Advanced Catalytic

Reactors
CHEN 411

Non elementary Homogeneous Reactions

r = k CAn
For Elementary Rx.:
n =1 1st order Rx
n =2 2nd order Rx
A large no. of homog. Rxs. involve the formation & Rx
of intermediate species Rx order is not an integer
non-elementary Rx.

Example :

CH 3 CHO CH 4 + CO
r = k [ CH 3 CHO ]

32

Example 2:

H 2 + I 2 2 HI
k 1 k 3 [ I 2 ][ H 2 ]
r=
k2 + k3 [ H 2 ]

Rxs. of the previous examples are:

non-elementary
in that there is no direct
correspondence between:
Reaction (Rx) order & stoichiometry
Such Rxs. come about as a result of
the overall Rx taking place by:
a mechanism consisting of a series of
Rx steps

1.1How rate laws are derived from

mechanism?
Example 1:

( CH 3 ) 2 N 2 C 2 H 6 + N 2
AZO
ethane + nitrogen
experimental data
at [ AZO ] rN 2 [ AZO ]
at [ AZO ] rN 2 [ AZO ]

Mechanism of the Rx.:

AZO + AZO
AZO * + AZO
AZO *

k3

k1

AZO + AZO *

k2

AZO + AZO

C2 H6 + N 2

RN 2 = N 2 r = k3 [ AZO ]
R

AZO*

= k1 [ AZO ] 2 - k 2 [ AZO*][ AZO ] - k 3 [ AZO*] = 0

PSSH: (Psuedo Steady State Hypothesis)

the rate of formation of the active
intermediate is assumed to be equal
to its rate of disappearance.
i.e.net rate of formation of AZO* =0
RAZO* =0
AZO + AZO
AZO * + AZO
AZO *

AZO

k3

k1

AZO + AZO *

k2

AZO + AZO

C2 H6 + N 2

= k1 [ AZO ] - k 2 [ AZO*][ AZO ] - k 3 [ AZO*] = 0

{
}
=
k
[
AZO
]
[
AZO
*]
k
[
AZO
]
+
k
=
0
1
2
3
AZO*
2

k1 [ AZO ]
[ AZO*] =
k 2 [ AZO ] + k 3

But,

RN 2 = N 2 r = k 3 [ AZO ]
2

k1 [ AZO ]
RN 2 = k3
k 2 [ AZO ] + k 3

Which agrees with exp. data

at [ AZO ] rN 2 [ AZO ]
at [ AZO ] rN 2 [ AZO ] 2

Example 2 :
The pyrolysis is believed to take place according to the following mechani sm:
CH 3CHO

k1

CH *3 + CHO *

CH 3 * +CH 3CHO
*

CHO + CH 3CHO
2CH *3

k4

k2

CH 3 * +CO + CH 4

k3

CH *3 + 2CO + H 2

C2 H6

Derive the rate expression for the rate of

disappearance of acetaldehyde.

Example 3 :Thermal cracking of ethane

C2H6 2CH3*

, k1

CH3* + C2H6 CH4 + C2H5* , k2

C2H5*

C2H4 + H*

, k3

H* + C2H6 C2H5* +H2

2C2H5* C4H10 , k5

, k4

Example 4: Flame Retardants

Hydrogen radicals are important to sustaining
combustion Rxs. Consequently, if chemical
compounds that can scavenge the H radicals are
introduced, the flames can be extinguished. The
following is the mechanism in absence of inhibitors:
O2 O* +O*
k1
H2O + O* 2OH*
k2
CO + OH* CO2 + H* k3
H* + O2 OH* + O*
k4
Assume PSSH holds for O*& OH* radicals.
Derive a rate law for the consumption of CO.
Derive an eq. for [H*] as a fn. of time.
Sketch [H*] vs time

1.2 How mechanisms are derived

from a rate law?k k [ AZO ] 2

RN 2 =

1 3

k 3 + k 2 [ AZO ]

Back to Example 1 for AZO decomposition:

1. Species having the conc in denominator of rate
probably collide with the active intermediate.
AZO + AZO* AZO + AZO
2. If a cst. appears in the denominator spontaneous
decomposition of active intermediate.
AZO* C2H6 + N2
3. Species having the conc in numerator of rate probably
produce the active intermediate.
AZO + AZO AZO + AZO*

k1k 3 [ AZO ]
RN 2 =
k 3 + k 2 [ AZO ]
AZO + AZO
AZO * + AZO
AZO *

k3

k1

AZO + AZO *

k2

AZO + AZO

C2 H6 + N 2

Example 5: Hydrogen Bromide Rx.

Experimental rate data showed that the Rx :
32
1. 1st order wrt [H2]
k1 [ H 2 ][ Br2 ]
RHBr =
2. rHBr f( HBr) at [HBr] &
[ HBr ] + k 2 [ Br2 ]
rHBr as [HBr] at [HBr]
3. 3/2 order in Br2 at [Br2]
1/2 order in Br2 at [Br2]
What is the rate expression that is consistent
with the experimental observations?
Propose a mechanism that is consistent with
the rate expression synthesized from exp.
data

Experience tells us that a fractional order of Br 2 in the

numerator suggests that the primary reactive
intermediate is Br* formed from Br2 and terminated
by the reaction of 2 Br*.
Br2 2Br* ,
k1
Initiation
Br* + H2 HBr + H*,

k2

H* + Br2 HBr + Br* , k3

H* + HBr H2 + Br*,
2Br* Br2 ,

Propagation

k4
k5

Termination

Notes:
H2 2H* has high energy of dissociation
neglected

Example 6: 2GCH3 2GCH2 + H2

A B + H2
1. R f[H2]
2. As [GCH2]

k1 [ A ] 2
r=
k2 [ A ] + k3 [ B ]

3. Initial rate is 1st order wrt GCH3.

4. At [GCH2] & [GCH3] R is 2nd order wrt
GCH3.
What is the rate expression that is consistent
with the experimental observations?
k1
*
Suggest a mechanism
.
A
B+ H

B+H

k2

A+ H

k3

B + H2

Example 6: (contd.) 2GCH3 2GCH2 + H2

A B + H2

Check of the suggested mechanism:

k1

B + H*

k1 [ A ]
r=
k2 [ A ] + k3 [ B ]

B+H

k2

A+ H

k3

B + H2

rA = -k1[A] + k2 [B].[H*] k3[A].[H*]

----1
rH* = k1[A] - k2 [B].[H*] - k3[A].[H*] =0

k1 [ A ]
[H ] =
k 2 [ B ] + k3 [ A ]

----2

1+2=
rA + rH* = -2 k3[A].[H*]

k1 [ A ]
rA = -2k 3 [ A ].
k 2 [ B ] + k3 [ A ]

Example 7: Motor oil degradation

One of the major reasons for engine oil degradation

is the oxidation of the motor oil (RH). To retard such
process, most oils contain an antioxidant. Without
an inhibitor to oxidation the suggested mechanism:
I2 2I*
I* + RH R* + HI
R* + O2 RO2*
RO2* + RH ROOH + R*
2RO2* inactive

Derive an expression of rate of degradation

of oil
-------------------------------------------------RO2* + AH ROOH + A*
A* + RO2* inactive