CHE 516

ADVANCE REACTION ENGINEERING

PROF. J A OMOLEYE
Dr. Ranti Agboola
TEXTS:
-THE CHEMICAL REACTOR -- --OMNIBOOK
Levenspiel,
-ADVANCED ENGINEERING CHEMISTRY – Dr
M R Senapati
- Reaction Engineering e-book
 TESTS & EXAMS
• Assignments & 2 Tests (CA) - 30%
• Final examination - 70%
• Do honest work and avoid cheating
• Copying other student’s 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 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
• Turn off Audio during virtual Lecture to avoid
Distraction
CHEMICAL REACTION ENGINEERING.
REACTOR VS A POT OF SOUP (SIMILARITIES
AND DIFFERENCES)
 REACTOR VS A POT OF SOUP
(SIMILARITIES AND DIFFERENCES)

• SIMILARITIES:
• - both are containers
• - contain ingredients for processing
• - rate of processing a function of temperature
• - stirred hence a stirrer
• - atmospheric pressure operation
• - scale (laboratory)
• - heterogeneous hence transport challenge, KA
 Differences
• - Chemical vs physical process
• - components: chemical vs bio -source
• - edibility
• - high vs atmospheric pressure
• - rates: -r = f(T,KA,P/C,n) r = f(T, KA,t)
• - machine vs manual stirring
• - heat loss
• - scale (laboratory vs industrial)
• - Pattern (batch, cstr, pfr, etc)
 HOMOGENEOUS REACTION SYSTEM
REVIEW
• WHAT DO YOU UNDERSTAND BY
HOMOGENEOUS REACTION SYSTEM
• –reaction of NaOH (l) + HCL(l)
• – reaction of NaOH (l) + Palm Oil (l)
(SAPONIFICATION REACTION)
• WHAT FACTORS INFLUENCE RATE OF
HOMOGENOUS REACTION SYSTEM?
• –rA = kCAo(1-XA) where k = koexp(- EA/RT)
• HOW DO WE KNOW WHAT SIZE OF REACTION
VESSEL TO USE FOR A PARTICULAR REACTION
Homogeneous Reactor Type and Volume
• WHAT FACTOR DETERMINES WHICH REACTOR
TYPE TO USE, CSTR OR PFR?
• A REACTION HAS A MINIMUM POINT ON THE
GRAPTH OF 1/(-rA) vs XA. WHAT REACTOR TYPE IS
NEEDED? V/FAO = ∆XA /(-rAf) = XA/(-rA)
• WHAT IS THE PURPOSE OF LABORATORY
EXPERIMENT IN REACTOR DESIGN?
• HOW DO WE DETERMINE RATE CONSTANT
EXPERIMENTALLY IN ORDER TO DESIGN OUR
REACTOR WHEN ORDER OF REACTION IS KNOWN?
• –rA = kCAo(1-XA) Hence, ln(CAo/CA) = kt
 REVIEW OF RATE EQUATIONS
(A) BATCH REACTOR: t/CAo =∫(dXA/- rA)
(B) Differential Reactor: V/FAo = (dXA/-rA)
(C) Plug Flow Reactor: Vr/FAo =∫ dXA/-rA
(D) Mixed Flow Reactor V/FAo = (XAf-XAo)/-rAf
The essence of reaction engineering is the
prediction of the reactor size, reaction
conditions and the reaction pattern to obtain a
given quantity of product of a desired purity
within a given time. (to slide 32)
 HETEROGENEOUS CATALYSIS
SOLID CATALYSED REACTIONS, INTRODUCTION
- homogeneous: 1 changing phase (gas or liquid)
- Heterogeneous: Involves more than one phase
- complex bcos of effects of heat & mass transfer
- Example of Reactors for 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
 Example of Reactors for 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 with 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:
-r’A = -(dNA/dt)/W = k’CA, (mols reacted/kgcat.s)
• Catalyst surface area:
-r’’A = -(dNA/dt)/S = k’’CA, (molsreacted/m2cat surf.s)

. Vol. of catalyst pellet:

-r’’’A = -(dNA/dt)/Vp = k’’’CA, (molsreacted/m3solid.s) 
 .

• conversion from one basis to another (Mol/s)

• Making -(dNA/dt) the subject of above Eqns:
• rV = r’W = r’’S = r’’’Vp = r’’’’Vr
writing each r, r’ etc in terms of kCA:
kV = k’W = k’’S = k’’’Vp = k’’’’Vr
• 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
• rA V = rA’W = rA’’S = rA’’’Vp = rA’’’’Vr 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 = -rA’dW = rA’’dS = rA’’’dVp = rA’’’’dVr

•
 Example
• How long will it take to obtain 80% conversion
in a batch reactor whose rate ,r is given by,
• -r’A = -(dNA/dt)/W = k’CA, (mols
reacted/kgcat.s), with an initial concentration
of 2moles/m3 if k’ = 0.4m3gas/kg.s?
• Solution:
• Performance equation for batch reactor:
• t/CAo =∫(dXA/- rA)
• Substituting for rate,
• t/CAo =∫(dXA/- rA)
• t/CAo =∫(dXA/k’CAo(1-XA))
• t =(-1/k’)ln(1-XAo)
• Subst.
• t = (-1/0.40)ln(0.2) = ysec
 .

