCH CC
3
2H6
k3CC
2H5
k 4CHCC
2H6
k5 CC
2H5
Need to replace CCH3 and CH

rCH
k1CC2H6
k 2CC2H6
0 2k1CC
2H6
k 2CCH CC
CCH CCH
3
3
2k
1
k2
2H6
2k1CC
2H6
k 2CCH CC
Do the same for CH
CH
2H6
k3CC
2H5
k 4CC
2H6
L10-19
Goal: replace CC2H5
The net rates of reaction of active intermediates C2H5, CH3, H are (PSSH):
r1,C2H6 k1CC2H6
rxns 3 & 5:
r
k C
C
2 CH3 C2H6
2,C2H6

rCH 2r1,C H r2,C H
3
2 6
2 6
-r3,C
2H4
-k 3 C C
2H5
r4,C2H6 k 4CHCC2H6

rH r3,C2H4 r4,C2H6
r5,C2H5 k 5 CC2H5
Plug rate eqs into eq above, assume rate=0 (PSSH) & solve for reactive species
rC
2H5
k 2CCH CC
3
2H6
k3CC
2H5
k 4CHCC
2H6
k5 CC
2H5
Plug in expressions for CCH3 and CH into

2k1 C k3CC2H5
H
C2H5 rate eq for C2H5 & solve for C2H5 CCH3 k
k 4CC H
2 6
2
assuming rate = 0 (PSSH)
k3CC H
2
2k1
2 5 C
rC H k 2
CC H k3CC H k 4
k
C
0
C2H6
5
C2H5
2 5
2
6
2
5
k2
k 4CC H
2 6
L10-20
Goal: replace CC2H5
r1,C2H6 k1CC2H6
rxns 3 & 5:
r
k C
C
2 CH3 C2H6
2,C2H6

rCH 2r1,C H r2,C H
3
2 6
2 6
-r3,C
2H4
-k 3 C C
2H5
r4,C2H6 k 4CHCC2H6

rH r3,C2H4 r4,C2H6
r5,C2H5 k 5 CC2H5
Plug rate eqs into eq above, assume rate=0 (PSSH) & solve for reactive species
rC
2H5
k 2CCH CC
3
2H6
k3CC
2H5
k 4CHCC
2H6
k 5 CC
2H5
k3CC H
2k1
2 5 C
k2
CC H k3CC H k 4
C2H6 k 5 CC2H5
2
6
2
5
k2
k 4CC H
2 6
k3CC H
2 5
CH
k 4CC H
2k
0 CCH3 1
k2
2 6
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
2k1CC H
2
2
6
2 6 C
CC H
C2H5
2 5
k5
k5
L10-21
Goal: replace CC2H5
r1,C2H6 k1CC2H6
rxns 3 & 5:
r
k C
C
2,C2H6

rCH 2r1,C H r2,C H
3
2 6
2 6
-r3,C
2H4
k5
2H6
CC
2H5
CCH3
2k
1
k2
CH
k3CC
0.5
rC
2H4
k 3 CC
2H5
rC2H4
2H5
r5,C2H5 k 5 CC2H5
2H5
k 4CC
2k1
= k3
CC2H6
k
5
-k 3 C C
r4,C2H6 k 4CHCC2H6

rH r3,C2H4 r4,C2H6
2k1CC
2 CH3 C2H6
2H6
Plug expressions for

reactive species into eq
for rC2H4 above
The CC2H4 depends on CC2H6.

How does CC2H6 change with
time?
-rC2H6 = k1CC2H6 + k 2CCH3 CC2H6 + k 4 CHCC2H6 Need to eliminate the

reactive species
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
From the previous slide:

CCH3 2k1 k 2
CH
k 3 2k1
k 4 k5
1
2
CCH3
CH
k3CC
rH r3,C2H4 r4,C2H6 0
2H5
k 4CC
2H6
CC2H5
2k1
CC2H6
k5
1
2
1
CC2H6 0.5
2k
1
k2
-rC2H6 = k1CC2H6 + k 2CCH3 CC2H6 + k 4 CHCC2H6
-rC2H6 = k1CC2H6
-rC2H6 = k1CC2H6 + 2k1CC2H6
k 2k1
2k
+ k 2 1 CC2H6 + k 4 3
k2
k 4 k5
2k1
+ k3
CC2H6
k5
0.5
CC2H6
CC2H6 0.5
0.5
-rC2H6 = 3k1CC2H6
2k1
+ k3
CC2H6
k5
0.5
L10-23
2k1
CC2H6
k5
rC2H4 = k 3
1
2
2k1
CC2H6
k5
-rC2H6 = 3k1CC2H6 + k 3
1
2
For a constant-volume batch reactor :

