Section 15.

4 Falsified Kinetics 737

The solution to Equation (E15-2.8) yields f13 5 0.9

φ13  0.9 
- 5 (0.01)  ---------
R3 5 R1 ------ - 5 5.5 3 1024 m
φ11  16.5
A particle size of 0.55 mm is necessary to virtually eliminate diffusion control
(i.e., h 5 0.95).
Analysis: This example is important because it shows us how, with only two mea-
surements and some assumptions, we can determine internal diffusion limitations
for the two pellet sizes, and predict the pellet size necessary to completely eliminate
internal diffusion.

15.4 Falsified Kinetics

You may not be There are circumstances under which the measured reaction order and activa-
measuring what tion energy are not the true values. Consider the case in which we obtain
you think you are.
reaction-rate data in a differential reactor at two different temperatures, T1 and
T2, where precautions are taken to virtually eliminate external mass transfer
resistance (i.e., CAs = CAb). From these data, we construct a log-log plot of the
measured rate of reaction –r′A as a function of the gas-phase concentration, CAs
(Figure 15-7). The slope of this plot is the apparent reaction order n9 and the
measured rate law takes the form
n′
Measured rate: –r′Am = k′nCAs (15-40)
T2 > T1
log

–r´A
Measured rate with
apparent reaction
order n9
T2 Slope = n´
T1

CAs log

Figure 15-7 Determining the apparent reaction order (–rA = ρb (–r′A)).

We will now proceed to relate this measured reaction order n9 to the true reac-
tion order n. Using the definition of the effectiveness factor, noting that the
actual rate, –r′A , is the product of h and the rate of reaction evaluated at the
n
external surface, k n CAs , i.e.,
Actual rate: –r′A = η ( –r′As ) = η ( k n CAs
n
) (15-41)
For large values of the Thiele modulus, fn , where internal mass is limiting, we
can use Equation (15-38) to substitute into Equation (15-41) to obtain
3 2 n 3 D 1–n 2 n
–r′A = ----- ---------- k nCAs = ---- ------e CAs ---------- k nCAs
φn n + 1 R kn n+1

Simplifying

3 2De 1/2 (n + 1)/2

–r′A = ---- --------------
-k C (15-42)
R ( n + 1 ) n As
738 Diffusion and Reaction Chapter 15

We equate the true reaction rate, Equation (15-42), to the measured reaction
rate, Equation (15-40), to get

True
Measured














2  ---
3- ( n11 ) ⁄ 2




–r′A = ---------- De k n1 ⁄ 2CAs n′
= k′nCAs (15-43)
n+1 R 

The functional dependence of the reaction rate on concentration must be the

same for both the measured rate and the theoretically predicted rate
( n11 ) ⁄ 2 n′
CAs = CAs
therefore the measured apparent reaction order n9 (nApparent) is related to the
true reaction order n (nTrue) by

The true and the 1+n

apparent reaction n′ = ---------- (15-44)
order 2

In addition to an apparent reaction order, there is also an apparent activa-

tion energy, EApp . This value is the activation energy we would calculate using
the experimental data from the slope of a plot of ln ( –r′A ) as a function of
(1/T) at a fixed concentration of A. Substituting for the measured and true spe-
cific reaction rates in terms of the activation energy gives
2EApp ⁄ RT 2ET ⁄ RT
k′n = A Appe kn = A T e

















Measured True

into Equation (15-43), we find that

ntrue = 2napparent – 1 1⁄2

 –E   –EApp n′
–r′A 5  ---- ---------- De A T1 ⁄ 2 exp  --------T-
3 2 (n11) ⁄ 2
CAs 5 A App exp  -------------
- CAs
R n+1   RT   RT 
Taking the natural log of both sides gives us

3 2 ET E App
ln ---- ---------- D A 1 ⁄ 2 C (n11) ⁄ 2 – ---------- n′
- = ln [ A AppCAs ] – ----------
- (15-45)
R n + 1 e T As 2RT RT
where ET is the true activation energy.
As with the dependence rate on concentration, the temperature dependence
must be the same for the analytical rate. Comparing the temperature-dependent
terms on the right- and left-hand sides of Equation (15-45), we see that the true
activation energy is equal to twice the apparent activation energy.
The true activation
energy ET = 2EApp (15-46)

