European Journal of Mechanics B/Fluids 29 (2010) 483–493

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European Journal of Mechanics B/Fluids

journal homepage: www.elsevier.com/locate/ejmflu

Convection, diffusion and reaction inside a spherical porous pellet in the

presence of oscillatory flow
Jai Prakash a , G.P. Raja Sekhar a,∗,1 , Sirshendu De b , Michael Böhm c
a
Department of Mathematics, Indian Institute of Technology Kharagpur, Kharagpur 721 302, India
b
Department of Chemical Engineering, Indian Institute of Technology Kharagpur, Kharagpur 721 302, India
c
Centre for Industrial Mathematics, University of Bremen, 28334 Bremen, Germany

article info abstract

Article history: The problem of convection, diffusion and reaction inside a spherical porous pellet is investigated
Received 15 July 2009 analytically. Unsteady Stokes equation is used for the flow outside the porous pellet and Darcy’s
Received in revised form law is used inside the pellet. A solenoidal decomposition method is employed for the hydrodynamic
22 April 2010
problem. Following the above findings, the convection–diffusion–reaction problem is formulated and
Accepted 18 May 2010
Available online 31 May 2010
solved analytically for a first order reaction. The behavior of the nutrient transport is discussed with
respect to various parameters like Darcy number, Peclet number, frequency and Thiele modulus. Also
Keywords:
the effectiveness factor corresponding to the first order reaction is computed.
Stokes flow © 2010 Elsevier Masson SAS. All rights reserved.
Darcy’s law
Porous pellet
Thiele modulus
Oscillatory flow
Nutrient transport

1. Introduction
Oscillatory flow has been an interesting subject of study for
years. Many applications of oscillatory flow to engineering prob-
lems have been investigated. Some of the examples are electro-
chemical reactors [1], soils [2], biofilms [3], and ultrafiltration [4].
It is well known that the mass transfer of a species is enhanced by
several orders of magnitude when it is present in a fluid medium
subjected to oscillatory motion. There are several examples of mass
transfer processes where oscillatory flow plays an important role.
Mass transport enhancement via oscillatory flow has been stud-
ied for numerous geometries: a curved tube (Eckmann and Grot-
berg [5]), a flexible tube (Dragon and Grotberg [6]), a tube with
conductive walls (Jiang and Grotberg [7]) and many more.
Large-pore permeable particles are currently used as catalysts
adsorbents, high performance liquid chromatography packing,
supports for biomass growth, ceramic membranes. The concept
behind various applications is that in large-pore materials
∗ The problem of convection and diffusion in permeable isother-
Corresponding author. Tel.: +91 3222 283684.
E-mail addresses: rajas@maths.iitkgp.ernet.in, rajasgp@gmail.com
(G.P. Raja Sekhar).
1 Part of work is done while the corresponding author is at Institute for Applied
Analysis and Numerical Simulation, University of Stuttgart, Pfaffenwaldring 57, D
70569 Stuttgart, Germany as Alexander von Humboldt Experienced Researcher.
0997-7546/$ – see front matter © 2010 Elsevier Masson SAS. All rights reserved.
doi:10.1016/j.euromechflu.2010.05.002
intraparticle mass transport is not only due to diffusion but also
due to convection inside the pores. In the present article, our
aim is to discuss the mass transport inside a spherical porous
catalyst in an oscillatory flow in which the convection–diffusion
process is coupled with isothermal first order reaction kinetics.
The coupling of chemical kinetics and mass transport process in
porous catalytic particles has been the subject of intense study for
a long time. An extensive study of the earlier work can be found
in the treatise, The Mathematical Theory of Diffusion and Reaction in
Permeable Catalysts by Aris [8]. In fact, several studies have shown
that the total transport rate inside the particle can be enhanced
significantly due to the contribution of intraparticle convection in
large-pore catalysts. The importance of intraparticle convection on
catalyst particles is shown by Komiyama and Inoue [9]. They solved
the problem of intraparticle convection–diffusion and reaction in
a finite cylinder parallel to the flow for a first order reaction
and provided a technique to obtain the intraparticle velocity.
A theoretical justification describing the effect of intraparticle
convection for an irreversible, isothermal first order reaction is
given by Nir and Pismen [10] for rectangular (slab), cylindrical and
spherical geometries.
mal particles was discussed by Rodrigues et al. [11] and the anal-
ogy between slab and spherical geometries was established. Lu
et al. [12] extended this convection–diffusion study to convec-
tion–diffusion–reaction study with first order reaction. Convec-
tive flow inside non-isothermal catalyst was studied by Rodrigues
484 J. Prakash et al. / European Journal of Mechanics B/Fluids 29 (2010) 483–493