dCC2H4
dt
2k1
= k3
CC2H6
k5
1
2
dCC2H6
dt
= 3k1CC2H6
2k1
+ k3
CC2H6
k5
1
2
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
C2H6
k1
CH3 C2H6
C2H5
k3
L10-24
2CH3
CH
4
k2
C2H4
H C2H6
k4
C2H5
2C2H5
k5
C2H5 H2
C4H10
1. Mole balances: 2. Rate laws for each species:

(Batch)
dC1
= r1
C2H6 dt
dC2
CH3 dt = r2
r1 = -k1C1 - k 2C1C2 - k 4C1C6

r2 = 2k1C1 - k 2C2C1
dC3
CH4 dt = r3
dC4
= r4
C2H5
dt
dC5
C2H4 dt = r5
dC6
= r6
H
dt
dC7
= r7
H2
dt
r3 k 2C1C2
C4H10 dC8 = r8
1
r8 = k 5C42
2
dt
All these O.D.Es can be

solved simultaneously
r4 = k 2C1C2 - k 3 C4 + k 4C1C6 - k 5C4 2

r5 = k 3 C4
r6 = k 3C4 - k 4 C1C6
r7 = k 4C1C6
The comparisons of the results

obtained from the two methods are
shown on page 391 of textbook.
The two results are identical,
indicating the validity of the PSSH
under these conditions
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:
rO3
kCO3 2CM
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.
Postulating Mechanism for O3 Decomposition

(Step 1)
L10-26
reactive intermediate
step is probably:
B A *
Collision products
2. If the denominator contains a constant term, then one rxn step is probably:
A *
3. If the numerator contains a species concentration, then one rxn step is
probably:
A * other products?
Apply: rO
3
kCO3 2CM
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)
Postulating Mechanism for O3 Decomposition

(Step 1 continued)
L10-27
step is probably:
B A *
Collision products
Apply: r
O3
kCO3 2CM
CO2 CM k 'CO3

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
Which one?
M must participate in one of the other reactions
CM is multiplied by CO2 in the denominator, so combine PR3 with PR1
M O2 O O3 M (PR1b)
L10-28
Postulating Mechanism for O3 Decomposition (Steps 2

& 3)
step is probably:
B A *
Collision products
2. If the denominator contains a constant term, then one rxn step is probably:
A *
3. If the numerator contains a species concentration, then one rxn step is
probably:
A * other products?
Apply: rO
3
kCO3 2CM
CO2 CM k 'CO3

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

Ozone Decomposition
Apply: r
O3
kCO3 2CM
CO2 CM k 'CO3
CM and CO2 in denominator:

CO3 in denominator:
CO3 and CM in numerator:
L10-29

M O2 O O3 M
O3 O 2O2
Reactive
O3 M M O2 O intermediate
k
M O2 O
Postulated mechanism: O3 M 1
Does this add up to
k 1
the overall reaction?
+ O O
k2
2O
3
2
2O3 3O2
yes!
Now derive a rate equation for the postulated mechanism and check if
it describes the experimentally observed rate equation
L10-30

kCO3 2CM
Nonelementary kinetics, result of

rO3
multiple elementary rxns & active
CO2 CM k 'CO3
intermediates
k
M O2 O Reactive
Postulated mechanism: O3 M 1
intermediate
k 1
O3 O

k2
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
L10-31
Pseudo-Steady State Hypothesis

k
must replace CO in the
rate equation
1
Postulated mechanism: 1.) O3 M M O2 O
2.) O3 O
k 1
k2
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

L10-32
Concentration of Reactive O
Postulated mechanism: 1.) O3 M k1 M O2 O
2.) O3 O
rO3
kCO3 2CM
CO2 CM k 'CO3
k 1
k2
2O2
rate equation
Observed rate equation

(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

CO
rO3
k1CO3 CM
k 1CMCO2 k 2CO3 Plug CO into rO3

k1CO3 CM
k1CO3 CM k 2CO3 k 1CMCO2
k 1CMCO2 k 2CO3
Now we will rearrange and simplify to see if it matches the experimental data
L10-33
Rearranging the Postulated Rate Eq.

