Overall Effectiveness Factor

• Overall effectiveness factor takes into

consideration diffusion, flow and reaction in
packed beds.
• Consider a situation where external and
internal resistance to mass transfer to and within
the pellet are of the same magnitude
• During steady state, transport of reactant from
bulk to external surface of catalyst is equal to net
rate of reaction of the reactant within and on
the pellet
Overall Effectiveness Factor
 Molar Rate
• Molar rate of mass transfer from bulk to
external surface is given by
MA = WAR x ac x ΔV
ac = external surface area per reactor volume
• MA represent the net (total) rate of reaction
on and within the pellet.
 Molar Rate
• Molar rate can also be represented by
MA = -r”A x (external area + internal area)
• External area
=acΔV
• Internal area
= Saρc(1-Ф) ΔV
ρb

= SaρbΔV
 Molar Rate
• Inserting all the terms, yields
MA = -r”A [acΔV + SaρbΔV]
• Combining both equation,
WARac = -r”A [ac + Saρb ]
• For most catalyst, internal surface area is
greater than external surface area, therefore
WARac = -r”A [Saρb ] (1)
• Recall that
MA = WAR x ac x ΔV = kc(CAB-CAS) ac x ΔV
 Molar Rate
• Also recall that, internal effectiveness factor,
-r”A = -r”AS x η
= k1CAS x η
• Substitute the above term into Eq (1),
WARac = k1CASηSaρb (2)
• Equate Eq (2) with molar flux,
kcac (CAB-CAS) = k1CASηSaρb
 Molar Rate
• Rearranging and solve for CAS,
CAS = (kcacCAB)/(kcac+ηk1Saρb)
• Recall that,
-r”A = k1CAS x η
= (η k1kcacCAB)/(kcac+ηk1Saρb)
• Divide by kcac,
= η (k1CAB)/(1+ηk1Saρb/ kcac)
 Molar Rate
• Overall effectiveness factor, Ω is similar to
internal effectiveness factor, η but instead of
based on concentration of surface, CAS, it is
based on concentration of bulk, CAB.
Ω = actual overall rate/ rate that would result
if entire surface were exposed to bulk
concentration, CAB
• The relationship is given by
-r”A = Ω (-r”AB)= Ω k1CAB
 Molar Rate
• Thus, the equation gives
Ω = (η)/ (1+ηk1Saρb/ kcac)
• Recall that, actual reaction rate is related by
-rA = -r’Aρb = -r”ASaρb
• For reaction rate at bulk concentration,
-rA = -rABΩ = -r’ABΩρb = -r”ASaρbΩ = k1CABSaρbΩ
Weisz-Prater Criterion for Internal Diffusion
• Weisz-Prater criterion is used to estimate if
internal diffusion is limiting the reaction
• Rearranging the equation,
η= 3
1 coth 1  1
 2
1

Ф2η= 3(Ф1 coth Ф1 – 1)

• The term on the left hand is known as Weisz-
Prater parameter, CWP
CWP = η x Ф2
= (observed reaction/reaction at CAS) x
(reaction at CAS/diffusion rate)
Weisz-Prater Criterion for Internal Diffusion
• CWP = η x Ф2
= (observed reaction/diffusion rate)
= (-rA(obs)/-r’AS ) x
(-r’ASρcR2)/(DeCAS)
= (-rA(obs) ρcR2 /(DeCAS)
• Therefore, we can deduce that if
CWP<<1, diffusion is not limiting and no
concentration profile exist
CWP>>1, internal diffusion is limiting and
concentration profile exist
Mears’ Criterion for External Diffusion
• Mears criterion uses the rate of reaction (-r’A) to
learn if mass transfer from bulk to catalyst pellet
can be neglected. Mears proposed that if the
value less than that, then mass transfer effect can
be neglected.
(-r’AρbRn)/(kcCAB) < 0.15
n = reaction order
R = catalyst pellet radius, m
ρb= bulk density of bed, kg/m3= (1-Ф) ρc
CAB= bulk concentration, kmol/m3
kc = mass transfer coefficient, m/s
Mears’ Criterion for External Diffusion
• Mass transfer coefficient can be obtained by
using Thoenes-Kramers correlations and when
that condition is satisfied, it implies that no
concentration gradient exist between bulk gas
and external surface of catalyst pellet.
 Mass Transfer and Reaction in a
Packed Bed
• Consider a reaction in a packed bed of
catalyst, instead of a pellet.

• Do mole balance at steady state,

AcWAZ( at Z) – AcWAZ(at Z+ΔZ) + r’AρbAcΔZ =0
 Mass Transfer and Reaction in a
Packed Bed
• Divide by AcΔZ and taking the limit of ΔZ→0,
- dWAZ /dz + r’Aρb =0
• Recall the molar flux,
WAZ = -DABdCAB/dz + yAB (WAZ +WBZ)
= -DABdCAB/dz + yAB cU
= -DABdCAB/dz + UCAB
• Insert into differential equation,
DAB (d2CAB/dz2 ) – U (dCAB/dz) + r’Aρb = 0
 Mass Transfer and Reaction in a
Packed Bed
• Recall that,
-r’A = -r’AB x Ω
= -r”ABSa x Ω
= kSaCAB x Ω
• Therefore, the final equation becomes,
• DAB (d2CAB/dz2 ) – U (dCAB/dz) - kSaCABΩρb = 0
 Mass Transfer and Reaction in a
Packed Bed
• Normally, diffusion in the axial direction is
usually neglegible, therefore,
– U (dCAB/dz) - kSaCABΩρb = 0
• Rearranging,
-U (dCAB/CAB) = kSaΩρb dz
• Boundary conditions, CAB = CABO at Z=0,
ln (CAB/CABO) = -kSaΩρbz/U
• Conversion at exit length, Z =L,
X = 1- (CAB/CABO) = 1-exp(-kSaΩρbz/U)