internal flow field and the effect of intraparticle convection

Nomenclature on porous catalyst particles was shown by Stephanopoulos
and Tsiveriotis [16]. They considered the combined convec-
a radius of the porous pellet [m] tion–diffusion–reaction problem with zeroth order kinetics to ob-
k permeability of the porous pellet [m2 ] tain the intraparticle flow field and intraparticle nutrient transport
r radial distance inside the pellet. However, as mentioned earlier, the mass transfer
X position vector of species will be enhanced significantly in the presence of oscil-
ve oscillatory velocity external to the porous pellet latory motion. Hence, it is worth investigating the corresponding
[m/s] problem in case of oscillatory flow. Recently, Khaled and Vafai [17]
pe oscillatory pressure external to the porous pellet wrote a review article on the role of porous media in modeling flow
[N/m2 ] and heat transfer in biological tissues. It is mentioned that in appli-
Ve amplitude of the oscillatory velocity external to the cations like osteoinductive devices for repair of bone defects, ad-
porous pellet [m/s] sorptive separation by high performance liquid chromatography,
Pe amplitude of the oscillatory pressure external to the transport of macromolecules in deformed artery walls convective
porous pellet [N/m2 ] transport needs to be considered.
Vi velocity internal to the porous pellet [m/s] The present article considers the mass transport inside
Pi pressure internal to the porous pellet [N/m2 ] a spherical porous catalyst in an oscillatory flow in which
p0 constant [N/m2 ] the convection–diffusion process is coupled with isothermal
U characteristic velocity [m/s] first order reaction kinetics. Unsteady Stokes equation is used
V0 basic velocity [m/s] outside the porous pellet and Darcy’s law inside the porous
pellet. The intraparticle flow field is obtained by the solenoidal
V∗ velocity due to the disturbance [m/s]
decomposition of the external velocity field. The computed
A, B scalars
hydrodynamic part is used to evaluate the nutrient transport
fn modified spherical Bessel function of first kind
via the combined convection–diffusion–reaction equation. It is
gn modified spherical Bessel function of second kind
well known that mass transfer resistance is expressed in terms
Sn , Tn spherical harmonics of mass transfer coefficient. The non-dimensional form of mass
Pnm associated Legendre polynomial transfer coefficient is Sherwood number. Sherwood number is
ci concentration inside the porous pellet [mole/m3 ] proportional to Peclet number (Sh ∼ Pe1/3 ) [16]. It is established
k′ rate constant [s−1 ] in Eq. (36) of Stephanopoulos and Tsiveriotis [16] that the
D diffusivity [m2 /s] ratio of internal to external mass transfer resistances for the
c0 concentration at surface of the porous pellet permeable spherical particle is much greater than 1. Therefore,
[mole/m3 ] one can neglect the external mass transfer resistance in the
c̃ dimensionless concentration treatment of convection–diffusion–reaction problem inside a
Da Darcy number permeable particle. The combined convection–diffusion–reaction
Pe Peclet number problem is solved for first order reaction occurring in the
|Vθe | magnitude of external tangential velocity spherical porous pellet subject to the Dirichlet boundary condition.
|V i | magnitude of internal velocity Analytical expressions are obtained for concentration profiles and
the behavior of concentration profile with various parameters
Greek symbols involved is discussed. It is shown in [10] that intraparticle
convection enhances the effectiveness of a first order reaction.
θ inclination Hence, the variation of effectiveness factor with parameters
ϕ azimuth angle involved is analyzed. Some comparisons are done with the existing
α slip coefficient results.
λ dimensionless parameter
ω frequency of oscillation [s−1 ] 2. Mathematical formulation
̟ dimensionless frequency of oscillation
ρ density of the fluid [kg/m3 ] A spherical porous pellet of radius a and permeability k is
µ dynamic viscosity [kgm−1 s−1 ] considered in an arbitrary oscillatory Stokes flow of a viscous
incompressible fluid (Fig. 1). It is assumed that the flow outside
ν kinematic viscosity [m2 /s]
the porous pellet is governed by unsteady Stokes flow and the
φ Thiele modulus
flow inside is described by steady Darcy’s law. It may be noted
χn eigenvalue of differential operator
that Looker and Carnie [18] have shown that homogenization
ψn symbol for the eigenfunction of a differential
of unsteady Stokes equations inside porous medium gives time
operator independent Darcy’s equation and hence the flow inside the pellet
ηc effectiveness factor governed by steady Darcy’s law is justified. Consequently, the flow
inside the pellet (r < a) is governed by the Darcy’s law and
continuity equation:
and Quinta [13]. They considered a slab geometry and the effect
of intraparticle convection on the effective diffusivity measure- k
Vi = − ∇ P i, (1)
ment was analyzed. Lopes et al. [14] have shown that when in- µ
traparticle convection is important, non-isothermal effect plays a
significant role in the intraparticle flow field of catalyst particles. ∇ · Vi = 0, (2)
Cardoso et al. [15] have considered the interaction between trans- where, k is the permeability of the porous medium, µ is the
port of heat by conduction and convection, transport of reactants coefficient of viscosity of the fluid. The flow outside the pellet (r >
by diffusion, convection and chemical reaction within a porous cat- a) is described by the unsteady Stokes and continuity equations:
alyst particle of slab geometry. They used combination of pertur- ∂ ve
bation and integral techniques to derive approximate analytical ρ = −∇ pe + µ∇ 2 ve , (3)
solutions for the concentration profile for a first order, non- ∂t
isothermal reaction. The coupling of external flow field with ∇ · ve = 0, (4)
 J. Prakash et al. / European Journal of Mechanics B/Fluids 29 (2010) 483–493 485

