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CHAIN REACTIONS
CHAPTER 5
FACULTY OF CHEMICAL ENGINEERING CPE624 1
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Chain Reactions
Example




Initiation step
Propagation
Termination
Propagation steps occur faster than
initiation and termination steps


FACULTY OF CHEMICAL ENGINEERING CPE624 2
CH
CO CH CHO CH +
4 3
2
3 6 2 3
3 2 2 3 3
3 1 1 3 4 3
3
] [ 2
] [
] ][ [
] [ ,
- = -
- = - + -
- = - + - +
= - + -
CH k r H C CH
CO CH k r CH CO CO CH
CH A k r CO CH CH CH A
A k r CHO CH A
t t
p p
p p
i i
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Pseudo steady state approximation
PSS setting time derivative equal to zero
Mass balance equations are developed by
assuming steady state, so that PSS of intermediate
species is in steady state and concentration is small.
CPE624 FACULTY OF CHEMICAL ENGINEERING 3
Example: Explain the physical meaning of pseudo-steady-
state approximation, when applied to a CSTR and a PFR.

Explanation:
-PSS valid if the concentration of a species is small.
- In PFR or batch system, the time derivative is set equal to zero,
d[CH3CO
.
]/dt = 0, not the concentration equal to zero.
Physical meaning: The concentration of free radical is constant.
-For CSTR, PSS approximation is indeed that the concentration be small or
[CH3CO
.
]/ = 0
Physical meaning: The concentration of free radical is small.



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FACULTY OF CHEMICAL ENGINEERING CPE624 4
CH
Example: The mechanism of the autocatalytic above mentioned
reaction is given above. Using pseudo-steady-state approximation
(PSS) derive an equation to determine the concentration of free
radical.
CH3CHO CH4 + CO
Mechanism given

CH3CHO CH3 + CHO (initiation, i)
CH3CHO + CH3 CH4 + CH3CO (propagation, p
1
)
CH3CO CO + CH3 (propagation, p
2
)
2CH3 C2H6 (termination, t)

Find concentration of CH3 ; either PFR or CSTR

Mass Balance:
{[CH3CHO]-[CH3CHO]
o
} /t = -k
i
[CH3CHO] kp
1
[CH3CHO][CH3]
{[CH3 ]-[CH3 ]
o
/t = -k
i
[CH3CHO] kp
1
[CH3CHO][CH3 ] + k
p2
[CH3CO ]
- 2k
t
[CH3 ]
2
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FACULTY OF CHEMICAL ENGINEERING CPE624 5
CH
{[CH3 CO ]-[CH3 CO ]
o
/t = kp
1
[CH3CHO][CH3 ] - k
p2
[CH3CO ]

{[CO]-[CO ]
o
/t = k
p2
[CH3CO ]

{[CH4]-[CH4 ]
o
/t = kp
1
[CH3CHO][CH3 ]

[CH3 ] and [CH3CO ] are very reactive, thus the concentrations are very low.

{[CH3 CO ]-[CH3 CO ]
o
/t = kp
1
[CH3CHO][CH3 ] - k
p2
[CH3CO ] = 0

kp
1
[CH3CHO][CH3 ] = k
p2
[CH3CO ]

[CH3CO ] = kp
1
/k
p2
[CH3CHO][CH3 ] (1)

{[CH3 ]-[CH3 ]
o
/t = -k
i
[CH3CHO] kp
1
[CH3CHO][CH3 ] + k
p2
[CH3CO ]
- 2k
t
[CH3 ]
2
= 0 ..(2)
Insert (1) into (2)
Ki[CH3CHO] - kp
1
[CH3CHO][CH3 ] + k
P2
x kp
1
/k
p2
[CH3CHO][CH3 ] - 2k
t
[CH3 ]
2
=
0

K
i
[CH
3
CHO] - 2k
t
[CH3 ]
2
= 0

[CH
3
]
2
= k
i
/2k
t
[CH
3
CHO]
[CH3 ]

= (k
i
/2k
t
)
1/2
[CH
3
CHO]
1/2




















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Autocatalytic reactions
The major processes are the propagation steps
Adding p1 and p2 steps yield:


Autocatalytic the reaction generates the catalyst
that promotes the reaction.
Major products generate by propagation step
Minor products made by initiation and termination
steps.
Kinetic chain length ratio of r
p
to r
t
.
CPE624 FACULTY OF CHEMICAL ENGINEERING 6
- + + - +
3 4 3
CH CO CH CH A
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Generic chain reaction
The reaction propagates by radical R.



n
i
and n
t
are the number of molecules react in
initiation and termination steps respectively.
PSS approximation on C
R
yield the overall rate
expression
CPE624 FACULTY OF CHEMICAL ENGINEERING 7
C B A +
X R n
R C B R A
R A n
t
i
-
- + + - +
-
,
,
| |
| || |
| |
t
i
n
R t t
R A p p
n
A i i
C k r
C C k r
C k r
=
=
=
| |
t
i
t
n
n
A p
n
t t
i
C k
k n
k
r
+
|
|
.
|

