CHE 516

ADVANCE REACTION ENGINEERING

PROF. J A OMOLEYE

TEXTS: THE CHEMICAL REACTOR

OMNIBOOK - Levenspiel,
ADVANCED ENGINEERING
CHEMISTRY Dr M R Senapati
 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)
70% minimum class attendance mandatory, as
condition to sit final examination.
 LECTURE ROOM ATMOSPHERE
Ensure you are sited 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 CATALYSIS
SOLID CATALYSED REACTIONS, INTRODUCTION
- homogeneous: 1 changing phase (gas or liquid)
- complex bcos of effects of heat & mass transfer
- Example of 1 phase:
- packed bed reactor (porous catalyst)
- fluidized bed (powdered catalyst)
- monolith reactor(cylinders of coated wall)
- catalyst tube (1cylind. wall coated and porous)
 Examples of changing phase.

(2) CATALYST TUBE

(4.)
(3.) REACTOR.

Walls coated
with catalyst;
may be porous
Thick wall
 Examples of two or more changing phases.

(1.)
 .
Examples with 2 or more changing phases
- pellet with progressive poisoning by feed
impurity (gas)
- deactivation occurring during reaction (gas)
- trickle bed reactor(gas, liq. Cat coated
packing)
- slurry reactor(gas, liquid wth suspended
catalyst)
 Definition of reaction Rates (28/9)
With respect to vol of void., cat. Weight, cat surface
area, cat. Vol and total reactor vol
Vol of void in the reactor:
-rA = -(dNA/dt)/V = kCA, (molsreacted/m3void.s)
Weight of cat. Pellets:
-rA = -(dNA/dt)/W = kCA, (mols reacted/kgcat.s)
Catalyst surface area:
-rA = -(dNA/dt)/S = kCA, (molsreacted/m2cat surf.s)

. Vol. of catalyst pellet:

-rA = -(dNA/dt)/Vp = kCA, (molsreacted/m3soiid.s)
 .
conversion from one basis to another (Mol/s)
Making -(dNA/dt) the subject of above Eqns:
rV = rW = rS = rVp = rVr
writing each r, r etc in terms of kCA:
kV = kW = kS = kVp = kVr
Dimensions of various rate constants (1st ord)
(Making k subject of rate equation)
k(s-1), k(m3gas/kg.s), k(m3gas/m2surf)
K(m3gas/m3solid.s), k(m3gas/m3reactor.s)
REACTORS PERFORMANCE EQUATNS
Derived from :
Input = output + accumulation + Disap.Reactn
(A) Batch Reactor:
For homogeneous rxn: t/CAo =(dXA/- rA)
For heterogeneous rxn, replace r with r etc, in
rV = rW = rS = rVp = rVr to
t/CAo = dXA/-rA =V/W dXA/-rA = V/S dXA/-rA
= V/Vp dXA/-rA = V/Vr dXA/-rA

(B) Differential Reactor: (dV/FAo = dXA/-rA)

FAodXA = -rAdV = -rAdW = rAdS = rAdVp = rAdVr
 .
(C) Plug Flow Reactor
Vr/FAo = dXA/-rA (homogeneous system)

W/FAo = dXA/-rA (Packed Bed)

S/FAo = dXA/-rA (Monolith Reactor)

Vp/FAo = dXA/-rA (Porous Pellet/Fluidized Bed)

(D) Mixed Flow Reactor (V/FAo = (XAf-XAo)/-rAf)

FAo(XAf-XAo) = -rAfV = -rAf W = -rAf S = -rAf Vp =
-rAf Vr
 .
5th oct 2011
Residence time (homog. Mixed reactor) = VCAo/Fao = -CAoXA/-r
Space Time (Homogeneous Plug Reactors) = VCAo/Fao= -CAodXA/-rA
Weight Time (Catalytic Plug Flow Reactor) = W CAo/Fao = -CAodXA/-rA
CA = CAo(1-xA)/(1+AxA) For pure A, A=0
With this expression , integrating (PFR), we have:
k = (1+A)ln(1/1-XA) - AxA (first order)
k = (1+A)ln(1/1-XA) - AxA (first order)
* Come up with the expressions for the 2nd order
Rxn with the help of generalised integral tables.
 Performance Equation of combined
homogeneous and Heterogenous catalytic
Reactions
This is a case of conversion on the catalyst
surface and in the gas/liquid stream.
Total rate of disappearance of A given by:
(dNA/dt)total = (dNA/dt)homog + (dNA/dt)heterog
= V(-rA)homog + W(-rA)heterog
(From slide 6)
divide by W (-rA)total = (V/W) (-rA)homog + (-rA)heterog
Divide by V (-rA)total = (-rA)homog + (W/V)(-rA)heterog
 TYPE OF EXPERIMENTAL REACTORS
(Packed Bed) -Diagrams
Batch reactor: t = (CAoV/W)dXA/- rA (0 to Xaf)

Differential reactor = (WCAo/FAo) = CAoXA/-rA

Plug flow reactor = (WCAo/FAo) =CAo dXA/-rA (0 to Xaf)

Mixed flow reactor = (WCAo/Fao ) = CAoXAf/-rA

Recycle reactor =(WCAo/FAo)=CAoXAf/-rA (fast recy)

Recycle reactor = (R+1) CAodXA/-rA (slow recy)

from RXAf/(R+1), to XAf)
Note the diff. Between reactor types & catalyst rate basis
.
.
 SAMPLE CALCULATIONS
(1) What quantity of catalyst is required for a first
order reaction in mixed flow catalytic reactor if a
conversion of 80% is desired and the reactant
flowing at 100moles/s enters with an initial
concentration of 2x10-3 mole/liter ?.
k=2litres/kg,s. What is the weight time for the
process?
Soln:
Performance eqn for cat. mixed flow reactor:
= (WCAo/Fao ) = CAoXAf/-rA -----------------(1)
 .
From eqn (1),
W = (FaoXAf)/-rA where -rA = k CAo(1 - Xaf)
=2(2x10-3)(1-0.8)
= 8x10-3 mole/kg.s
Hence, W = (100x0.8)/ 8x10-3 kg = 10,000kg
Weight time = (WCAo/Fao ) = 0.004kg.s/m3
*note that the above rate expression is for
homogeneous reaction and is not
representative of an heterogeneous reaction
kinetics.
 .
Example (2): A closed loop reactor is used for
catalytic rate study. Feed gas with reactant is
introduced into the system and is rapidly
circulated through the catalyst loop, From the
following composition-time data. Find a kinetic
equation in units of mol[gm-min to represent this
reaction. V=100 Cm3 (volume void).
Non porous catalyst is 2gm, 1cm3 bulk void
fraction=0.5
A=R, 32oc, pure A
t (min) 0 3 6 9 12
,mm Hg 760 240 130 90 65

 .
Solution:
Task: obtain specific rate equation
The reactor type is BATCH
t = (CAoV/W)dXA/- rA (0 to Xaf)---------- (1)
reaction is first order; use simple rate 1st order
equation:
-rA = kCA
-rA =k CAo(1-xA)/(1+AxA) where A = 0
Hence subst rA into eqn (1) and integrate:
 .0
t = (CAoV/W)[-ln(1-xA) + ln1] xAf
t = V[ln(1-xAf)]wk
a plot of t vs ln(1-xAf) is linear with a slope of V/wk
where
xA = (CAo - CA}/ CAo
and CA = n/V = P/RT R = 83.016 cm3. atm/gmol.k
= 62330cm3.mmHg/gmol.k

with V and w known k can be determined .

t(min) 0 3 6 9 12
CA ( 40000 12630 6840 4740 3420
xA 0 .684 0.829 0.882 0.915
HETEROGENEOUS REACTION KINETICS
Consider a gaseous reaction on the surface of a
porous solid catalyst:
The rate of reaction for the particle may depend
on:
(a) Surface kinetics or rate of reaction on the
surface of the catalyst. (changes with
deactivation of the catalyst
(b) Resistance to pore diffusion of reactants into
the catalyst leading to concentration gradient
along the pore length.
 STEADY STATE REACTION SYSTEM.
Rates of heterogeneous Reactions are subject to
mass transfer rate into the catalyst pores.
(A) LINEAR EXPRESSION (1st order)
Qg = kg(Cg -Cs) (rate of mass transfer)-------(1)
Qs = ksCs (rate of reaction) -------------- (2)
A steady state, rate mass transfer is equal to the
rate of reaction:
Q g = Qs
kg(Cg -Cs) = ksCs hence, Cs = (kg/ kg+ ks)Cg ----(3)
(rate of mass transfer = rate of reaction)
 .
Subst for Cs in eqn (2):
Qs = -1/(1/kg + 1/ks)Cg = -koverallCg
Subst for Cs in eqn(1):
Qs = -1/(1/kg + 1/ks)Cg
Hence,
Qs = Q g = [-1/(1/kg + 1/ks)]Cg = -koverallCg --- (4)
koverall = 1/R (overall resistance to reaction
is additive of the various resistances to
reaction and mass transfer ks is rate constant
and kg is mass transfer coefficient.
 .
(B) Combining non-linear rate expressions.12/10/11
Mass transfer step: Qg = kg(Cg -Cs) -------- (1)
Reaction step: Qs = ksCs2 ---------- (5)
At steady state, Qg = Qs
kg(Cg -Cs) = ksCs2
Hence, C = [-k + (k 2 + 4 k k C )0.5]/2k ] ---- (6)
s g g g s g g
Subst for Cs in (1) or (5):
Qs = Qg = -kg /2ks[2ksCg + kg - (kg2 + 4 kg ks Cg)0.5] ---- (7)
the individual resistances are not additive nor
combine in a simple way when the individual
rate expressions are not all linear.
 RATE CONTROLLING STEP Ignore this equation 4
Qs = Qg = -kg /2ks[2ksCg + kg - (kg + 4 kg ks Cg
2 )0.5] ---- (7)
this slide

Eqn (7) can be simplified by introducing the concept of Rate

controlling step:
Chemical rxns vary widely with temp and steps. Many times
one step or another poses dominant resistance than others:
such step is called the rate controlling step.
E.g. If chemical reaction step is rate controlling, then
1/ks 1/ kg or kg ks the above eqn can thus be
simplified.
Also if mass transfer step is rate controlling another
form of simplified expression can be obtained.
 FLUID PARTICLE REACTION
(of great industrial application)
A(fluid) + bB(solid) = Products (fluid, fluids+solid, solids)
Solid particles remain unchanged in size during
reaction when:
They contain large amount of impurities which
remains as a non-flaking ash
Form a firm product material with solid products
or fluid and solid products
 .
NOTE: Particles shrink in size during reaction
when a flaking ash or product material is
formed or when pure B is used in the
reaction with fluid products
Examples:
NO CHANGE IN SIZE
Roasting or oxidation of sulphides ores to yield
metal oxide
2ZnS (s) + 3 O2(g) = 2 ZnO(s) + 2SO2(g)
Or 4FeS2(s) + 11O2(g) = 8SO2(g) + 2Fe2O3(s)
( diagrm p6) ie. the volume void inside the ferrous sulphide will change but the size will remain the
same especially when it has changed to ferrous oxide.
 .
(2) The preparation of metals from their
oxides by reaction in reducing atmospheres.
i.e Iron is prepared from crushed and sized
magnetite ore continuous counter current ,
three stage , fluidized-bed reactor as in:
Fe3O4(s) + 4H2(g) = 3Fe(s) + 4H2(g)
(3) The nitrogenation of Calcium Carbide to
produce Cyanamide
CaC2(s) + N2(g) = CaCN(s) + C (amorphous)
The protective surface treatment of solids
such as the plating of metals
 .
Change in Size 19/10/11
(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) = CO(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) THERE IS NO OXYGEN IN THIS RXN

The manufacture of Sodium thiosufate 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
SELECTION OF A MODEL
Model of reaction means conceptual picture of
reaction a model show s the route the reaction is taking.

Every model for the progress of the reaction

comes with its mathematical representation or
Rate Equation. there are two kinds of model: when the reactants do not change is size and when the
change in size.

If the model chosen corresponds closely to what

really takes place then the rate expression will
closely predict and describe the actual kinetics
if your model is tested and it predicts well the ni
 .
For non-catalytic heterogeneous reactions, the
two simple idealized models are :
The progressive conversion Model
The unreacted-core Model

THE PROGRESSIVE CONVERSION MODEL

The reactant gas enters and reacts throughout the
particle at all times most likely at different rates
and locations within the particle. Thus the solid
reactant is converted continuously and
progressively throughout the particle as shown
below:
(Diagram p9)

 .
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
 (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 (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 particle
shape.