corresponding non-dimensionalization forces that the solution of

Looker
√ and Carnie is valid for larger values of Brinkman parameter
a/ k. Similar limitations hold for the present investigation as
we employ Saffman’s condition at the porous–liquid interface
together with the continuity of pressure and continuity of normal
velocity. Hence, the boundary conditions on r = 1 are given by:
(i) Continuity of pressure field: P e = P i
(ii) Continuity of normal velocity component: Vre = Vri
(iii) Saffman’s boundary condition for the tangential components
of velocity field:
√ √ e
Fig. 1. Geometry of the problem. e Da ∂ Vθe e Da ∂ Vϕ
Vθ = , Vϕ = ,
α ∂r α ∂r
where ρ is the density of the fluid. For the case of oscillatory flow
where α is the dimensionless slip coefficient.
with frequency ω, we set the velocity and pressure fields ve and pe
as ve = Ve e−iωt and pe = P e e−iωt . Thus, the governing equations
transform to 2.2. Method of solution

−iρωVe = −∇ P e + µ∇ 2 Ve , (5) It may be noted that Eq. (9) which is the Stokes equation in the
e case of oscillatory flow is mathematically similar to the Brinkman
∇ · V = 0. (6)
equation that is frequently used for porous media except that the
Here V and P represent the velocity and pressure fields outside
e e
meaning of the parameter λ is different. Hence, some features of
the porous pellet, and Vi and P i are those of the flow inside the the existence theory for the Brinkman equation can be adopted.
porous pellet. The physical quantities are non-dimensionalized by Padmavathi et al. [22] have assumed that any velocity vector and
using the variables X̃ = Xa , Ṽ = UV , P̃ = PU . Here U is the pressure scalar satisfying equations of the form Eqs. (9) and (10)
µa
can be expressed as
magnitude of the far field uniform velocity. Therefore, the non-
dimensional equations for the flow inside the porous region (r < Ve = ∇ × ∇ × (Ae X) + ∇ × (Be X), (11)
1) take the form
∂
P e = p0 + [r (∇ 2 − λ2 )Ae ], (12)
Vi = −Da∇ P i , (7) ∂r
∇ · Vi = 0, (8) where X is the position vector of the current point, p0 is a
constant, and Ae and Be are unknown scalar functions satisfying the
and the corresponding equations for the fluid region (r > 1) equations
reduce to
∇ 2 (∇ 2 − λ2 )Ae = 0, (∇ 2 − λ2 )Be = 0. (13)
(∇ 2 − λ2 )Ve = ∇ P e , (9)
Moreover, Raja Sekhar et al. [23] have shown via solenoidal
∇ · Ve = 0, (10) decomposition of the velocity vector that the expressions given
2
where λ2 = − iωνa , and Da = ak2 is the Darcy number. Note that in Eqs. (11)–(13) form the general solution of Brinkman equation.
Furthermore, this complete general solution has been used to solve
we have omitted the symbol ˜ from Eqs. (7)–(10).
problems dealing with viscous flow past porous objects [24–26].
In the present investigation, we employ this complete general
2.1. Boundary conditions solution. Let us now assume that the velocity field V0 of the basic
flow, i.e., of the unperturbed flow in the absence of any boundaries
The obvious boundary condition at a permeable interface is is given by
the continuity of the normal velocity, which is consequence of
the incompressibility. In order to have a completely determined V0 = ∇ × ∇ × (A0 X) + ∇ × (B0 X), (14)
∞ h
flow of the free fluid, some condition on the tangential component X i
of the free fluid velocity needs to be specified at the interface. A0 = αn r n + βn fn (λr ) Sn (θ, ϕ),
n=1
Classically, vanishing of the tangential velocity of the free fluid
at the porous interface was supposed. However, this condition ∞
X
is not satisfactory for porous interface. Beavers and Joseph [19] B0 = γn fn (λr )Tn (θ, ϕ), (15)
proposed a new condition postulating that the difference between n=1

the slip velocity of the free fluid and the tangential component where Sn (θ , ϕ) and Tn (θ , ϕ) are spherical harmonics of the form
of seepage velocity is proportional to the shear rate of free
n
fluid. They have verified this law experimentally and found that X
Sn (θ, ϕ) = Pnm (ζ )(Anm cos mϕ + Bnm sin mϕ), ζ = cos θ , (16)
the proportionality constant depends linearly on square root of
m= 0
permeability. Saffman further studied the experimental boundary
n
condition of Beavers and Joseph and pointed out that the seepage X
velocity was much smaller than the other quantities hence may Tn (θ, ϕ) = Pnm (ζ )(Cnm cos mϕ + Dnm sin mϕ), ζ = cos θ , (17)
m=0
be dropped [20]. In general, while matching Darcy’s law with the
Stokes equation, continuity of pressure and continuity of normal where Pnm are associated Legendre polynomials and Anm , Bnm , Cnm ,
velocity components are used along with Saffman’s slip condition Dnm are the known coefficients. The coefficients αn , βn , γn are
for tangential velocity components [21]. Looker and Carnie [18] arbitrary constants and corresponding to a given basic flow in the
showed that Saffman’s boundary condition can be applied for absence of any boundaries, αn , βn , γn take a suitable form. For
oscillatory Stokes flows at least under low frequency. The example in case of uniform flow along the z-axis, we have α1 =
486 J. Prakash et al. / European Journal of Mechanics B/Fluids 29 (2010) 483–493
  
1/2, β1 = 0, γ1 = 0. In addition, the scalar functions A0 and B0 (1 − l2 λ2 )Z1 + (l2 λ2 + 2){X1 g1 (λ) + λ(α + l)(1 − l2 λ2 )g2 (λ)} g1 (λr ) 
satisfy Eq. (13). It may be noted that the scalars Ae , Be represent the −

2rZ1 g1 (λ)

flow field and the vector equations are now reduced to equivalent


scalar equations.
On the other hand, if the basic flow with the velocity field V0 × cos θ, (21)
is perturbed by the presence of a stationary porous pellet with the

 
radius r = 1, then the velocity field Ve of the resulting flow outside  X1 g1 (λ) + λ(α + l)(1 − l2 λ2 )g2 (λ) 2
Vθe = − 1 − −  g1 (λr ) − λg2 (λr )
 
the porous pellet is given by Ve = V0 + V∗ , where V∗ is the velocity  r 3 Z1 r
due to the disturbance flow such that V∗ → 0 as r → ∞. It may
be noted that in the above decomposition, the basic flow as well as  
(1 − l2 λ2 )Z1 + (l2 λ2 + 2){X1 g1 (λ) + λ(α + l)(1 − l2 λ2 )g2 (λ)} 
the perturbed flow are oscillatory in nature. Hence, the resulting
×

flow in the exterior region (r > 1) is given by 2Z1 g1 (λ)


∞ h
αn′ i
(22)
X
Ae = αn r n + + βn fn (λr ) + βn′ gn (λr ) Sn (θ , ϕ), (18) × sin θ,
n= 1
r n+1
and inside the porous pellet (r < 1)
∞ h
Vri = −l2 δ1 cos θ,
i
(23)
X
Be = γn fn (λr ) + γn′ gn (λr ) Tn (θ , ϕ), (19)
n=1 i 2
Vθ = l δ1 sin θ, (24)
where fn (λr ) and gn (λr ) are modified spherical Bessel functions
where
of first and second kind, respectively. Since in the porous region h i
(r < 1) the pressure field is harmonic and finite at the origin, it λ2 (lλ2 − 6α − 6l)g1 (λ) + 3λ(α + l)g2 (λ)
can be expressed as δ1 = ,
Z1
∞
and δ1 , X1 , and Z1 correspond to δn , Xn , and Zn when n = 1. The
X
P i = p0 + δn r n Sn (θ , ϕ), (20)
explicit solution calculated above for the hydrodynamic problem
n=1
has been used in order to evaluate the nutrient transport via the
where (r , θ, ϕ) are spherical coordinates with respect to the origin combined convection–diffusion–reaction equation (25).
chosen at the center of the sphere r = 1. In the above expressions The use of Saffman condition brings limitations on the
αn′ , βn′ , γn′ and δn are unknown constants that are determined from permeability range. Looker and Carnie [18] concluded that Saffman
the boundary conditions and are obtained in terms of the known condition is applicable under low frequency. Vainshtein and
coefficients αn , βn and γn as follows: Shapiro [27] calculated the force acting on a permeable particle
αn′ = (n + 1) in oscillatory flow using the Brinkman and the Darcy equation.
h i However, they have used continuity of velocity components
{Xn gn (λ) + λ(α + l)(1 − l2 λ2 )gn+1 (λ)}αn + λ(α + l)Yn βn together with the continuity of stress components. It may be
× , noted that in case of Brinkman equation these boundary conditions
Zn are accepted by a large community, whereas in case of Darcy
(n + 1){(1 − l λ )αn + fn (λ)βn } + (n + 1 + nl2 λ2 )αn′
2 2
equation, the continuity of tangential velocity needs to be replaced
βn′ = − , by Beavers–Joseph/ Saffman type slip condition. Vainshtein and
(n + 1)gn (λ)
Shapiro
√ [27] identified a critical value of the Brinkman parameter,
γn {(α − nl)fn (λ) − lλfn+1 (λ)}
γn′ = , a/ k, that controls the applicability of Darcy equation. They
(nl − α)gn (λ) − lλgn+1 (λ) also observed that this critical value diminishes with decreasing
δn = λ2 {nαn′ − (n + 1)αn }, frequency of oscillations and reaches that of a non-oscillating
particle ≈10. It seems that critical value can be as large as 200
where
for high frequency of oscillations. For low and moderate values
Xn = λ2 {l2 (n + 1)α − l3 (n2 + λ2 − 1) − l}, of frequency, one can identify the corresponding critical value
of the Brinkman parameter. Hence, the hydrodynamic problem
Yn = fn (λ)gn+1 (λ) + fn+1 (λ)gn (λ),
h of oscillatory flow past a porous sphere with Darcy equation
Zn = l{n(n + 1)(n + 2) − (n2 + λ2 − 1)(nλ2 l2 + n + 1)} inside subject to Saffman condition limits one to consider only a
i particular range of permeability.
+ α(n + 1)(nλ2 l2 + 2n + 1) gn (λ)
− λ(α + l)(nλ2 l2 + n + 1)gn+1 (λ), 3. Nutrient transport inside the porous pellet
√
l= Da. The hydrodynamic velocity components internal to the porous
The velocity components both outside and inside the pellet can pellet that are computed in the previous section are incorporated
be obtained using the above expressions. In case of uniform in the definition of the combined transport–reaction problem. In
what follows a solution is presented for the case of a spherical
flow along z-axis, setting V0 = U k̂, we may notice that the
porous catalyst. Assuming an isothermal first order reaction
corresponding expressions for A0 and B0 in dimensionless form are
kinetics and diffusivity D, the nutrient mass balance can be written
A0 = 21 r cos θ, B0 = 0. Comparing with the general expressions
as
given in Eq. (15), we have α1 = 12 , β1 = 0 and γ1 = 0. In this case,
the corresponding velocity components in fluid region (r > 1) are Vi · ∇ ci = D∇ 2 ci − k′ ci . (25)
On using the expressions for velocity V given in Eqs. (23) and (24),
i

 X1 g1 (λ) + λ(α + l)(1 − l2 λ2 )g2 (λ) we have from Eq. (25)
Vre = 1 +

r 3 Z1
− Ul2 δ1 k̂ · ∇ ci = D∇ 2 ci − k′ ci .

(26)
 J. Prakash et al. / European Journal of Mechanics B/Fluids 29 (2010) 483–493 487

Eq. (25) applies to a spherical pellet with a concentration boundary With respect to the inner product
condition at the porous–liquid interface equal to the bulk nutrient Z 1
concentration
hf , g i = f (x)g (x)dx, (39)
−1
ci = c0 on r = a. (27)
the differential operator of Eq. (36) is self-adjoint and its
Now, the physical quantities are non-dimensionalized by using eigenfunctions are orthogonal. Using this inner product, Eqs. (34)
ci
the variables X̃ = Xa , c̃ = c . After non-dimensionalization the and (35) can be projected to the eigenfunction space, yielding
0
governing equation together with the boundary condition is given ! !
by 2 Pe2 l4 δ12 1 ∂
∂ Hn 2 1
φ + Hn = 2 ξ − n(n + 1) Hn , (40)
4 ξ ∂ξ ∂ξ ξ2
−Pe l2 δ1 k̂ · ∇ c̃ = ∇ 2 c̃ − φ 2 c̃, (28)
Z +1 !
c̃ = 1, on r = 1, (29) 2 Pe l2 δ1 ζ
Hn (1) = exp Pn (ζ )dζ . (41)
with 2n + 1 −1 2

k′ a2 Ua The solution of Eq. (40) with Eq. (41) as boundary condition is given
φ2 = , Pe = , (30) by the following series:
D D
where φ is the Thiele modulus corresponding to the above problem Hn (ξ ) = an (ξ )n Fn (ξ ). (42)
and Pe is the Peclet number. The solution of Eq. (28) with boundary
condition (29) is obtained by introducing the transformation Therefore Eq. (40) reduces to the form
!
(2n + 1) ′ Pe2 l4 δ12
!
Pe l2 δ1 z ′′
Fn + 2
Fn − φ + Fn = 0, (43)
c̃ = ĉ exp − , z = r cos θ, (31) ξ 4
2

which reduces Eq. (28) to the form since ξ is a regular singular point of Eq. (43), we assume the
solution of the form
Pe2 l4 δ12 ∞
ĉ = (∇ 2 − φ 2 )ĉ in r < 1. (32) X
4 Fn (ξ ) = bm ξ m , (44)
m=0
The corresponding boundary condition takes the form
! and solve Eq. (43). As a result, we get b1 = 0 and obtain the
Pe l2 δ1 cos θ following recurrence relation
ĉ = exp , on r = 1. (33)
2 !
Pe2 l4 δ12
In spherical coordinates, (r , θ, ϕ), Eqs. (32) and (33) become
φ2 + 4