This measurement of the apparent reaction order and activation energy results
primarily when internal diffusion limitations are present and is referred to as
disguised or falsified kinetics. Serious consequences could occur if the labora-
tory data were taken in the disguised regime and the reactor were operated in a
Section 15.5 Overall Effectiveness Factor 739

Important industrial
consequence of
falsified kinetic
runaway reactions.
Safety considerations!
different regime. For example, what if the particle size were reduced so that
internal diffusion limitations became negligible? The higher activation energy,
ET , would cause the reaction to be much more temperature sensitive, and there
is the possibility for runaway reaction conditions causing an explosion to occur.

15.5 Overall Effectiveness Factor

For first-order reactions, we can use an overall effectiveness factor to help us
analyze diffusion, flow, and reaction in packed beds. We now consider a situa-
tion where external and internal resistance to mass transfer to and within the
pellet are of the same order of magnitude (Figure 15-8). At steady state, the
transport of the reactant(s) from the bulk fluid to the external surface of the cat-
alyst is equal to the net rate of reaction of the reactant within and on the pellet.

Here, both internal

and external
diffusion are
important.

Figure 15-8 Mass transfer and reaction steps.

The molar rate of mass transfer from the bulk fluid to the external surface is
Molar rate = (Molar flux) ⋅ (External surface area)
M A = W Ar ⋅ (External surface area/Volume)(Reactor volume)
= W Ar ⋅ ac ∆V (15-47)

where ac is the external surface area per unit reactor volume (cf. Chapter 14)
and DV is the volume.
This molar rate of mass transfer to the surface, MA , is equal to the net
(total) rate of reaction on and within the pellet

M A = –r″A ( External area + Internal area )

External area
External area = -------------------------------------- × Reactor volume
Reactor volume
= ac ∆V
Internal area Mass of catalyst Volume of catalyst
Internal area = --------------------------------------- × --------------------------------------------- × --------------------------------------------- × Reactor volume
Mass of catalyst Volume of catalyst Reactor volume
= S a × ρc × ( 1 – φ ) × ∆V
2
m g 3
= ------ × ------3 × m
g m

ρb






= S a ρc ( 1 – φ ) ∆V

= S a ρb ∆V
 740 Diffusion and Reaction Chapter 15

ρb = Bulk density Recall that ρc is the density of catalyst pellet, kg per volume of pellet and ρB
= ρc (1 – φ) is the bulk density of catalyst, kg-cat per reactor volume.
φ = Porosity
See nomenclature note We now combine the above equations, to obtain total molar flow into all
in Example 15-4. the catalyst in volume ∆V

M A = –rA″ [ ac ∆V +S a ρb ∆V ] (15-48)

Combining Equations (15-47) and (15-48), and canceling the volume DV,
we see the flux to the pellet surface, WAz ac, is equal to the rate of consumption
of A in and on the catalyst.
WAr ac 5 –rA″ ?(ac 1 Sa rb )
For most catalysts, the internal surface area is much greater than the external
surface area (i.e., Sa rb @ ac ), in which case we have

W Ar ac = –rA″ S a ρb

Comparing units on the r.h.s. and l.h.s. of Equation (15-49), we find

 mol m 2   mol  m 2  g 
 m2 ⋅ s ⋅ m3  =  m2 ⋅ s  g  m3 
     
where –rA″ is the overall rate of reaction within and on the pellet per unit sur-
face area, –rA′ is the rate of reaction per mass of catalyst

− rA′ = − rA′′Sa

and –rA is the overall rate per volume of reactor, i.e.,

− rA = − rA′ρb
then
WAz ac = − rA = − rA′′Saρb (15-49)

with the corresponding units for each term in Equation (15-49) shown below.
2 2
mol
-× m
mol mol- m g- cat-
-----------
2
------3 = -----------
3
- = -----------
2
× ------------ × -----------
3
m ⋅s m m ⋅s m ⋅s - g cat m
The relationship for the rate of mass transport to the external catalyst surface is
MA 5 WAr ac DV 5 kc (CAb 2 CAs )ac DV (15-50)