2.) O3 O
k 1
k2
rate equation
2O2
k1CO3 CM
k 1CMCO
Plug in CO rO3 k1CO3 CM k 2CO3 k 1CMCO2

Multiply out
rO3
brackets
rO3
rO3
rO3
k 2CO3
k1k 2CO3 2CM k 1k1CM2CO2 CO3 Get common

k1CO3 CM
denominator
k 1CMCO k 2CO
2
k1CO3 CM k 1CMCO2 k 2CO3

k 1CMCO2 k 2CO3
k1k 2CO 2CM k 1k1CM2CO CO

3
k 1CMCO2 k 2CO3
k1k 1CM2CO2 CO3 k1k 2CO3 2CM k1k 2CO3 2CM k 1k1CM2CO2 CO3
k 1CMCO2 k 2CO3
2k1k 2CO3 2CM
k 1CMCO2 k 2CO3
Conventional to
2k1k 2 k 1 CO3 2CM
remove constant rO3
CMCO2 k 2 k 1 CO3
from 1st term
Comparison Between Postulated

and Experimental Rate Equation
2.) O3 O
k 1
k2
2O2
L10-34
cannot appear in the
rate equation
Compare rate eq for postulated mechanism to the experimental rate eq

rO3
2k1k 2
k 1 CO3 2CM
CMCO2 k 2 k 1 CO3
Rate equation for

postulated mechanism
2k1k 2
k
k 1
rO3
kCO3 2CM
CO2 CM k 'CO3
Experimentally observed
rate equation
k2
k'
k 1
These are the same postulated rate law explains the experimental data

L10 Nonelementary Rxns

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L10 Nonelementary Rxns

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L10-1

Review: Multiple Rxns & Selectivity

instantaneous rate selectivity, SD/U

(at any point or time in reactor)

NU Final moles of undesired product

Maximize selectivity / yield to maximize production of desired product

Review: Maximizing SD/U for

What reactor conditions and

Specific rate of desired reaction kD increases:

High CA favors undesired

PFR/PBR w/ side streams feeding

Review: Reactions in Series: Cj & Yield

Time is the key factor here!!!

Spacetime for a flow reactor

L10: Nonelementary Reaction Kinetics

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

Nonelementary reaction kinetics: no direct correspondence between

Review (L4): Reversible

rA,net rA rfA rbA

Thermodynamic equilibrium relationship

Determining Mechanism to Describe

Instead experiments show that the kinetics are:

Postulating a Reaction Mechanism

Collision products A* is a reactive intermediate

Experimentally observed rate equation for

NO collides with reactive intermediate, NO3

Constant in denominator: NO3 produces NO and O2 (reverse of previous?)

A Reaction Mechanism for

Experimentally observed rate equation for

CNO & CO2 in numerator:

Does this add up to

Postulated Mechanism for

Nonelementary kinetics, result of

Write rNO for the postulated reaction mechanism

rNO rxns that form NO - rxns that consume NO

Pseudo-Steady State Hypothesis

rNO k1CNOCO2 k 1CNO3 k 2CNO3 CNO Factor out to simplify

Concentration of Reactive Intermediate

Observed rate equation

rNO k1CNOCO2 k 2CNO k 1 CNO3

Solve for CNO3 in

rNO k1CNOCO2 k 2CNO k 1

Plug CNO3 into -rNO

Rearranging the Postulated Rate Eq.

Plug in CNO3 rNO k1CNO CO2 k 2CNO k 1

Comparison Between Postulated

Compare rate eq for postulated mechanism to the experimental rate eq

Clicker Q: Are these rate equations the same?

Free Radical Polymerizations (4 steps)

Initiator (I) decomposes to 2 free radicals

Chain elongation, new

Live polymer chain transfers radical to monomer.

4a. Termination by addition: R j Rk

4b. Termination by disproportionation: R j Rk

PSSH Applied to Thermal Cracking

r2,C2H6 k 2CCH3 CC2H6

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:

CH3 was formed in rxn 1 and consumed in rxn 2:

H was formed in rxn 3 and consumed in rxn 4: