Lecture on

Fluid-solid Catalytic Reactions: Internal Mass Transfer

Effects

Instructor

Prof. Bishnupada Mandal

Room No. 102, Block - K
Department of Chemical Engineering
Indian Institute of Technology Guwahati

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 Lecture 7: Internal Mass Transfer Effects

Lecture Outline
• Recap on previous lecture
• External heat transfer limitations
• Introduction to internal mass transfer limitations
• Derivation of concentration profile of reactant for single
cylindrical pore geometry
• Concept of effectiveness factor and Thiele modulus
• Derivation of concentration profile of reactant for
catalyst slab and spherical geometry
 External Heat Transfer Limitations:

 So far, we have dealt almost exclusively with reactions occurring at

constant temperature (isothermally), and have written equations to
describe changes in concentrations, but not changes in
temperature.

 However, since heat transfer limitations near and within a catalyst

particle are closely related to mass transfer limitations, it makes
sense for us to treat them together in this set of notes.

 We will pay much more attention to equations describing changes

in temperature (energy balances) and will very often deal with non-
isothermal reactions and reactors.
 External Heat Transfer Limitations:

 It is often the case that temperature changes across the external

boundary layer are more important than concentration changes.
These are correlated in the same way, using a heat transfer
coefficient.

q = hf (Tb – Ts)

 where q is the heat flux (energy per area per time) to the particle
surface

 hf is a heat transfer coefficient, and

 Tb and Ts are the bulk and surface temperatures, respectively.

 External Heat Transfer Limitations:
 An energy balance at the surface shows that this flux must be equal to
the rate at which energy is consumed by reaction.

 This is the reaction rate multiplied by the heat of reaction, ∆Hrxn r″.

 But this is not as simple as the analysis of mass transfer, because the
reaction rate is strongly and nonlinearly dependent on the temperature
(where as it depends linearly on concentration for the assumed 1st
order reaction).

 For combined heat and mass transfer limitations, we can write the
coupled balance equations:
kr C As  k g  C Ab  C As 
H rxn kr C As  h f Tb  Ts 
 External Heat Transfer Limitations:

 For combined heat and mass kr C As  k g  C Ab  C As 

transfer limitations, we can write the
coupled balance equations: H rxn kr C As  h f Tb  Ts 

 Including the Arrhenius dependence   Ea 

A exp   C As  k g  C Ab  C As 
of the rate constant on temperature,  RTs 
this is   Ea 
H rxn A exp   C As  h f Tb  Ts 
 RTs 

 Eliminating CAs from the equations hf

using C As  C Ab  Tb  Ts 
H rxn k g
 External Heat Transfer Limitations:

 Including the Arrhenius dependence  E 

of the rate constant on temperature, A exp  a  C As  k g  C Ab  C As 
 RTs 
this is
 E 
H rxn A exp  a  C As  h f Tb  Ts 
 RTs 

 Eliminating CAs from the equations

hf
using C As  C Ab  Tb  Ts 
H rxn k g
 Gives
  Ea  hf 
H rxn A exp   C Ab  Tb  Ts   h f Tb  Ts 
 RTs   H rxn k g 

 This can’t readily be solved analytically, but can be solved numerically.

 External Heat Transfer Limitations:

 We can show graphically that this equation can lead to multiple

steady states (multiple solutions of this equation) for the temperature
in the catalyst when ∆Hrxn is negative (exothermic reaction). The
below equation can be rearranged to give

  Ea  hf 
H rxn A exp   C Ab  Tb  Ts   h f Tb  Ts 
 RTs   H rxn k g 

  Ea 
k g A exp   C Ab
h f Ts  Tb    H rxn   RTs 
 E 
k g  A exp  a 
 RTs 
 External Heat Transfer Limitations:

 The term on the left-hand-side can

  Ea 
be identified as the heat transfer k g A exp   C Ab
rate (flux of heat away from the h T  T    H   RTs 
 E 
f s b rxn
particle) while the term on the k g  A exp  a 
right-hand-side can be identified  RTs 
as the heat release rate by the
chemical reaction.

 It is the effective rate constant (the harmonic mean of the reaction

rate constant and the mass transfer coefficient) multiplied by the
heat of reaction and the bulk concentration of reactant.