2 2
--------- =  -----------
mole-  -----
m 3 m
----  ---------  ------ m
Again, comparing mol mol m 3
- m =
units on the l.h.s. s  m2s   m3  s   m3   m3
and r.h.s.

where kc is the external mass transfer coefficient (m/s). Because internal diffu-
sion resistance is also significant, not all of the interior surface of the pellet is
accessible to the concentration at the external surface of the pellet, CAs . We
Section 15.5 Overall Effectiveness Factor 741

have already learned that the effectiveness factor is a measure of this surface
accessibility [see Equation (15-41)]:
2rA 5 rAsh

Rate at
Actual = Actual rate
surface -----------------------------------------------------------------------
rate Rate at surface conditions
conditions

Assuming that the surface reaction is first order with respect to A, we can uti-
lize the internal effectiveness factor to write
2rA 5 hk1CAs (15-51)
Recall that

( k 1 = k 1″ S aρb )

We need to eliminate the surface concentration from any equation involv-

ing the rate of reaction or rate of mass transfer, because CAs cannot be mea-
sured by standard techniques. To accomplish this elimination, we use
Equations (15-49), (15-50), and (15-51) in order to equate the mass transfer
rate of A to the pellet surface, –WArac, to the rate of consumption of A within
the pellet, ηk1CAs
WAr ac 5 hk1CAs
Then substitute for WAr ac using Equation (15-50)
kc ac (CAb 2 CAs ) 5 hk1CAs (15-52)
Solving for CAs , we obtain
Concentration at
the pellet surface as k c ac
a function of bulk CAs = -----------------------
-C (15-53)
gas concentration
k c ac + ηk 1 Ab

Substituting for CAs in Equation (15-51) gives

ηk 1k c acCAb
–rA = ---------------------------
- (15-54)
k c ac + ηk 1

In discussing the surface accessibility, we defined the internal effective-

ness factor h with respect to the concentration at the external surface of the
pellet, CAs , as

Actual overall rate of reaction

η = -------------------------------------------------------------------------------------------------------------------------------------------------------- (15-28)
Rate of reaction that would result if entire interior surface were
exposed to the external pellet surface conditions, CAs, T s
742 Diffusion and Reaction Chapter 15

Two different We now define an overall effectiveness factor that is based on the bulk
effectiveness factors concentration

Actual overall rate of reaction

Ω = ------------------------------------------------------------------------------------------------------------------ (15-55)
Rate that would result if the entire surface were
exposed to the bulk conditions, CAb, T b

Dividing the numerator and denominator of Equation (15-54) by kc ac , we

obtain the net rate of reaction, 2rA, in terms of the bulk fluid concentration,
which is a measurable quantity:
η
–rA = ------------------ k 1CAb (15-56)
ηk
1 + ---------1-
k c ac

The actual rate of reaction is related to the reaction rate evaluated at the bulk
concentration of A. Consequently, the overall rate of reaction in terms of the
bulk concentration CAb is

–rA = Ω ( –rAb ) = Ω k 1CAb (15-57)

where
Overall effectiveness η
factor for a Ω = ------------------ (15-58)
first-order reaction ηk
1 + ---------1-
k c ac

Note that the rates of reaction based on surface and bulk concentrations are
related by
–rA = Ω ( –rAb ) = η ( –rAs ) (15-59)
where
–rAs = k 1CAs
–rAb = k 1CAb
The actual rate can be expressed in terms of the rate per unit volume, 2rA , the
rate per unit mass, –r′A , and the rate per unit surface area, –rA″ , which are
related by the equation
–rA = –r′Aρb = –rA″ S a ρb
Section 15.6 Estimation of Diffusion- and Reaction-Limited Regimes 743

Recall that k″1 is given in terms of the catalyst surface area (m3/m2 ?s), k 1′ is
given in terms of catalyst mass (m3/g-cat ? s), and k1 is given in terms of reac-
tor volume (1/s)

k1 = ρb k1′ = ρb ⋅ Sa ⋅ k1′′
We saw in Chapter 14 that as the velocity of the fluid increases, the external
mass transfer coefficient kc increases (cf. 14-49). Consequently, for large flow
rates resulting in large values of the external mass transfer coefficient kc, we
can neglect the ratio in the denominator

η
High flow rates Ω= ≈η
of fluid ηk (15-60)
1+ 1
kc ac
Neglect
and the overall effectiveness factor approaches the internal effectiveness factor

Ω≡η (15-61)

15.6 Estimation of Diffusion- and Reaction-Limited

Regimes
Dial In many instances it is of interest to obtain “quick and dirty” estimates to learn
soap which is the rate-limiting step in a heterogeneous reaction.

15.6.1 Mears Criterion for External Diffusion Limitations

The Mears criterion, like the Weisz–Prater criterion, uses the measured rate of
reaction, –r′A , (kmol/kg-cat?s) to learn if external mass transfer from the bulk
gas phase to the catalyst surface can be neglected.6 Mears proposed that when
the Mears number is

Is external – r′A ( obs ) ρbRn

diffusion limiting? MR = -----------------------------------
- (15-62)
k cCAb

Here, we measure –r′A (obs), CAb, ρb, R and n, and then calculate kc to deter-
mine MR, where
n 5 reaction order
R 5 catalyst particle radius, m
rb 5 bulk density of catalyst bed, kg/m3
5 (1 2 f)rc (f 5 porosity)
rc 5 solid density of catalyst pallet, kg/m3
CAb 5 bulk reactant concentration, mol/dm3
kc 5 mass transfer coefficient, m/s

6 D. E. Mears, Ind. Eng. Chem. Process Des. Dev., 10, 541 (1971). Other interphase
transport-limiting criteria can be found in AIChE Symp. Ser. 143 (S. W. Weller, ed.),
70 (1974).
744 Diffusion and Reaction Chapter 15

Mears proposed that when

MR < 0.15
external mass transfer effects can be neglected and no concentration gradient
exists between the bulk gas and external surface of the catalyst pellet. This
proposal by Mears was endorsed unanimously by the Jofostan legislature. The
mass transfer coefficient can be calculated from the appropriate correlation,
such as that of Thoenes–Kramers, for the flow conditions through the bed.
Mears also proposed that the bulk fluid temperature, T, will be virtually
the same as the temperature at the external surface of the pellet when

Tb ≅ Ts –∆HRx ( –r′A ) ρb RE
- < 0.15
------------------------------------------ (15-63)
hT 2R g

where h 5 heat transfer coefficient between gas and pellet, kJ/m2 ?s?K
Rg 5 gas constant, 8.314 J/mol?K
DHRx 5 heat of reaction, kJ/mol
E 5 activation energy, kJ/kmol
and the other symbols are as in Equation (15-62).

15.7 Mass Transfer and Reaction in a Packed Bed

We now consider the same isomerization taking place in a packed bed of cat-
alyst pellets rather than on one single pellet (see Figure 15-9). The concentra-
tion CAb is the bulk gas-phase concentration of A at any point along the length
of the bed.

Figure 15-9 Packed-bed reactor.

We shall perform a balance on species A over the volume element, DV,

neglecting any radial variations in concentration and assuming that the bed is
operated at steady state. The following symbols will be used in developing our
model:
Ac 5 cross-sectional area of the tube, dm2
CAb 5 bulk gas concentration of A, mol/dm3
rb 5 bulk density of the catalyst bed, g/dm3
v0 5 volumetric flow rate, dm3/s
U 5 superficial velocity 5 v0 /Ac , dm/s
Section 15.7 Mass Transfer and Reaction in a Packed Bed 745

Mole Balance A mole balance on DV, the volume element (Ac Dz), yields
[ Rate in ] 2 [ Rate out ] 1 [ Rate of formation of A ] 5 0
A cW Az z 2 A cW Az z 1∆z 1 r′A ρb A c ∆z 50
Dividing by Ac Dz and taking the limit as Dz → 0 yields
rA
dW Az




– ------------- + r′A ρb = 0 (15-64)
dz
Combining Equation (14-5) and (14-7), we get
dCAb
WAz 5 2DAB -----------
- 1 yAb (WAz 1 WBz )
dz
Also, writing the bulk flow term in the form
BAz 5 yAb (WAz 1 WBz ) 5 yAb cU 5 UCAb
Equation (15-64) can be written in the form
d2CAb dCAb
DAB -------------
2
- – U -----------
- + rA = 0 (15-65)
dz dz
The term DAB (d 2CAb /dz 2 ) is used to represent either diffusion and/or
Now we will see
how to use h and V dispersion in the axial direction. Consequently, we shall use the symbol Da for
to calculate the dispersion coefficient to represent either or both of these cases. We will
conversion in a come back to this form of the diffusion equation when we discuss dispersion
packed bed.
in Chapter 18. The overall reaction rate, –rA, is a function of the reactant con-
centration within the catalyst. This overall rate can be related to the rate of
reaction of A that would exist if the entire surface were exposed to the bulk
concentration CAb through the overall effectiveness factor V
–rA = –rAbΩ (15-57)
For the first-order reaction considered here
–rA = Ωk 1CAb (15-66)
Substituting this equation for –rA into Equation (15-65), we form the dif-
ferential equation describing diffusion with a first-order reaction in a catalyst bed
2
Flow and first- d CAb dCAb
order reaction in a Da -------------
2
- – Ωk 1CAb = 0
- – U ----------- (15-67)
packed bed dz dz
As an example, we shall solve this equation for the case in which the flow rate
through the bed is very large and the axial diffusion can be neglected. Young
and Finlayson have shown that axial dispersion can be neglected when7
Criterion for –rA( obs )dp U0dp
neglecting axial -------------------------- < ----------- (15-68)
dispersion/diffusion U0CAb Da

7 L. C. Young and B. A. Finlayson, Ind. Eng. Chem. Fund., 12, 412.

746 Diffusion and Reaction Chapter 15

where U0 is the superficial velocity, dp the particle diameter, and Da is the

effective axial dispersion coefficient. In Chapter 18 we will consider solutions
to the complete form of Equation (15-67).
Neglecting axial dispersion with respect to forced axial convection
dCAb d2CAb
- » Da -------------
U ----------- -
dz dz 2
Equation (15-67) can be arranged in the form

dCAb Ωk 1CAb
-----------
- = –------------------
- (15-69)
dz U
With the aid of the boundary condition at the entrance of the reactor
CAb CAb 5 CAb0 at z 5 0
Equation (15-69) can be integrated to give
z
Conversion in a Ωk 1z
packed-bed reactor CAb = CAb0 exp –-----------
- (15-70)
U
1.0 The conversion at the reactor’s exit, z 5 L, is
X
CAb k 1ΩL
X = 1 – ----------
- = 1 – exp –------------
- (15-71)
CAb0 U
z

Example 15–3 Reducing Nitrous Oxides in a Plant’s Effluent

In Section 7.1.4 we saw that Nitric Oxide (NO) plays an important role in smog for-
mation and there are great incentives for reducing its concentration in the atmo-
sphere. It is proposed to reduce the concentration of NO in an effluent stream from
a plant by passing it through a packed bed of spherical, porous carbonaceous solid
pellets. A 2% NO and 98% air mixture flows at a rate of 1 × 10–6 m3/s (0.001 dm3/s)
through a 2-in.-ID tube packed with porous solid pellets at a temperature of 1173 K
Green and a pressure of 101.3 kPa. The reaction
chemical reaction
engineering NO 1 C → CO 1 1--2- N2

is first order in NO; that is,

–r′NO 5 k″1 S aCNO

and occurs primarily in the pores inside the pellet, where

Sa 5 Internal surface area 5 530 m2/g

k″1 5 4.42 3 10210 m3/m2 ?s

2
–10 3 2 m –7 3
k′1 = k″1 S a = [ 4.42 × 10 m ⁄ m ⋅ s ] 500 ------ = 2.34 × 10 m ⁄ g ⁄ s
g
 Section 15.7 Mass Transfer and Reaction in a Packed Bed 747

From those values of k″1 and k′1 we find

–6 3 –7 3 –1
k 1 = ρb k′ = ( 1.4 × 10 g ⁄ m )( 2.34 × 10 m ⁄ g ⁄ s ) = 0.328s

2% NO 0.004% NO

1. Calculate the Weisz–Prater parameter, CWP. Is internal mass transfer limiting?

2. Calculate the Mears parameter, MR, for external diffusion limited. Is external
mass transfer limiting?
3. Calculate the weight of solid porous catalyst necessary to reduce the NO con-
centration of 0.004%, which is below the Environmental Protection Agency’s
This example is long and limit.
detailed. Don’t fall
asleep, as you need to
know every detail of how Porous
to carry out these catalyst
calculations. CAb CAs CA pellet

External Internal
resistance resistance

Additional information:
At 1173 K, the fluid properties are
n 5 Kinematic viscosity 5 1.53 3 1028 m2/s
De 5 Effective diffusivity 5 1.82 3 1028 m2/s
DAB 5 Gas diffusivity 5 2.0 1028 m2/s
Also see the Web site The properties of the catalyst and bed are
www.rowan.edu/
greenengineering rc 5 Density of catalyst particle 5 2.8 g/cm3 5 2.8 3 106 g/m3
f 5 Bed porosity 5 0.5
rb 5 Bulk density of bed 5 rc (1 2 f) 5 1.4 3 106 g/m3
R 5 Pellet radius 5 3 3 1023 m
g 5 Sphericity = 1.0

Solution
It is desired to reduce the NO concentration from 2.0% to 0.004%. Neglecting any
volume change at these low concentrations gives us
CAb0 – CAb 2 – 0.004
X = ------------------------ = --------------------- = 0.998
CAb0 2

where A represents NO.

The variation of NO down the length of the reactor is given by Equation
(15-69). Replacing k1 by k′1ρb
dCAb Ωk 1 CAb k′1 ρbCAb
-----------
- = –------------------- = –Ω ---------------------
- (15-69)
dz U U
748 Diffusion and Reaction Chapter 15

Multiplying the denominator on the right and left hand sides of Equation (15-69) by
the cross-sectional area, Ac , and realizing that the weight of the catalyst up to a
point z in the bed is
(Mole balance)
+ W 5 rb Ac z
(Rate law)
+ the variation of NO concentration with solids is
(Overall
effectiveness dCAb Ωk′1 CAb
-----------
- = –-------------------- (E15-3.1)
factor) dW A cU

Because NO is present in dilute concentrations (i.e., yA0 ! 1), we shall take

« ! 1 and set A c U = v0 . We integrate Equation (E15-3.1) using the boundary con-
dition that when W 5 0, then CAb 5 CAb0

CAb  Ωk′1W 
X =  1 – ----------- = 1 – exp  – -----------------  (E15-3.2)
 CAb0  v0 

where

η
Ω=
k ′ρ (15-58)
1+ η 1 b
kc ac
Rearranging, we have
v0 1
W = ----------
- ln ----------- (E15-3.3)
Ωk′1 1 – X

4. Calculating the internal effectiveness factor for spherical pellets in which a

first-order reaction is occurring, we obtained
3
h 5 -----2 (f1 cothf1 2 1) (15-32)
φ1
As a first approximation, we shall neglect any changes in the pellet size
resulting from the reactions of NO with the porous carbon. The Thiele modu-
lus for this system is8

k1′ρc k ′′S ρ
φ1 = R =R 1 a c (E15-3.4)
De De
where
R 5 pellet radius 5 3 3 1023 m
De 5 effective diffusivity 5 1.82 3 1028 m2/s
rc 5 catalyst pellet density 5 2.8 g/cm3 5 2.8 3 106 g/m3
k″1 5 specific reaction rate (m/s) 5 4.42 3 10210 m3/m2 /s

Substituting in Equation (E15-3.4)

( 4.42 × 10–10 m ⁄ s )( 530 m2 ⁄ g )( 2.8 × 106 g ⁄ m3 )

f1 5 0.003 m -------------------------------------------------------------------------------------------------------------
-
1.82 × 10–8 m2 ⁄ s

f1 5 18
8 L. K. Chan, A. F. Sarofim, and J. M. Beer, Combust. Flame, 52, 37.
Section 15.7 Mass Transfer and Reaction in a Packed Bed 749

Because f1 is large

3 3
η≅ = = 0.167
φ1 18
1. Calculate CWP
2
CWP = ηφ

5 (0.167)(18)2 5 54.
CWP >> 1 and internal diffusion limits the reaction
2. To calculate the external mass transfer coefficient, the Thoenes–Kramers cor-
relation is used. From Chapter 14 we recall
Sh9 5 (Re9)1/2 Sc1/3 (14-65)
For a 2-in.-ID pipe, Ac 5 2.03 3 1023 m2 . The superficial velocity is
v 1026 m3 ⁄ s -
U 5 -----0- = ---------------------------------- = 4.93 × 1024 m ⁄ s
A c 2.03 × 1023 m2
Procedure
Calculate
Re9 Udp ( 4.93 × 1024 m ⁄ s ) ( 6 × 1023 m )
Re9 5 ------------------
- = ------------------------------------------------------------------------
- = 386.7
Sc (1 – φ) ν ( 1 – 0.5 )( 1.53 × 1028 m2 ⁄ s )
Then
Sh9
Then
Nomenclature note: f with subscript 1, f1 5 Thiele modulus
kc f without subscript, f 5 porosity

ν 1.53 × 1028 m2 ⁄ s
Sc 5 ---------- = ---------------------------------------
- = 0.765
DAB 2.0 × 1028 m2 ⁄ s
Sh9 5 (386.7)1/2 (0.765)1/3 5 (19.7)(0.915) 5 18.0

1–φ  DAB 0.5  2.0 × 1028 ( m2 ⁄ s )

k c 5 ----------  ---------- Sh′ = -------  -----------------------------------------  ( 18.0 )
φ  dp  0.5  6.0 × 1023 m 

k c 5 6 3 1025 m/s

3. Calculating the external area per unit reactor volume, we obtain

6 (1 – φ) 6 ( 1 – 0.5 )
ac = ------------------ = -------------------------
dp 6 × 1023 m (E15-3.5)
2 3
= 500 m ⁄ m
4. Evaluating the overall effectiveness factor. Substituting into Equation (15-58),
we have
η
Ω = --------------------------------------------
1 + ηk″1 S a ρb ⁄ k c ac
0.167
Ω = --------------------------------------------------------------------------------------------------------------------------------------------------
0.167 )( 4.4 × 10–10 m3 ⁄ m2 ⋅ s )( 530 m2 ⁄ g )( 1.4 × 106 g ⁄ m3 -)
(----------------------------------------------------------------------------------------------------------------------------------------
1+
( 6 × 10–5 m ⁄ s )( 500 m2 ⁄ m3 )
0.167
= ------------------ = 0.059
1 + 1.83
In this example we see that both the external and internal resistances to mass
transfer are significant.
750 Diffusion and Reaction Chapter 15

5. Calculate the Mears criterion, MR, to see if mass transfer limits the reaction.
– r′A ρ bRn Ω( –rAb )Rn
MR = ---------------------
- = --------------------------
k cCAb k cCAb

Ωk′1 CAbρbR Ωk′ρbR

= -----------------------------
- = -------------------
k cCAb kc

( 0.059 )( 2.34 × 10 m ⁄ g ⁄ s ) 1.4 × 10 ------3 ( 3 × 10 m )

–7 3 –6 g –3
 m
= ------------------------------------------------------------------------------------------------------------------------------
–5
-
6 × 10 m ⁄ s
5 0.97
MR (i.e., 0.97 > 0.15) and diffusion limits the reaction.
6. Calculating the weight of solid necessary to achieve 99.8% conversion. Sub-
stituting into Equation (E15-3.3), we obtain

1 × 10–6 m3 ⁄ s 1
W = ----------------------------------------------------------------------------------------------------
- ln ---------------------
( 0.059 )( 4.42 × 10–10 m3 ⁄ m2 ⋅ s )( 530 m2 ⁄ g ) 1 – 0.998
= 450 g
7. The reactor length is
450 g
W - = -----------------------------------------------------------------------------
L = -----------
Ac ρb ( 2.03 × 10–3 m2 )( 1.4 × 106 g ⁄ m3 )
= 0.16 m
This catalyst weight and corresponding reactor length are rather small and as such
we could easily increase the feed rate to the reactor.