(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) τ = VCAo/Fao = -CAo∆XA/-r
Space Time (Homogeneous Plug Reactors) τ = VCAo/Fao = -CAo∫dXA/-rA
Weight Time (Catalytic Plug Flow Reactor) τ’= W CAo/Fao = -CAo∫dXA/-r’A
CA = CAo(1-xA)/(1+ԑAxA) For pure A, ԑA=0
With this expression , integrating τ(PFR), we have:
k τ = (1+ԑA)ln(1/1-XA) - ԑAxA (first order)
k’τ’ = (1+ԑA)ln(1/1-XA) - ԑAxA (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(-r’A)heterog
(From slide 6)
divide by W (-r’A)total = (V/W) (-rA)homog + (-r’A)heterog
• Divide by V (-rA)total = (-rA)homog + (W/V)(-r’A)heterog
 TYPE OF EXPERIMENTAL REACTORS
(Packed Bed) -Diagrams 16/10/12
Batch reactor: t = (CAoV/W)∫dXA/- rA’ (0 to Xaf)

•Differential reactor τ’ = (WCAo/FAo) = CAo∆XA/-rA’

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

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

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

• Recycle reactor τ’= (R+1) CAo∫dXA/-rA’ (slow recy)

from RXAf/(R+1), to XAf)
Note the diff. Between reactor types & catalyst rate basis
.

t = (CAoV/W)∫dXA/- rA’
.
 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:
• τ’ = (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 τ’ = (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 Rate const = 83.016 cm . atm/gmol.k
3

• t (min) 0 3 6 9 12
• ᴨ,mm Hg 760 240 130 90 65
3/9/13 (end of Lecture)
 .

• 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+ԑAxA) where ԑA = 0
• Hence subst –rA into eqn (1) and integrate:
 .

• t = (CAoV/WkCAo)[-ln(1-xAf)]
• t = -(V/wk)ln(1-xAf)
• 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 film diffusion of reactants unto
the catalyst surface leading to concentration
gradient with the bulk reactor .
SOLID - FLUID REACTION
 STEADY STATE REACTION SYSTEM.
• Rates of heterogeneous Reactions are subject to mass
transfer rate unto the catalyst/solid surface.
• (A) LINEAR EXPRESSION (1st order)
• Qg = kg(Cg -Cs) (rate of mass transfer)-------(1)
• Qs = ksCs (rate of reaction) -------------- (2)
• ks is rate constant and kg is mass transfer coefficient
• A steady state, rate mass transfer is equal to the rate of
reaction: Qg = Qs
• kg(Cg -Cs) = ksCs hence, Cs = (kg/ kg+ ks)Cg ----(3)
• (expression helps eliminate Cs in the rate equation)
 .

• Subst for Cs in eqn (2):

• Qs = -1/(1/kg + 1/ks)Cg = -koverallCg ------------- (i)
• Subst for Cs in eqn(1):
• Qg = -1/(1/kg + 1/ks)Cg ----------------------- (ii)
• Hence,
• Qs = Qg = [-1/(1/kg + 1/ks)]Cg = -koverallCg --- (4)
• koverall = 1/ƩR (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,
Cs = [-kg + (kg2 + 4 kg ks Cg)0.5]/2kg] ---- (6)
• 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
• Qs = Qg = -kg /2ks[2ksCg + kg - (kg2 + 4 kg ks Cg)0.5] ---- (7)
• 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. Assignment: obtain specific Equation
• 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
• A firm product material with solid products or
fluid and solid products are formed.
 .

• 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)
 .

• (2) The preparation of metals from their

oxides by reaction in reducing atmospheres.
i.e Iron is prepared from crushed and sized
magnetite ore in a continuous counter-currrent
, 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)
• 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

• 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
• 
• 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 =4ᴨR2
• Where kg in cm/s or m/s is the mass transfer
coefficient
• But, NB (moles of B) = molar density of B x vol of solid B
..

• NB = ρ B x V
• -dNB = -bdNA = - ρBdV
• = -ρBd(4ᴨrc3/3)
• -dNB = -bdNA = -4ᴨρBrc2drC ----------(2)
• -dNB = -4ᴨρBrc2drc -----------------(2a)
• -dNB/dt = -4ᴨρBrc2drc/dt -------(2b)
• Subst for –dNB/dt in (1),
• - rA’ = -(1/Sex)dNB/dt = -(4ᴨρB/4ᴨR2)rc2drc/ dt = bKgCAg
• -(4ᴨρB/4ᴨR2)rc2drc = bKgCAgdt -------------- (3a)
• Integrating, we obtain:
 .

