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 Author's personal copy

International Journal of Heat and Mass Transfer 54 (2011) 75–85

Contents lists available at ScienceDirect

International Journal of Heat and Mass Transfer

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

Effects of nonlinear chemical reactions on the transport coefficients associated

with steady and oscillatory flows through a tube
Suvadip Paul, B.S. Mazumder ⇑
Fluvial Mechanics Laboratory, Physics and Applied Mathematics Unit, Indian Statistical Institute, Kolkata 700 108, India

a r t i c l e i n f o a b s t r a c t

Article history: The paper concerns with the determination of effective transport coefficients associated with the
Received 5 June 2009 oscillatory flow through a tube where a solute undergoes nonlinear chemical reactions both within the
Received in revised form 8 June 2010 fluid and at the boundary. Method of homogenization, a multiple-scale method of averaging, is adopted
Accepted 25 August 2010
to derive the transport equation that contains advection, diffusion and reaction. The resultant equation
Available online 30 October 2010
shows how the transport coefficients are influenced by the rate and degree of the nonlinear chemical
reaction. Two different nonlinear reactions are considered at the bulk flow and the boundary. The reac-
Keywords:
tions at the boundary may be reversible and irreversible in nature. Several facts are established from the
Phase exchange
Homogenization
model by fixing the rate or degree of the nonlinear reactions. Results demonstrate that the reaction at the
Transport coefficient boundary is more influential than the bulk-flow reaction in determining the transport coefficients. Also
Nonlinear reaction fluid-phase reaction coefficient diminishes as the nonlinearity increases, whereas the trend is opposite
Phase partition coefficient for the nonlinear wall-phase reaction coefficient. Different controlling parameters are found to play sig-
nificant role on the transport coefficients when the ratio of wall-phase concentration to the fluid-phase
concentration is low.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction The phenomena of mass transport becomes more complex

Transport of solute through a tube has always been an impor-
tant topic in fluid mechanics. Due to its applications in the field
of chemical, environmental and biomedical engineering, mass
transport phenomena have been extensively studied during the
past fifty years. Investigation was initiated by Taylor [1] when he
published the landmark paper concerning the transport of a con-
taminant dissolved in a fluid flowing through a pipe of narrow
diameter. He demonstrated that an interaction between the trans-
verse variations in the fluid’s velocity field and the transverse dif-
fusion of the solute yielded an effective downstream mixing
mechanism for the solute. This mechanism has since been dubbed
‘Taylor Dispersion’. He found an approximate analytical formula
for the transport coefficient, more particularly for the dispersion
coefficient which is a measure of the rate at which a solute spreads
along the flow. Since then many related studies have been sur-
faced. Incorporating the effect due to molecular diffusion, Aris [2]
modified Taylor’s expression for the dispersion coefficient using
his method of moments. Later on Chatwin [3], Gill and Sankara-
subramanian [4], Smith [5], Sullivan [6], Pedley [7] and others con-
tribute significantly on this complex field.
⇑ Corresponding author. Tel.: +91 3325753033.
E-mail address: bijoy@isical.ac.in (B.S. Mazumder).
when the transported material is chemically reactive. Knowledge
of the transport coefficients associated with the flow of a reactive
species has applications as diverse as chromatographic separations
in chemical engineering, the spreading of pollutants in a stream,
the mixing and transport of drug and toxins in physiological sys-
tems and so on. Reactions originated from chemical or biological
processes are very common in aqueous environment. The fluid dy-
namic behaviour of the transport coefficients can be greatly influ-
enced by the presence of chemical processes like phase exchange,
partitioning, boundary uptake or chemical reactions. Transport
through these processes has widely been extended to applications
in biological or physiological transport (Davidson and Schroter [8],
Grotberg et al. [9], Phillips and Kaye [10]). Reactions may occur in
the bulk flow or at the boundary. It may be reversible or irrevers-
ible in nature and linear or nonlinear in degree. Linear reversible or
irreversible reactions at the boundary has received a considerable
attention by the researchers such as Gupta and Gupta [11], Purn-
ama [12], Mazumder and Das [13], Jiang and Grotberg [14], Sarkar
and Jayaraman [15], Mazumder and Mondal [16], Ng [17,18], Paul
and Mazumder [19] and others.
Thus prosperous literature exists on mass transport when the
transported substance is chemically inert or it undergoes a first or-
der chemical reaction either within the bulk flow or at the bound-
ary. But the case is different when the reactions are not linear. In
spite of its biological and industrial applications, less attention