bm = bm−2 . (45)
m(m + 2n + 1)
! !
2 Pe2 l4 δ12 2 ∂ ĉ 1 ∂
φ + ĉ = 2 ξ Since b1 = 0, bm = 0, m = 1, 3, 5, . . . , and for m even say
4 ξ ∂ξ ∂ξ
" # m = 2j, the expression for bm becomes
1 ∂ 2 ∂ ĉ
+ 2 (1 − ζ ) in r < 1, (34) !
ξ ∂ζ ∂ζ Pe2 l4 δ12
φ2 + 4
!
Pe l2 δ1 ζ b2j = b2j−2 . (46)
ĉ = exp , on ξ = 1 (35) 2j(2j + 2n + 1)
2
Eq. (46) can be written as
where ξ = r , ζ = cos θ . The differential operator with respect to !
ζ of Eq. (34) has the following form: 2 Pe2 l4 δ12
j
φ + 4
(L + χ)ψ = 0, (36) Y
b2j = b0 . (47)
where i=1
(n + 2i)2 + (n + 2i) − n(n + 1)
Therefore solution for Fn in terms of the variable r /a is given by
" #
d 2 d
L= (1 − ζ ) , !2j
dζ dζ !
∞
r X r
Fn = 1+
subject to the boundary conditions c̃ = 1 at z = ±1. a j=1
a
The only physically acceptable eigenfunctions of the above !
operator are the Legendre polynomials of first kind: Pe2 l4 δ12
2
φ + 4
ψn = Pn (ζ ) with eigenvalues χn = n(n + 1), j
Y
× , (48)
(n = 0, 1, 2, . . .). (37) i=1
(n + 2i)2 + (n + 2i) − n(n + 1)
Thus the following Legendre–Fourier series is assumed for the here b0 is taken as 1 for simplicity. Now from the boundary
solution of Eq. (34) condition given in (41), we have
! !
∞ ∞ +1
2n + 1 Pe l2 δ1 ζ
Z
X X r
ĉ = Hn (ξ )Pn (ζ ) = Hn Pn (cos θ). (38) Hn (1) = exp Pn (ζ )dζ ,
n=0 n=0
a 2 −1 2
488 J. Prakash et al. / European Journal of Mechanics B/Fluids 29 (2010) 483–493
( !)
+1
2n + 1 (−1)n dn Pe l2 δ1 ζ internal velocity with frequency and Darcy number. It is observed
Z
2 n
= (ζ − 1) exp dζ , that the internal velocity increases with both frequency and Darcy
2 2n n! −1 dζ n 2
number. Increase in Darcy number offers more volume flow in
to the porous region for a fixed pressure drop. Also, increase in
!n !
+1
2n + 1 Pe l2 δ1 Pe l2 δ1 ζ
Z
= (1 − ζ ) 2 n
exp dζ . (49) oscillation in the flow field induces enhancement in volumetric
2n+1 n! −1 2 2 flow inside the pellet for a fixed Darcy number.
We note that Hn (1) = an Fn (1), and hence from Eq. (49) we get
!n 4.2. Concentration profiles
+1 2
2n + 1 1
Z
Pe l δ1
an = (1 − ζ 2 )n The characteristics of the concentration profile is shown
2n+1 n! Fn (1) −1 2
graphically. Here nutrient concentration profile along the z-axis
! is given for a combination of various parameters involved in
Pe l2 δ1 ζ Eq. (51), like Darcy number (Da), frequency (̟ ), slip coefficient
× exp dζ . (50)
2 (α), Thiele modulus (φ) and Peclet number (Pe). Due to the
reaction inside the porous pellet, the concentration inside reduces
The expression (38) and the transformed equation (31) are used to compared to the bulk nutrient concentration at the surface. Also
obtain the nutrient concentration profile inside the pellet given by the concentration contours are influenced by the flow direction.
Fig. 4(a) shows the concentration profile in case of steady flow
!
Pe l2 δ1 r cos θ
i
c (r , θ) = c0 exp − i.e. ̟ = 0, for a fixed Da, α and φ . It can be seen that for
2a Pe = 0, there is a symmetry about the center of the pellet as
!n ! this is the case of diffusion only and the minimum concentration
∞
X r r occurs at z = 0. But for a non-zero Pe, the concentration
× an Fn Pn (cos θ), (51)
a a minimum is shifted in the direction of the flow due to convection.
n=0
The increase in minimum concentration with increasing Pe is
where Fn and an are given by Eqs. (48) and (50). It can be seen marginal. Effect of Peclet number on nutrient concentration profile
that 0 ≤ ci ≤ 1 in non-dimensional form and it is a convex is shown in Fig. 4(b) for the combination of parameters Da =
function. The above expression for the concentration corresponds 0.005, α = 0.5, φ = 1, ̟ = 3. It is seen that increasing Pe
to the Dirichlet boundary condition at the porous pellet surface. increases the overall nutrient concentration throughout the pellet.
Similar computations may help in order to use a flux condition and Since at low Peclet number diffusion dominates convection, the
the corresponding calculation is deferred for a future investigation. pellet cannot experience significant nutrient transport. However,
The above problem has been solved corresponding to first as Peclet number increases convection becomes a dominating
order reaction kinetics. There are other common kinetics such factor and hence nutrient transport increases inside the pellet. In
as, Michaelis–Menten kinetics, Monod kinetics, which occur in conclusion, as Pe increases, the nutrient concentration minimum
immobilized enzymes and growing populations of immobilized moves downstream while the overall nutrient content of the pellet
cells or microorganisms. But these kinetics lead to nonlinear increases.
problem and the present solution methodology is no more A comparison between steady and oscillatory flow is shown
valid to handle such type of kinetics. It may be mentioned in Fig. 5(a). It can be easily seen that oscillatory flow assists
that the kinetics dealt in the present article is a special case convection and hence more nutrient is transported inside the
of the Michaelis–Menten and Monod kinetic models, when the pellet compared to steady flow. Though the general tendency of
concentration tends to zero. Pe is to assist convection, in case of steady flow the effect of Pe
is marginal whereas in case of oscillatory flow it is substantial.
4. Results and discussion Effect of frequency on the nutrient concentration profile is shown
in Fig. 5(b) for the combination of parameters Pe = 100, Da =
The analytical solution derived in the previous sections allow us 0.005, α = 0.5, φ = 1. It is observed that as ̟ increases
to determine the velocity and nutrient concentration profiles. The the overall nutrient concentration increases inside the pellet. In
characteristics of the velocity and concentration profiles are shown conclusion, as ̟ increases, the nutrient concentration minimum
graphically. The frequency of oscillation is assumed to be between moves downstream while the overall nutrient content of the pellet
1 kHz and 10 kHz and a2 /ν = 10−3 s. increases.
Fig. 6(a) shows the concentration profile for the combination of
4.1. Velocity profiles parameters Pe = 100, ̟ = 3, α = 0.5, φ = 1 with varying
Da. Increasing Da offers less resistance and fluid flows easily
The tangential velocity component Vθe versus r /a is shown in through the pellet resulting enhancement of the overall nutrient.
Fig. 2. In general, fluid experiences less resistance in the presence The nutrient concentration minimum moves downstream with
of the porous pellet in comparison to impermeable particle, as increasing Darcy number. Fig. 6(b) shows the concentration profile
impermeable particle expects no slip on the surface. However, a for the combination of parameters Pe = 100, Da = 0.005, ̟ =
porous pellet with smaller Darcy number offers larger resistance 3, α = 0.5 with varying φ . When Thiele modulus is small,
compared to that of with larger Darcy number. It can be seen the reaction rate is less compared to the diffusion rate, and the
from Fig. 2(a) that when the frequency of oscillation is low, the pellet concentration becomes nearly uniform. For large values
magnitude of the uniform far field basic velocity slightly increases of the Thiele modulus, the reaction rate is large compared to
and near to the body the velocity reduces due to the resistance the diffusion rate and one can see sharp concentration gradients
offered by the particle. However, for large frequencies, the increase near the surface of catalyst. Stephanopoulos and Tsiveriotis [16]
in the magnitude of the uniform far field basic velocity is more considered the steady Stokes flow outside the porous pellet and
(Fig. 2(b)). When Da = 0, which corresponds to a solid particle, formulated the convection–diffusion–reaction problem for zeroth
the uniform far field velocity slightly increases before it realizes order reaction. They have obtained analytical expression for the
the resistance due to the particle and then decreases to satisfy the nutrient transport inside the pellet and observed starvation zone
no-slip condition. Fig. 3 shows the variation in magnitude of the inside the pellet for a particular choice of parameters involved. In
 J. Prakash et al. / European Journal of Mechanics B/Fluids 29 (2010) 483–493 489

a b

Fig. 2. Variation in magnitude of the external tangential velocity (Vθe ) with r /a.

a b

Fig. 3. Variation in magnitude of the internal velocity (V i ) with (a) frequency (̟ ). (b) Darcy number (Da).

a b

Fig. 4. Nutrient concentration profile along z-axis, Da = 0.005, α = 0.5, φ = 1. (a) steady case. (b) ̟ = 3.

order to avoid starvation a relationship between Peclet number
and the Thiele modulus was established. Prakash et al. [28] have
extended the study of Stephanopoulos and Tsiveriotis [16] to the
case of oscillatory flow and discussed the effect of frequency of
oscillation on nutrient transport and observed similar starvation
zones for some choice of parameters. It is noted that in the current
study which corresponds to first order reaction, we do not see
any such starvation zones. In case of zeroth order reaction, for
large values of the Thiele modulus, surface reaction is rapid. The
reactant is consumed fast into the interior of the pellet leading
to the exhaustion of the nutrient resulting to a starvation zone.
Whereas, in case of first order reaction kinetics, nutrient does not
get exhausted as the reaction proceeds and therefore no starvation
zones occur. It may be noted here that the starvation region
490 J. Prakash et al. / European Journal of Mechanics B/Fluids 29 (2010) 483–493

a b

Fig. 5. Nutrient concentration profile along the z-axis. (a) comparison between steady and oscillatory cases. (b) Pe = 100, Da = 0.005, α = 0.5, φ = 1 with ̟ .

a b

Fig. 6. Nutrient concentration profile along the z-axis. (a) Pe = 100, ̟ = 3, α = 0.5, φ = 1. (b) Pe = 100, Da = 0.005, ̟ = 3, α = 0.5.

mentioned above for zeroth order kinetics is a mere mathematical

description to limit the solution physically meaningful. In reality
the concentration at a location may not be zero or extremely
low, specially in cases like endogenous metabolism and substrate
uptake for cellular energetic, where the nutrient concentration
may be a finite value. Another idea to avoid such starvation is
to introduce the concept of dead zone. Valdés–Parada et al. [29]
derived an approximate solution for a stirred tank bioreactor with
nonlinear kinetics. The approximate solution contains a zero order
term that gives negative values of the concentration. In order to
avoid this they introduced a non-reaction zone called dead zone.
These kind of criterion [28,29] to avoid starvation display the
limitations of the models used.
In Fig. 7, we have shown the variation of concentration for the
combination of parameters Da = 0.005, ̟ = 3, α = 0.5, φ =
2.5 with varying Pe. It is seen that the concentration minimum
towards the center of the pellet decreases for large values of the
Thiele modulus. When Thiele modulus is equal to 1, rate of reaction Fig. 7. Nutrient concentration profile along the z-axis Da = 0.005, ̟ = 3, α =
0.5, φ = 2.5 with Pe.
and diffusion are comparable and the concentration minimum
towards the center does not decrease much but as the Thiele
modulus increases the reactant is consumed very fast into the to have convection the range of Pe is very high compared to
interior of the pellet and the concentration minimum towards a typical other material having large permeability. Hence, there
the center of the pellet decreases. In Fig. 8, we have shown a would be a trade-off between Da and Pe as depending on the
comparison with Da in the range similar to that of coarse gels material properties one has to choose suitable range. However,
(fibers) and polymers with that of a representative other material. since a particular material may have a fixed permeability, there
It may be noted that since fibers have low permeability, in order may be a limitation in order to vary permeability keeping effective
 J. Prakash et al. / European Journal of Mechanics B/Fluids 29 (2010) 483–493 491

