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ENGINEERING III
PROF. J A Omoleye, Dr, Mrs O Agboola
TEXTS:
-The Chemical Reactor - Omnibook Levenspiel,
-Advanced Engineering Chemistry Dr M R
Senapati
-Chemical Reaction Engineering Octave
Levenspiel
-Introduction to Chemical Reaction Engineering
Ronald W Missen, Charles A Mims, Radley A Saville
TESTS & EXAMS
Assignments & 2 Tests (CA) - 30%
Final examination - 70%
Do honest work and avoid cheating
Copying other students work unacceptable
even for assignments (However, feel free to do
collaboratory study)
75% minimum class attendance mandatory, as
condition to sit final examination.
Ensure you are registered to avoid challenge
with your result
LECTURE ROOM ATMOSPHERE
Ensure you are sitted in the Lecture room
before the arrival of lecturer (you may be
locked outside for late coming)
Within the period of lecture, total silence is to
be observed except when you have a
question, which should be directed to the
lecturer. (rowdiness must be avoided)
Please ensure you sign the attendance register
before you leave the lecture room
HETEROGENEOUS REACTION KINETICS
(porous particle) 7/9/16
(diagram p6)
Reaction of carbonaceous materials such as coal
briquette, wood etc (with low ash content) to
produce heat or heating fuel) eg.
C(s) + O2(g) = CO2(g)
2C(s) + O2(g) = 2CO(g)
C(s) + CO2(g) = 2CO(g)
With steam, water gas is obtained by the
reactions:
C(s) + H2O(g) = CO(g)+ H2(g)
C(s) + 2H2O(g) = CO2(g) + 2H2(g)
.
The manufacture of carbon disulfide from the
elements
C(s) +2S(s) = CS2(g)
The manufacture of Sodium Cyanide from
Sodium Amide
NaNH2(l) + C(s) = NaCN(l) + H2O(g)
The manufacture of Sodium thiosulfate from
Sulphur and Sodium sulphite
NaSO3(soln) + S(s) + Na2S2O3(soln)
Attack of metal chips by acids , the rusting of
iron etc
RATE EXPRESSIONS FOR FLUID-SOLID
REACTIONS
USEFULNESS:
Need to know how long some heterogeneous
reactions will last for a given conversion to be
achieved.
Only known through the use of some predictive
kinetic equations.
Certain constants in these equations must be
known.
This aspect of the course will teach you now to
determine them.
SELECTION OF A MODEL
Model of reaction means conceptual picture
of reaction
Every model for the progress of the reaction
comes with its mathematical representation
or Rate Equation.
If the model chosen corresponds closely to
what really takes place then the rate
expression will closely predict and describe
the actual kinetics
.
For non-catalytic heterogeneous reactions, the
two simple idealized models are :
The progressive conversion Model
The unreacted-core Model
.
UNREACTED CORE MODEL
The reaction is visualized first as occurring at
the outer skin of the particle. The zone of the
reaction then moves into the solid and may
leave behind the completely converted
material and inert solid (called ash). Thus
at any time, there exists an unreacted-core of
material which shrinks in size during reaction
as shown below:
(Diagram p10)
The unreacted core model is best suitable for
a wide variety of situations and more realistic
Unreacted core model of spherical
particles of unchanging size
The above model was developed by Yagi and
Kunii in 1995.
STEPS
(1) diffusion of gaseous A thro the film
surrounding the particles to the surface of the
solid
(2) penetration and diffusion of A thro the
blanket of ash to the surface of the unreacted
core
8/10/14
(3) reaction of gaseous. A with the solid at the
reaction surface
(4) Diffusion of the gaseous product thro the
ash back to the exterior surface of the solid
(5) Diffusion of the gaseous product thro the
gas film back unto the main body of the fluid
Some of the steps may not be present in some
reactions: for example, if there is no gaseous
product steps 4 and 5 do not contribute
directly to the resistance of the reaction.
.
Resistance of different steps vary in effect
such that some are major and can be
considered as the rate controlling step.
Diagram (p11)
.
DEVELOPMENT OF CONVERSION
EQUATION 19/26 10 - 2011
CONDITIONS:
(a) elementary irreversible reactions with
steps 4 & 5 absent
( b) spherical particles
(c) steps 1, 2 & 3 in turns are rate controlling
(A) diffusion thro gas film controls
(Diagram 12)
.
The concentration profile is as shown above
Rate of reaction of A depends on the rate of
transport of A thro the gas film
Beyond the gas film, reaction is instant, no
accumulation of reactant A can be seen, Cas=0
The conc. Driving force Cag- Cas is constant at all
times during reaction
The kinetic equation should be related to the
available surface the unchanging exterior
surface of the particle, Sex
.
A(g) + bB(s) = S(s)
dNB = bdNA From the stoichiometry:
Hence, - r = rB = b x rA
- r = -(1/Sex)dNB/dt = -b(1/Sex)dNA/dt (i)
Also, -r= -brA = -bKg(CAg CAs) [rate of
diffusion thro the gas film]
-r = bKgCAg CAs = 0 --------------------(ii)
Hence, - r = -(1/Sex)dNB/dt = bKgCAg ------------(1)
Where ext. surface area Sex =4R2
Where kg in cm/s or m/s is the mass transfer
coefficient
.. density of B x vol of solid
But, NB (moles of B) = molar
B
NB = B x V
-dNB = -bdNA = - BdV
= -Bd(4rc3/3)
-dNB = -bdNA = -4Brc2drC ----------(2)
-dNB = -4Brc2drc -----------------(2a)
-dNB/dt = -4Brc2drc/dt -------(2b)
Subst for dNB/dt in (1),
- rA = -(1/Sex)dNB/dt = -(4B/4R2)rc2drc/ dt =
bKgCAg
-(4B/4R2)rc2drc = bKgCAgdt -------------- (3a)
Integrating, we obtain:
t = BR/3bkgCAg[1-(rc/R). 3] -------------------------(3b)
t = f(rc)
in order to predict the time t = for end of
reaction, substitute radius of solid rc = 0 in eqn 3
= BR/3bkgCAg ------------------------------------- (4)
fraction of time left for reaction to complete is:
t/ = 1 (rc /R)3 ----------------------------(5)
CONVERSION
Conversion of B is given by:
xB = volume reacted/total vol of particles
= (total Vol Vol Unreacted)/total Vol
.
XB = 1 - (4rc3/3)/(4R3/3)
XB = 1 - (r/R)3 = t/ ----------------- (6)
Try the derivation for cylindrical and cuboid
particle shapes.
END
Insert on last page Row *
But NB (flux) = rcB hence,
-drc/dt = -bCA/B [rc2 / R2 kg + (R-rc)rc/RDe + 1/ ks ]
(film) (ash) (rxn)
REVIEW 2013
ASIGNMENT: Jumping the derivation step
Use of Maths Integral Table essential for good
understanding
EXAMINATION:
- Part A: 10 Questions 50marks
- Part B: 1 Question 20Marks
- come up with one typed sheet of Equations
(No write-up / explanation)
- Come with all you need, No sharing permitted.
- Areas of Emphasis: Plates 21 to 63 (ie Sample
calculation to Rate of Reaction for Shrinking core
diagram