(b) Diffusion thro Ash layer controls

(diagram pg15)
 .
Both the reactant A and the boundary of the
unreacted core move inward toward the
centre of the particle.
The rate of diffusion of A toward the centre is
about 1000 times the rate of movement of the
boundary. Hence the boundary can be
assumed constant wrt the movement of A.
1000 is roughly the ratio of density of solid to
gas
The unreacted core will also be assumed
constant wrt the concentration gradient of
(dCA/dr) of A within the ash layer(ss asumptn)
 Since diffusion thro the .ash layer is the rate
controlling step, the rate of reaction of A at any
time, will be given by the rate of diffusion thro
the ash layer to the reaction surface.
dNA/dt = 4r2 QA =4R2 QAS = 4rc2 Qac = const
where QA (mol/m2.s) = flux at different radius(r,R,
rc ) within the ash layer.
From Ficks law for equimolar counter diffusion:
QA = De dCA/dr where both QA & dCA/dr are +ve
De is the effective diffusivity (cm2/s)
-dNA/dt =4r2 De dCA/dr
 .
-dNA/dt dr/r2 = 4DedCA
Betwn R & rc and Cag, Cas & Cac = 0
-dNA/dt[1/ rc - 1/R] = 4DeCag ------------ (7)
But, -dNA = -4Brc2drC/b from eqn (2)
Subst for dNA in (7)
-B rc2(1/ rc - 1/R) drC = bDeCag dt
from rc= R to rc and time 0 to t
t = BR2/6bDeCAg[1-3(rC/R)2 + 2(rC/R)3] ---- (8)
For complete conversion of a particle ie rc=0
At time , = BR2/6bDeCAg ---------------(9)
 .
The progression of the reaction is given by:
t / = 1-3(rC/R)2 + 2(rC/R)3 ---------------- (10)
But from eqn (6), 1 - XB = (r/R)3
Hence,
t / = 1-3(1 - xB)2/3 + 2(1- xB) -------------- (11)
 .
The progression of the reaction is given by:
t / = 1-3(rC/R)2 + 2(rC/R)3 ---------------- (10)
But from eqn (6), 1 - XB = (r/R)3
Hence,
t / = 1-3(1 - xB)2/3 + 2(1- xB) -------------- (11)
C: Chemical Reaction Controls (17-24/11
Diagrm pg 18
The rate of reaction is proportional to the available
surface of the unreacted core
- r = -(1/Sex)dNB/dt = -b(1/Sex)dNA/dt = rrxn
-(1/ 4rc2)dNB/dt = -b(1/ 4rc2)dNA/dt = bksCAg
But dNB = BdV = B4rc2drc (in terms of the shrinking core
radius)
Substitute for dNB
-(1/ 4rc2). B4rc2 drc/dt = bksCAg
-B drc/dt = bksCAg
 .
-B drc = bksCAg dt
t = -B(R-rc)/ bksCAg----------------------- (12)
Time for complete reaction ie when rc = 0
is: = -BR/ bksCAg ------------------------ (13)
Fractional time left for reaction is given by:
t/ = 1 rc/R = 1 - (1-XB) --------------- (14)
 RATE OF REACTION FOR SHRINKING
SPHERICAL PARTICLES
No ash forms or remains on the solid. i.e
burning of pure carbon in air (the reacting
particle shrinks during reaction and finally
disappears)
Three steps are involved:
Step 1: Diffusion of reactant A from the main
body of gas through the gas film to the surface
of solid
 .
Step 2: Reaction on the surface between
reactant a and solid
Step3: Diffusion of reaction products from the
surface of the solid through the gas film back
into the main body of gas
(Diagram p20)
Rate expression
Chemical Reaction Controls
When chemical reaction controls, the
behaviour is similar to the one treated
previously with the derived expressions.
 .
Gas Film Controls
For Stokes regime, ie kg arround value of 1/dp
t = y B R2 /2bDCAg ----------------------(15)
= yB Ro2 /2bDCAg ----------------------- (16)
t/ = 1 (R /Ro)2 = 1 (1-XB)2/3 -------(17)
Where y= mole fraction of the reactant in the fluid
R= radius before reaction
Ro= radius before reaction
 UNCHANGING SIZE
Combination of Resistances
Assumption of one step is not appropriate
since the effect of each step varies with the
progress of reaction. For example while the
film resistance remains the same the ash
resistance is absent at the beginning of the
reaction but increases as reaction proceeds.
The reaction resistance increases with
decrease in the radius of the reaction
 .
The time to reach any stage of reaction is the
equal to the sum of times required to cross
each step:
tfinal = tfilm alone + tash alone + trxn alone
final = film alone + ash alone + rxn alone
RESITANCE OF EACH STAGE
Resistance due to film = 1//kg
Resistance due to Ash = R(R- kg)/ RcDe
Resistance due to Rxn = R2/ rc2 ks
 The rate of disappearance. of the solid can be given
by:
- r = -(1/Sex)dNB/dt = -bCA/ resistances
-(1/Sex)dNB/dt = -bCA/[1/kg + R(R-rc)/rcDe + R2/ rc2 ks ]
But NB (flux) = rcB hence,
-drc/dt = -bCA/B [rc2 / R2 kg + (R-rc)rc/RDe + 1/ ks ]
(film) (ash) (rxn)
the average equation from the beginning to the end of
reaction taking into account the variation of each
resistance is given by:
-(1/Sex)dNB/dt = ksCA = CA/[1/kg + R/2De + 3/ks ]
For shrinking size average rate is:
-(1/Sex)dNB/dt = CA /[1/kg +1/ks )