Analysis: One of the purposes of this example was to show how to carry out
detailed calculations of the diffusion and reaction rate in order to size (i.e., calculate
V or W) a reactor for a specified conversion, when both external and internal diffu-
sion resistances affect the rate of reaction. These calculations are tedious and
detailed, and it was my feeling that we should show and know all the intermediate
calculations, e.g., ac, h and V, so that the reader will have a better understanding of
how to make such calculations in the future.

15.8 Determination of Limiting

Situations from Reaction-Rate Data
For external mass transfer-limited reactions in packed beds, the rate of reaction
per unit mass of catalyst at a point in the bed is
–r′A 5 kc acCA (15-72)
Variation of The correlation for the mass transfer coefficient, Equation (14-66), shows that
reaction rate with kc is directly proportional to the square root of the velocity and inversely pro-
system variables
portional to the square root of the particle diameter
U1 ⁄ 2
k c ∝ ---------
- (15-73)
dp1 ⁄ 2
Section 15.9 Multiphase Reactors in the Professional Reference Shelf 751

We recall from Equation (E15-3.5), ac = 6(1 – φ)/dp, that the variation of exter-
nal surface area with catalyst particle size is
1
ac ∝ -----
dp
We now combine Equations (15-72), (15-73), and (15-74) to obtain
1⁄2
U
–r′A ∝ ---------
- (15-74)
dp3 ⁄ 2
Consequently, for external mass transfer–limited reactions, the rate propor-
tional to the velocity to the one-half power is inversely proportional to the par-
ticle diameter to the three-halves power.
From Equation (14-72), we see that for gas-phase external mass transfer–
limited reactions, the rate increases approximately linearly with temperature.
When internal diffusion limits the rate of reaction, we observe from Equa-
Many
heterogeneous tion (15-42) that the rate of reaction varies inversely with particle diameter, is
reactions are independent of velocity, and exhibits an exponential temperature dependence
diffusion limited. that is not as strong as that for surface-reaction-controlling reactions. For sur-
face-reaction-limited reactions, the rate is independent of particle size and is a
strong function of temperature (exponential). Table 15-1 summarizes the depen-
dence of the rate of reaction on the velocity through the bed, particle diameter,
and temperature for the three types of limitations that we have been discussing.
TABLE 15-1 LIMITING CONDITIONS

Variation of Reaction Rate with:

Type of
Very Important Limitation Velocity Particle Size Temperature
Table
External diffusion U 1/2 (dp )23/2 <Linear
Internal diffusion Independent (dp )21 Exponential
Surface reaction Independent Independent Exponential

The exponential temperature dependence for internal diffusion limita-

tions is usually not as strong a function of temperature as is the dependence for
surface reaction limitations (cf. Section 15.4). If we would calculate an activa-
tion energy between 8 and 24 kJ/mol, chances are that the reaction would be
strongly diffusion-limited. An activation energy of 200 kJ/mol, however, sug-
gests that the reaction is reaction rate–limited.

15.9 Multiphase Reactors in the Professional

Reference Shelf
Multiphase reactors are reactors in which two or more phases are necessary to
carry out the reaction. The majority of multiphase reactors involve gas and liq-
uid phases that contact a solid. In the case of the slurry and trickle bed reac-
tors, the reaction between the gas and the liquid takes place on a solid catalyst
surface (see Table 15-2). However, in some reactors the liquid phase is an inert
medium for the gas to contact the solid catalyst. The latter situation arises
when a large heat sink is required for highly exothermic reactions. In many
cases, the catalyst life is extended by these milder operating conditions.