• t = ρBR/3bkgCAg[1-(rc/R)3] -------------------------(3b)
• t = f(rc)
• in order to predict the time t = τ for end of reaction,
substitute radius of solid rc = 0 in eqn 3
• τ = ρBR/3bkgCAg ------------------------------------- (4)
• fraction of time spent for reaction is:
• t/ τ = 1 – (rc /R)3 ----------------------------(5)
• Derive for traction of time left to complete reaction
• CONVERSION
• Conversion of B is given by:
• xB = volume reacted/total vol of particles
• = (total Vol – Vol Unreacted)/total Vol
 .

• XB = [4ᴨR3/3 - 4ᴨrc3/3]/(4ᴨR3/3
• XB = 1 - (4ᴨrc3/3)/(4ᴨR3/3)
• XB = 1 - (r/R)3 = t/ τ ----------------- (6)
• (compare to Eqn(5)
• Try the derivation for cylindrical particle
shape.

• (b) Diffusion thro Ash layer controls

• (diagram pg15)
(Cac not Cas)
 .

• 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.
• Rate of Difusion: -dNA/dt = 4ᴨr2 QA =4ᴨR2 QAS = 4ᴨrc2 Qac
= const
• where QA is flux in (mol/m2.s) = flux at different
radius(r,R, rc ) within the ash layer.
• From Fick’s 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 =4ᴨr2 De dCA/dr
• Transfer r2 /dr to LHS
 .

• dNA/dt ∫dr/r2 = 4ᴨDe∫dCA (note dNA/dt constant)

• Betwn R & rc and Cag=Cas & Cac = 0
• dNA/dt[1/ rc - 1/R] = 4ᴨDeCag ------------ (7)
• But, dNA = -4ᴨρBrc2drC/b from eqn (2)
• Subst for dNA in (7):
• (4ᴨρBrc2drC/b) /dt[1/ rc - 1/R] = 4ᴨDeCag
• ρB ∫rc2(1/ rc - 1/R) drC = bDeCag ∫dt
• from rc= R to rc and time 0 to t
• t = ρBR2/6bDeCAg[1-3(rC/R)2 + 2(rC/R)3] ---- (8)
• For complete conversion of a particle ie rc=0
• At time τ, τ = ρBR2/6bDeCAg ---------------(9)
 .

• The progression of the reaction is given by:

• t / τ = 1-3(rC/R)2 + 2(rC/R)3 ---------------- (10)
• But from eqn (6), 1 - XB = (r/R)3
• Hence,
• t / τ = 1-3(1 - xB)2/3 + 2(1- xB) -------------- (11)
 .

• The progression of the reaction is given by:

• t / τ = 1-3(rC/R)2 + 2(rC/R)3 ---------------- (10)
• But from eqn (6), 1 - XB = (r/R)3
• Hence,
• t / τ = 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’rxn,B = -(1/Sex)dNB/dt = -b(1/Sex)dNA/dt
-(1/ 4ᴨrc2)dNB/dt = bksCAg ------------------------------------- (1)
But dNB = ρBdV = ρB4ᴨrc2drc (in terms of the shrinking core
radius)
• Substitute for dNB in (1)
• -(1/ 4ᴨrc2). ρB4ᴨrc2 drc/dt = bksCAg (Rate of
disappearance of B, not A)
• -ρB drc/dt = bksCAg
 .

• -ρB ∫drc = bksCAg ∫dt

• t = -ρB(R-rc)/ bksCAg----------------------- (12)
• Time for complete reaction ie when rc = 0
• is: τ = -ρBR/ bksCAg ------------------------ (13)
• Fractional time left for reaction is given by:
• t/ τ = 1 – rc/R = 1 - (1 - XB)1/3--------------- (14)
From eq(6) rc/R = (1 - XB)1/3
 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
• τfinal = τfilm alone + τash alone + τrxn 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/ Ʃresistances
-(1/Sex)dNB/dt = -bCA/[1/kg + R(R-rc)/rcDe + R2/ rc2
ks ]
*
the average rate equation from the beginning to
the end of reaction when taking into account
the variation of each resistance is given by:
-(1/Sex)dNB/dt = ks’CA = CA/[1/kg + R/2De + 3/ks ]
 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 changing boundary
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 around value of 1/dp
• t = y ρB (Ro2 -R2 )/2bDCAg ----------------------(15)
• τ = yρB Ro2 /2bDCAg ----------------------- (16)
• t/ τ = 1 – (R /Ro)2 = 1 – (1-XB)2/3 -------(17)
• Where y= mole fraction of the reactant in the fluid
• R= radius of reaction at time t
• Ro= radius before reaction
kg = Mass transfer coefficienFor shrinking core

Average rate is:

-(1/Sex)dNB/dt = CA /[1/kg +1/ks )
 Insert on last page Row *
But NB (flux) = rcρB hence,
-drc/dt = -bCA/ρB [rc2 / R2 kg + (R-rc)rc/RDe + 1/ ks ]
(film) (ash) (rxn)

IN SOLVING A PROBLEM ,
Determine first the type of model – shrinking Core or progressive
conversion
Next: if shrinking Core, is it constant size or shrinking size?
If constant size, is there any rate controlling step
If if shrinking size, what is rate controlling step?
If film is rate controlling, is it within the Stokes Regime?
 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