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Reaction Mechanism
in Chain
Reaction
and
Biological
Part 1
Reaction
Chain Reaction Mechanism
A CH 3 CH 4 CO CH 3
FACULTY OF CHEMICAL
CPE624/CHE625 5
ENGINEERING
Mass balance of species in
PFTR/Batch and CSTR
So, from the mechanism, you can write the mass
balance on each species and solve them in batch
reactor or continuous reactors (PFTR or CSTR) and
find the species concentrations as a function of
residence time.
General mass balance:
PFTR:
Batch reactor :
CSTR:
Class activity 1
A CH 3 CHO, ri k i [ A]
A CH 3 CH 4 CH 3CO r p1 k p1[ A][CH 3 ]
CH 3CO CO CH 3 rp 2 k p 2 [CH 3CO]
2CH 3 C2H 6 rt k t [CH 3 ]2
Write the mass balance equation on each
species for the mechanism above in a)
PFTR and b) CSTR
Solution:
In a PFTR In a CSTR
Pseudo steady state approximation
(PSSA)
PSSA is used when one tries to approximate a set of reactions by a simpler
single reaction by invoking the pseudo steady state on suitable intermediate
species.
PSSA is done by setting the time derivative of the species with the small
concentration (usually the radical species) to 0:
PFTR/Batch
CSTR
FACULTY OF CHEMICAL
8
CPE624/CHE625 ENGINEERING
Subtopic covered in Chapter 3 (Part 1)
Intro to Chain Reaction Mechanism
(Chapter 10 Schmidt, page 399-406)
Autocatalytic reactions
Pseudo steady state approximation/hypothesis
Generic (linear) chain reaction
Characteristics of Chain Reactions
(Chapter 10 Schmidt, page 406-408)
Initiators
Scavengers
Wall termination reactions
Chain Branching Reactions (Chapter 10 Schmidt, page 416-418)
Reactor Safety (Chapter 10 Schmidt, page 434-436)
Thermal & Chemical Autocatalysis
(Chapter 10 Schmidt, page 422-432)
Generic chain reaction
A B C
The reaction propagates by radical R.
ni A R , ri k i C A
ni
A R B C R , r p k p C A CR
nt R X rt k t CR
nt
Q2:
If surface area is very large, the surface reaction rate is also very large.
rate of termination at reactor wall will most frequently limited by
mass transfer rate.
Recall that at steady state,
rt = ktCRs = km (CRb
CRs)
Maximum
concentrati
on of the
reactive
intermediat
e is
achieved
when dCR/d
= 0 (for PFR
system) or
CR/ = 0 (for
CSTR
system)
Reactive
intermediate, i.e.:
free-radicals, R Source: Davis, McGraw-Hill
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: Hydrogen oxidation (a simple prototype of combustion reaction):
mechanism:
Chain
branching
reaction
Rapid rise in the concentration of radical species can accelerate the reaction
and possibly a chain-branching explosion.
Chain branching reaction
(cont.)
FACULTY OF CHEMICAL
CPE624/CHE625
ENGINEERING
Autooxidation
FACULTY OF CHEMICAL
CPE624/CHE625
ENGINEERING
Reactor Safety
Chemical industry is the safer industry
compare to the risk if you drive on the
road. Nevertheless, loss can be
catastrophic if happens.
Some example of disaster
-Texas City disaster I and II
Read
-Flixborough & Philips polyethylene page
434
Schmi
plane explosion dt
-Bhopal incident
FACULTY OF CHEMICAL
CPE624/CHE625
ENGINEERING
Flixboroug Bhopal
h Incident, Disaster,
June 1974 Dec 1984
OCCUPATIONAL
SAFETY & HEALTH ACT
1994
References
Schmidt, L.D. (2005). The Engineering of Chemical Reactions,
2nd edition, New York: Oxford University Press.
Fogler, H.S. (2006). Elements of Chemical Reaction
Engineering, 4th Edition, New Jersey: Prentice Hall.
Levenspiel, O. (1999). Chemical Reaction Engineering, 3rd
Edition, New York: John Wiley.
Pn. Hasyimi Rahmat, FKK UiTM Shah Alam.
Pn. Sharmeela Matali, FKK UiTM Shah Alam.
FACULTY OF CHEMICAL
CPE624/CHE625
ENGINEERING