 When plotted vs. Ts, the left-hand-side is a straight line, and the right-
hand-side is a sigmoidal (s-shaped) curve.
 External Heat Transfer Limitations:

  Ea 
k g A exp   C Ab
h f Ts  Tb    H rxn   RTs 
  Ea 
k g  A exp  
 s
RT

 These curves can intersect at 1 or

three points, depending on the
values of the parameters.

 This is illustrated in the plot shown,

where they intersect at 3 points (3
steady states possible).
 Introduction to Internal Mass Transfer Limitations
 The total reaction rate for a surface reaction, in the absence of
transport limitations, is proportional to the total surface area.
 Catalyst materials usually contain many small pores, because this
allows them to have much greater surface area than if they were
simply larger, solid pieces.
 The surface to volume ratio of an object (with fixed shape) is inversely
proportional to its size. For example, consider the surface to volume
ratio of spheres of different sizes.
 The surface area is
4 r 2

 The volume is  4 / 3  r 3

 So the surface to volume ratio is 3

r  or 6 
d
 Introduction to Internal Mass Transfer Limitations
 The surface area is
4 r 2
 The volume is  4 / 3  r 3

 So the surface to volume ratio is 3

r  or 6 
d

 So as we decrease the radius of the sphere, the surface area per

volume increases.
 Imagine that we start with a 3 cm diameter sphere, and we
repeatedly divide it into smaller pieces and roll them into spheres
(keeping the same total amount).
 Introduction to Internal Mass Transfer Limitations
 Imagine that we start with a 3 cm diameter sphere, and we
repeatedly divide it into smaller pieces and roll them into spheres
(keeping the same total amount).
 The increase in surface area would be as follows:
Sphere Number of Total Total Surface
Radius (cm) Spheres Volume Surface to Volume
(cm3) Area (cm2) Ratio
(cm-1)
3.00E+00 1.00E+00 1.13E+02 1.13E+02 1.00E+00
3.00E-01 1.00E+03 1.13E+02 1.13E+03 1.00E+01
3.00E-02 1.00E+06 1.13E+02 1.13E+04 1.00E+02
3.00E-03 1.00E+09 1.13E+02 1.13E+05 1.00E+03
3.00E-04 1.00E+12 1.13E+02 1.13E+06 1.00E+04
3.00E-05 1.00E+15 1.13E+02 1.13E+07 1.00E+05
3.00E-06 1.00E+18 1.13E+02 1.13E+08 1.00E+06
3.00E-07 1.00E+21 1.13E+02 1.13E+09 1.00E+07
3.00E-08 1.00E+24 1.13E+02 1.13E+10 1.00E+08
 Introduction to Internal Mass Transfer Limitations
 If we were carrying out a reaction on the Sphere Number Total Total Surface
surface of these spheres, then the total Radius of Volume Surface to
reaction rate would scale with the total (cm) Spheres (cm3) Area Volume
(cm2) Ratio
surface area. (cm-1)
3.00E+00 1.00E+00 1.13E+02 1.13E+02 1.00E+00
 So, for example, with the same amount of
3.00E-01 1.00E+03 1.13E+02 1.13E+03 1.00E+01
catalyst material, spheres of 3 µm diameter 3.00E-02 1.00E+06 1.13E+02 1.13E+04 1.00E+02
would give a reaction rate 10,000 times 3.00E-03 1.00E+09 1.13E+02 1.13E+05 1.00E+03
greater than spheres of 3 cm diameter. 3.00E-04 1.00E+12 1.13E+02 1.13E+06 1.00E+04
3.00E-05 1.00E+15 1.13E+02 1.13E+07 1.00E+05
 The same effect is achieved by making the 3.00E-06 1.00E+18 1.13E+02 1.13E+08 1.00E+06
catalyst porous. Many catalysts have an 3.00E-07 1.00E+21 1.13E+02 1.13E+09 1.00E+07
average pore size below 10 nm, which 3.00E-08 1.00E+24 1.13E+02 1.13E+10 1.00E+08
allows them to have surface areas of
hundreds of square meters per gram of
catalyst.
 How many square meters of floor space do you have in your house or apartment? Unless
you are an unusually wealthy student, it is less than the surface area of a gram of the
catalyst that you would find in a catalytic cracking unit.
Derivation: Concentration Profile for Single Cylindrical Pore
 In order for us to take advantage of
the large surface area provided by
porous catalysts, reactants must be
able to diffuse into the pores and
access all of the surface area.
 As a first step in analyzing this
diffusive transport, let us consider
diffusion and reaction in a single pore
of length l and diameter dp.

