Lecture on

External Diffusion and Heat Transfer Effects

Instructor

Prof. Bishnupada Mandal

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

Copyright ©: All contents in this lecture, no matter the form it takes (whether digital, print, or
media) is protected under copyright law. The contents are only for the purpose of academic use.
Lecture 6: External Diffusion and Heat Transfer Effects

Lecture Outline
• Recap on previous lecture
• External Mass Transfer Limitations
• External Heat Transfer Limitations
 Introduction
 Having considered the rates and mechanisms of reactions at solid surfaces,
we will now investigate how those chemical rate processes are coupled to
the physical rate processes that transport reactants to the active sites on
the surface and transport products away from those sites.
 As discussed in the previous lectures, for a catalytic reaction occurring in a
porous catalyst pellet, we can envision the overall reaction as a series of
seven sequential steps:
(1) Transport of reactants to the exterior surface of the catalyst pellet.
(2) Transport of reactants to active sites inside the pores.
(3) Adsorption of reactants onto the surface at active sites.
(4) Reaction on the surface.
(5) Desorption of products from the surface.
(6) Transport of products out of the pores to the pellet surface.
(7) Transport of products from the pellet surface to the bulk fluid.
 Steps in a Catalytic Reaction
 For the generic catalytic reaction A → B, this can be
illustrated schematically as:
 We will first focus on steps 3, 4, and 5
– which we might call the reactive
steps, as opposed to steps 1, 2, 6,
and 7, which involve only transport
and not chemical transformations.
 In subsequent lectures, we will
consider the effects of transport
limitations that can be both external
(steps 1 and 7) and internal (steps 2
and 6) to the catalyst pellet.
 Introduction

 For a spherical
catalyst particle, we
expect that transport
limitations lead to a
profile of reactant
concentration that
qualitatively looks
like the curve labeled
(c) in the picture
shown.
 Introduction

 Far from the catalyst pellet,

there is some bulk
concentration of reactant
(CAb).
 This is the variable that we
would like to use in our
reactor design equations,
and is generally the
concentration in which we
are interested.

 There is, in general, some concentration drop across a boundary layer near
the external surface of the particle, so that the concentration at the external
surface of the particle (CAs) differs from the bulk concentration.
 Introduction
 If the concentration at the
particle surface were
exactly the same as that in
the bulk, there would be no
driving force for transport
of reactant from the bulk to
the surface.
 The concentration drop
across the boundary layer
is usually described in
terms of a mass transfer
coefficient, kg.
 The flux of A across the boundary layer (moles per area per time) is given by
NA = kg(CAb – CAs).
 Introduction
 The reactant concentration
decreases further within the
particle, as the reactant
simultaneously diffuses
into the pores and reacts on
the pore walls.
 If there were no
concentration gradient,
there would be no driving
force for transport of
reactant into the particle.

 The coupled diffusion and reaction inside the particle has been the subject of
much study, and will be discussed in detail later on.
 Introduction

 In general, we want to
model the simultaneous
reaction and diffusion in the
pores to obtain a total
reaction rate for the whole
particle as a function of the
concentration at the
particles exterior surface.
 We want to model the
transport across the
boundary layer so that,
finally, we obtain the
reaction rate in terms of the
bulk concentration.
 Introduction
 There are 3 limiting cases
for the concentration
profiles. These are
illustrated above, as labeled
in the plot.
 If external mass transfer
(diffusion from the bulk to
the exterior surface of the
particle) is rate limiting,
then the majority of the
concentration drop will be
across the external  The reaction rate, in terms of the bulk
boundary layer, as shown in concentration, will be approximately
curve (d). given by kgCAb (moles per time per
external particle surface area).
 Introduction

 If internal mass transfer

(pore diffusion) is the rate
limiting step, then the
majority of the
concentration drop will be
inside the catalyst pellet, as
illustrated in curve (b).
 The reaction rate will
depend on factors like the
pellet size and pore
geometry.
 Introduction

 If there are no transport

limitations (reaction is rate-
limiting) then the
concentration will be nearly
equal to the bulk
concentration throughout
the pellet, as illustrated in
curve (a).
 If resistances to reaction,
external mass transfer, and
internal mass transfer are
all comparable, then a
concentration profile like
curve (c) will be observed.
 External Mass Transfer Limitations
 Before analyzing the more
complicated diffusion and
reaction inside the pellet, we will
consider the external mass
transport to the particle surface.
 Diffusion across a boundary layer
with reaction at a solid surface is
illustrated schematically.
 If the reactant is consumed in a 1st order reaction at the solid surface,
then the reaction rate is r″ = kr CAs.
 The mass transfer rate across the boundary layer is NA = kg(CAb – CAs).
 Both of these rates are in moles (or molecules) per area per time.
 External Mass Transfer Limitations
 If the reactant is consumed in a
1st order reaction at the solid
surface, then the reaction rate is
r″ = kr CAs.
 The mass transfer rate across the
boundary layer is NA = kg(CAb –
CAs).

 At steady state, these two rates must be equal (otherwise there would
be accumulation or depletion of A at the surface).
 This allows us to eliminate the unknown concentration at the surface
(CAs) and write the rate in terms of the bulk concentration (CAb)
 External Mass Transfer Limitations
 We can write:
kr CAs = kg(CAb – CAs)
 Rearranging:

 and the rate is k g kr

r  NA 
''
C Ab  keff C Ab
kr  k g

 where the effective rate constant

 External Mass Transfer Limitations
 The rate is k g kr
r  NA 
''
C Ab  keff C Ab
kr  k g

 where the effective rate constant

 The two limiting cases of this expression are

(1) a reaction-limited situation, where kr << kg, and therefore keff ≈ kr
(2) a mass transfer limited situation where kr >> kg, and therefore keff ≈ kg.
 External Mass Transfer Limitations
 If, instead of a 1st order reaction
at the surface we had an nth
order reaction at the surface,
then the rate would be related to
the bulk concentration by
n
 r'' 
r  kr  C Ab 
''

 kg
 
 Except for special cases (i.e. n = 0, 1, 2) this can’t be easily solved to
give the rate explicitly in terms of CAb, but it can always be solved
iteratively.
 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).