\
|
=
1
1
| |
eff
n
A eff
C k r =
A
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Characteristic of chain reactions
Large temperature dependences.
Sensitive to trace impurities that can alter the
initiation and termination rates
Initiators and Scavengers (promoters and poisons)
have large influences.
Initiators
Initiated by adding species I that easily forms radical
Initiate the reaction faster than reactant.
Scavengers
Termination step - radical species decomposed /reacted
with other radical species to form an inactive species X
Adding scavengers S
X is important in determining overall reaction rate


CPE624 FACULTY OF CHEMICAL ENGINEERING 8
S R ts ts
C C k r X S R = + ,
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Wall termination reactions
Surface reaction steps important in controlling
chain reactions.
Wall termination reactions introduce a complexity
to all chain reactions the overall reaction rate as
a function of the size of reactor.
In a small reactor, termination reactions on surface
keep the radical intermediate small and inhibit
chain reaction.
In large reactor, the termination rate is smaller.



CPE624 FACULTY OF CHEMICAL ENGINEERING 9
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Example: Briefly explain the terms initiator and
scavenger for a chain reaction


Initiator: Species (I) that can easily form radicals in a
chain reaction and can initiate the reaction faster
than the reactant.

Scavenger: Species (S) added into a chain reaction
that can readily scavenge the chain propagator to
terminate the reaction.
CPE624 FACULTY OF CHEMICAL ENGINEERING 10
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Autooxidation
Autooxidation autocatalytic process and
it is an oxidation that converts alkanes into
alkyl peroxides.
CPE624 FACULTY OF CHEMICAL ENGINEERING 11
ROOH O H R +
2
- + + -
- + -
- + -
R ROOH H R O
ROO O R
H R H R
RO

,
2
A research student forgot to close a bottle of an organic compound tightly and kept on a table. The student left for vacation and when he came back after one month, he saw the table and everything on the table destroyed. Illustrate the reaction steps and mechanism that occurred in the bottle.
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Autooxidation
CPE624 FACULTY OF CHEMICAL ENGINEERING 12
A research student forgot to close a bottle of an organic
compound tightly and kept on a table. The student left for
vacation and when he came back after one month, he saw the
table and everything on the table destroyed. Illustrate the
reaction steps and mechanism that occurred in the bottle.
Example
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Example
Consider the chain reaction in a CSTR:



a) Write the mass balance equations for A, B, R and X in a
CSTR assuming constant density.
b) What is the overall reaction rate with respect to C
A
?
c) Find for 98% conversion of A in CSTR assuming
pseudo steady state if C
A0
= 2 moles/liter, k
i
= 0.002 sec
-1
,
k
p
= 10 liter/mole sec and k
t
= 0.05 sec
-1
.
d) What are C
R
and C
x
for this conversion?



CPE624 FACULTY OF CHEMICAL ENGINEERING 13
X R
R C B R A
R A

+ + +

| |
| || |
| |
R t t
R A p p
A i i
C k r
C C k r
C k r
=
=
=
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CPE624 FACULTY OF CHEMICAL ENGINEERING 14
(a) Initiation: A R ; r
i
= k
i
C
A

Propagation: A + R B + C + R; r
i
= k
p
C
A
C
R

Termination: R X; r
t
= k
t
C
R


(b) Overall reaction rate:
C
R
/t = k
i
C
A
k
t
C
R
= 0
C
R
= k
i
/k
t
x C
A

r = k
p
C
A
C
R

= k
i
k
p
/k
t
C
A
2


(c) Solving CSTR equation:
t r = C
Ao
C
A

t = (C
Ao
C
A
)/r = (C
Ao
C
A
)/C
A
2
x k
t
/k
i
k
p


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CPE624 FACULTY OF CHEMICAL ENGINEERING 15

= [2 moles/L - 2(1-0.98)]/(0.04)
2
x 0.05/ s/0.002/s x 10 l/s


= 1225 x 2.5 = 3062.5 s
=
51 min





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Chain branching reaction
Produce more than one free radical species in
propagation step. Thus, the propagation steps
increase the concentration of radical species and
destabilize the kinetics.
Example:

Rapid rise in the concentration of radical species can
accelerate the reaction and possibly a chain-
branching explosion.

CPE624 FACULTY OF CHEMICAL ENGINEERING 16
- + - + - OH O R ROOH
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Model of chain branching reaction
Consider the reaction of :

The mechanisms are:

CPE624 FACULTY OF CHEMICAL ENGINEERING 17
C B A +
X R
R C B R A
R A

+ + +

,
,
o
R t t
R A p p
A i i
C k r
C C k r
C k r
=
=
=
A p t
A i
R
C k k
C k
C
) 1 (
=
o
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References
Schmidt, L.D. (2005). The Engineering of Chemical
Reactions, 2
nd
edition, New York: Oxford University
Press.
Fogler, H.S. (2006). Elements of Chemical Reaction
Engineering, 4
th
Edition, New Jersey: Prentice Hall.
Levenspiel, O. (1999). Chemical Reaction
Engineering, 3
rd
Edition, New York: John Wiley.

CPE624 FACULTY OF CHEMICAL ENGINEERING 18

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