 We will assume that reactant (A) and product (B) are diffusing in and out
of the pore, and that the reaction A → B occurs everywhere on the pore
walls, with a rate given by r = kr CA.
Derivation: Concentration Profile for Single Cylindrical Pore
 At the mouth of the pore, the reactant
concentration is CAs. Within the pore,
it is CA(x), where x is distance inside
the pore, and x = 0 at the pore mouth.
The diffusive flux of A inside the pore
is given by dC A
N A   DA
dx

 At the end of the pore (x = l), we will assume that either the wall is
unreactive or that the pore goes all the way through the catalyst pellet, so
that x = l is halfway through the catalyst, and the concentration profile is
symmetric about x = l.
 In either case, the diffusive flux at x = l is zero, and this gives us the
condition that dC A
0
dx
Derivation: Concentration Profile for Single Cylindrical Pore
 We can do a shell balance on a
differential length of pore inside the
catalyst:
Flux in – Flux out + Production by reaction = 0

 d p2 dCA   d p
2
 dC A 
 DA    DA    d p dxkr C A  0
4  dx  x 4  dx  x  dx

 Dividing this equation through by  d p2

DA dx
4

 and taking the limit as dx goes to zero gives us the differential equation
describing the diffusion inside the pore:
d 2 C A  4k r 
 C 0
dx 2  d D  A
 p A
Derivation: Concentration Profile for Single Cylindrical Pore
 We have the differential equation
describing the diffusion inside the
pore: 2  
d CA 4k r
2
   C A  0
dx  d p DA 

 This is often re-written as d 2C A

2
  2
CA  0
dx
1

 Where  4kr 
 
2

 d D 
 p A

 We need to solve this 2nd order ODE with the boundary conditions CA
(x=0) = CAs and
 dC A 
  0
 dx  x l
Derivation: Concentration Profile for Single Cylindrical Pore
 We have ODE: d 2C A
2
  2
CA  0
dx

 We need to solve this 2nd order ODE with the

boundary conditions CA (x=0) = CAs and  dC   0
A

 dx  x l

 This equation has the general solution

 where C1 and C2 are constants to be determined from the boundary

conditions.
 At x = 0, the boundary condition gives: CAs = C1 + C2
 At x = l, the boundary conditions gives
 From which
Derivation: Concentration Profile for Single Cylindrical Pore
 This equation has the general solution

 BC1 At x = 0: CAs = C1 + C2
 BC2 At x = l:
C As C As el C As e l
 Substituting this into the 1st BC gives C2  2  l
 l  l  C1  l  l
1 e e e e e

 So, the concentration profile is

 Effectiveness Factor
 So, the concentration profile is

 We are not actually interested in the details of the concentration profile,

but just in the overall effect on the reaction rate.
 We therefore want to integrate this concentration distribution over the
pore length to get an average reaction rate that we can compare to the
rate we would have with no diffusion limitations.
 This is usually described by an effectiveness factor, which is defined as
l

actual rate k Cr A ( x)dx

1 cosh( (l  x))
l
Effectiveness factor     0
  dx
ideal rate kr C As l l 0 cosh(l )
 Thiele Modulus
 This is usually described by an effectiveness factor, which is defined as
l

actual rate k Cr A ( x)dx

1 cosh( (l  x))
l
Effectiveness factor     0
  dx
ideal rate kr C As l l 0 cosh(l )