0017-9310/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijheatmasstransfer.2010.08.028
 Author's personal copy

76 S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer 54 (2011) 75–85

Nomenclature

a radius of pipe T2 time scale for axial diffusion/dispersion

C concentration of mobile phase u axial component of velocity
Cs concentration of immobile phase us steady part of velocity
D molecular diffusion coefficient uw oscillatory part of velocity
Da Damkohler number t time
Deff effective dispersion coefficient x axial coordinate
DTs steady component of dispersion coefficient
DTw oscillatory component of dispersion coefficient Greek letters
k reversible reaction rate constant a partition coefficient
L characteristic longitudinal distance C rate of irreversible reaction at the boundary
m degree of nonlinear reaction at the boundary  perturbation parameter
n degree of nonlinear reaction in the bulk flow k rate of nonlinear reaction in the bulk flow
P pressure gradient ks rate of nonlinear reaction at the boundary
Pe Peclet number m kinematic viscosity
R nonlinear reaction term occurring in the bulk flow q density
Rs nonlinear reaction term occurring at the boundary w amplitude of pressure pulsation
R retardation factor x frequency of pressure pulsation
r radial coordinate d oscillation parameter
Sc Schmidt number K Womersley number
T0 time scale for radial diffusion
T1 time scale for advection and reaction

has been made to the effects of nonlinear reactions upon a system
of solutes undergoing Taylor Dispersion. Established literature pro-
vides no insight for the effective transport coefficients when the
nonlinearity is of the order of two or more. Though Barton [20]
and Smith [21] considered the effect of second order reaction on
dispersion phenomena, but such limited attempts are too deficient
considering its vast environmental and biological importance. In
two successive papers, Revelli and Ridolfi [22,23] have shown the
effect of nonlinear chemical reactions on suspended material in
sediment-laden turbulent streams. Still there remains a lot to
know about the effect of higher order chemical reactions on solute
transport.
The mathematical models that describe chemical reaction
kinetics provide chemists and chemical engineers with tools to
better understand and describe chemical processes such as food
decomposition, microorganism growth, stratospheric ozone
decomposition, and the complex chemistry of biological systems.
These models can also be used in the design or modification of
chemical reactors to optimize production, more efficiently segrega-
tion of products, and elimination of harmful by-products. When
performing catalytic cracking of heavy hydrocarbons into gasoline
and light gas, for example, kinetic models can be used to find the
temperature and pressure at which the highest yield of heavy
hydrocarbons into gasoline will occur. The kinetics of chemical
reactions, which determines the order of nonlinear reactions, illu-
minate the process by which a reaction takes place. The principal
factor in kinetics is the rate of the reaction. Many factors, such as
concentration and temperature, influence the rate of a reaction. Gi-
ven the ubiquity of chemical reactions, kinetics can be applied to a
wide variety of practical situations. An understanding of kinetics
enables the precise dealing of important reaction rates in biological
and industrial fields. Chemical kinetics helps to reveal the nuances
of important rate-based processes such as metabolism. In turn, this
knowledge helps scientists and other professionals to determine
the best course of action for one’s personal nutrition. Nonlinear
chemical reactions have a wide variety of application in the world
of medicine. In addition to the ways in which the human body
undergoes processes of respiration and metabolism, nonlinear
reactions also play a large part in the supervision of drugs. For
example, the mechanisms for the sustained release of drugs are
based on the half-life of the substances used and sometimes the
pH of the body as well. Practically, this affects the way in which
dosages are determined and prescribed. The rate of reactions and
the various conditions under which they occur are crucial for
determining certain aspects of environmental protection.
The main objective of the present paper is to examine the influ-
ence of nonlinear reactions on the transport coefficients, when the
flow is driven by a pressure gradient comprising steady and peri-
odic components. We present here a rigorous mathematical model
for the evolution of the concentration of reacting solutes that travel
within a fluid flowing down a pipe of circular cross-section. The
intention is to provide analytical expressions for the transport
coefficients and to look into the effect of nonlinear chemical reac-
tions on those coefficients. With this in view, a two dimensional
mathematical model is formulated to take into account advection,
diffusion and reaction. The mathematical homogenization theory
(Mei et al. [24]) is adopted to take cross-sectional and time aver-
ages of the two dimensional model, and the most general case is
dealt with in which the reactions are nonlinear both in the bulk
flow and boundary.
2. Velocity distribution
We consider a fully developed, axi-symmetric laminar flow of a
homogeneous, incompressible viscous fluid through a pipe of ra-
dius a. We have used a cylindrical coordinate system in which
the radial and axial co-ordinates are r and x respectively. The flow
is assumed to be unidirectional and so the velocity has only axial
component u(r, t) which satisfies the Navier–Stokes equation as:
 