a b

Fig. 8. Nutrient concentration profile along the z-axis for polymers, fibers with ̟ = 5, α = 0.5, φ = 1.

a b

Fig. 9. Variation of effectiveness factor (ηc ) with φ . (a) Pe = 200, Da = 0.007, α = 0.5. (b) Pe = 200, ̟ = 5, α = 0.5.

a b

Fig. 10. Variation of effectiveness factor (ηc ) with frequency (̟ ). (a) Da = 0.005, α = 0.5, φ = 1. (b) Pe = 100, α = 0.5, φ = 1.

diffusivity and vice versa. Hence, the simulations shown may be briefly by Nir and Pismen [10]. Hence, it is worth investigating
understood keeping this limitation in view. the impact of various parameters on the effectiveness factor.
The ratio of the observed reaction rate to the rate in the
absence of intraparticle mass transfer resistance is defined as the
4.3. Effectiveness factor effectiveness factor. The effectiveness factor in case of first order
reaction for a spherical geometry is defined as [10]
Strieder and Aris [30] have shown via variational inequalities
1
that the effect of first order reaction will be enhanced by 3
Z
∂ c̃
ηc = dζ . (52)
intraparticle convection and the same fact has been explained 2φ 2 −1 ∂r r =1
492 J. Prakash et al. / European Journal of Mechanics B/Fluids 29 (2010) 483–493
Fig. 11. Variation of Cmin with Darcy number (Da).
After some algebra we obtain
∞ [1] N. Carpenter, E. Roberts, Mass transport and residence time characteristics of
3π  Pe l2 δ 
1
(−1)n (2n + 1)In2+1/2
X
ηc =
φ 2 Pe l2 δ1 n=0 2
    2 
Pe l δ1 
 β In+3/2 β2

Pe l2 δ1 In+3/2 2
 [3] H. Nagaoka, Mass transfer mechanism in biofilms under oscillatory flow
×  −  2  ,
 2 In+1/2 β
 2 I
n+1/2
Pe l δ1 
2 2

q 1307–1324.
with β = Pe2 l4 δ12 + 4φ 2 .
Fig. 9 depicts the variation of effectiveness factor with Thiele
modulus for various values of ̟ and Da. It is clear that in the range
of φ < 1, the effect on ηc is marginal whereas the drop is striking
in the more practical range of 1 < φ < 10. Fig. 10(a) shows
the effectiveness factor for the combination of parameters Da =
0.005, α = 0.5, φ = 1 with varying ̟ . It is observed that
effectiveness factor increases with increase in Pe for a fixed ̟ .
This is because as Pe increases the surface reaction rate decreases
as a result effectiveness factor increases. Fig. 10(b) shows the
effectiveness factor for the combination of parameters Pe =
100, α = 0.5, φ = 1 with varying Da. Increasing Da enhances
the effectiveness factor for a fixed Pe and φ .
4.4. Variation of minimum concentration
For a fixed combination of other parameters, the variation of
minimum concentration with Da is shown in Fig. 11. It is seen that
the concentration minimum increases with increasing Da, due to
increased volume flow inside the pellet.
5. Conclusion
The nutrient transport inside a spherical porous pellet in an
oscillatory flow has been studied. The model assumes a spherical
porous pellet placed in an oscillatory Stokes flow. Darcy’s law is
used inside the porous pellet and unsteady Stokes equation is used
outside the pellet. Velocity and pressure fields are obtained and
the convection–diffusion–reaction problem is formulated for a first
order reaction kinetics. Effect of various parameters on the velocity
as well as concentration profile is shown. It is observed that the
internal velocity increases both with frequency and permeability,
hence for a fixed Darcy number, increase in frequency enhances
the volume flow inside the pellet. The effect of frequency on the
nutrient concentration profile is discussed for various combination
of parameters involved and a significant effect of frequency of
oscillation is seen on the nutrient transport inside the pellet. Effect
of the Thiele modulus on concentration profile is shown. It is seen
that for small values of the Thiele modulus nutrient diffuses very
well into the interior of the pellet and for large values of the
Thiele modulus the surface reaction is rapid and the concentration
minimum decreases towards the center of the pellet. Also the
effectiveness factor is obtained and the variation with various
parameters is shown graphically. A significant enhancement in the
effectiveness factor is observed.
Acknowledgements
The first author (JP) would like to recognize the support of
Council of Scientific and Industrial Research (CSIR), India. The
second author (GPRS) acknowledges the support by Alexander von
Humboldt Foundation, Germany for the Fellowship.
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