 The integral of the hyperbolic cosine function is the

hyperbolic sine function, so upon evaluating this integral,
we get
 The quantity λl that appears in this expression is a dimensionless
group that is generally called the Thiele modulus. It is usually
represented by the symbol, . Looking back at our definition of λ, we
see that the Thiele modulus is
1
 4kr  2

 
 d D 
 p A
 Effectiveness Factor vs. Thiele Modulus
 We have
1
 4kr  2

 
 d D 
 p A

 A plot of the effectiveness factor vs. the Thiele modulus looks like
 When the Thiele modulus is small, there
are no diffusion limitations, and the
effectiveness factor is 1.
 When the Thiele modulus is large, pore
diffusion is rate limiting, and the
effectiveness factor is inversely
proportional to the Thiele modulus.
 At a Thiele modulus of 1, the
effectiveness factor is about 0.76 – the
rate is about 24% below what it would be
if there were no pore diffusion
limitations.
 Effective Diffusion Coefficient
 The analysis for a single, ideal pore developed can be extended to treat
diffusion and reaction in a porous solid.
 For describing the diffusion of fluids in the pores of a solid catalyst, an
effective diffusion coefficient can be defined so that the flux per unit
external surface area of the pellet is given by the equation
dC A
N A   DeA
dx

 where NA is the flux, x is distance perpendicular to the pellet surface,

and DeA is the effective diffusivity.
 In most cases, we do not consider a convective component of the
transport inside the pores – the gas in them is assumed to be stagnant.
This is a good approximation because of their small size.
 Effective Diffusion Coefficient
 In most cases, we do not consider a convective
component of the transport inside the pores – the dC A
N A   DeA
gas in them is assumed to be stagnant. This is a dx
good approximation because of their small size.
 However, if there is a change in mole number on reaction so that the
moles of product diffusing out differs from the moles of reactant
diffusing in, then there will be a non-zero overall molar velocity inside
the pore.
 The mass-average velocity will still be zero – since mass is conserved
in the reaction.
 The effective diffusion coefficient is related to the ordinary diffusion
coefficient by the void fraction of the particle, εs, and the “tortuosity
factor” of the pores, .
 Effective Diffusion Coefficient
 The void fraction gives the fraction of the pellet
dC A
volume that consists of pores. One minus the N A   DeA
void fraction is the fraction of the pellet volume dx
that consists of solid material.
 Since the flux is defined in terms of the total external surface area of
the particle and diffusion in the total particle volume, the diffusion
coefficient needs to be multiplied by the void fraction to account for the
fact that only part of the external surface area consists of pores.
 Also, the concentration gradient in the expression above is computed
in terms of distance perpendicular to the catalyst surface.
 However, the actual pores are not straight cylinders, but follow some
sort of tortuous path that can be much longer than the straight-line
distance between points in the catalyst.
 Effective Diffusion Coefficient and Slab Geometry
 This is accounted for by dividing the diffusion coefficient by the
‘tortuosity factor’, . This tortuosity is the pore length per unit change in
the x coordinate, which goes in a straight line perpendicular to the
external surface of the catalyst.

 So, the effective diffusion coefficient may be related

to the actual diffusion coefficient by
 and the flux per unit area of catalyst is given by dC A
N A   DeA
 If our porous catalyst is in the form of a slab of dx
thickness 2l, then the analysis that we performed for
the single pore can be applied to the catalyst slab, tanh  

with the ordinary diffusion coefficient replaced by the 
effective diffusion coefficient described above. In that
case, the effectiveness factor is still
 Effective Diffusion Coefficient and Slab Geometry
 Effectiveness factor: tanh    Where the Thiele


modulus is now

 Since the pores are not uniform cylinders with a well-defined diameter, it is useful to
replace the pore diameter with an effective pore diameter that is defined based on
observable properties of the catalyst.
 For an infinitely long cylinder with diameter d, the surface to volume ratio is 4/d
 We usually can measure the surface area per unit mass of our catalyst (Sg).
 The pellet volume per unit mass is the inverse of the particle density (1/ρc).
 So, the average surface area to volume ratio of the catalyst is Sg ρc.
 This allows us to define an effective diameter by equating this to the surface to
volume ratio of an infinite cylinder.


 Analysis for a Spherical Catalyst Pellet
 We could carry out the same analysis for a spherical catalyst pellet
that we did for the single pore and slab. In that geometry, the equation
describing the concentration inside the pellet would be

 with boundary conditions dC A

0 at r = 0, and CA = CAs at r = R (the pellet
radius) dr
 R  sinh( r )
 This has the solution C A (r )  C As  
 r  sinh( R )
 where S g  c kr

DA s
3  coth    1
 which leads to an effectiveness factor 
 