@u 1 @p 1 @ @u
¼ þm r ;
@t q @x r @r @r
where @p@x
is the axial pressure gradient, q is the fluid density and m is
the kinematic viscosity.
The horizontal pressure gradient, which drives the flow, con-
sists of steady and harmonically fluctuating components,
1 @p
 ¼ P½1 þ wReðeixt Þ;
q @x
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S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer 54 (2011) 75–85 77

where P > 0 is the steady part of the pressure gradient, w is a factor (kg m3)1ns1 and (kg m2)1ms1) and the corresponding degrees
such that Pw is the amplitude of the oscillatory part of the pressure of nonlinearity are given by the exponents n and m. When n and m
gradient, and x is the frequency of the pressure pulsation. are zero, k and ks simply play the role of a source term. It should be
The no-slip conditions on the boundary of the pipe produces the remarked that if k = ks = 0, a great deal is known from the work of
following velocity profile, Ng [17].
uðr; tÞ ¼ us ðrÞ þ Re½uw ðrÞeixt ; ð1Þ The boundary conditions for (2) can now be formulated as:
@C
where the steady component (us(r)) of the velocity is, ¼ 0; r ¼ 0 ð3Þ
 @r
 r 2 
@C @C s
us ðrÞ ¼ hus i 1 
a D  CC ¼ ¼ kðaC  C s Þ  ks C m
s ; r ¼ a; ð4Þ
@r @t
and its unsteady component (uw(r)) is given by where C is the irreversible absorption rate.
 
Pw J ðrrÞ
uw ðrÞ ¼ i 1 0 : 4. Assumptions
x J 0 ðraÞ
 
Here hus i ¼ Pa
2
is the velocity averaged over the cross-section of The following assumptions are made for carrying out the per-
8m
turbation analysis:
the pipe (the angle brackets denote averaging across the tube sec-
tion). J0 is the zeroth-order Bessel function of the first kind, and
pffiffiffiffiffiffiffiffiffiffiffiffi 1. A sufficiently long time has passed since the discharge of the
r2 =ix/m or r = (1i)/d where d ¼ 2m=x solute into the flow so that the length scale for the longitudinal
spreading of the reactive species is much greater than the tube
3. Governing equation and boundary conditions radius. By this we mean that x = O(L) and r = O(a), where L is a
characteristic longitudinal distance for the solute transport.
We consider the transport of a chemically reactive solute along a The ratio
tube whose walls are made of retentive and reactive materials. It is
assumed that the solute is completely miscible in the fluid and
 ¼ a=L << 1
undergoes nonlinear reactions with it in the bulk flow. Also at the is small enough to use as ordering parameter.
boundary of the tube, the solute is subject to linear and nonlinear 2. The time period of flow oscillation is so short that within this
reactions with the wall material. As a result a portion of the solute period there can be no appreciable transport effects down the
is absorbed irreversibly by the wall material and some portion takes tube. In other words, flow oscillations are sufficiently fast and
part in a reversible phase exchange process with the flowing fluid. a large number of flow oscillations are required for the spread-
The phase of the solute that flows with the fluid and that retains at ing of solute over the length O(L) along the tube. However, the
the boundary are termed as mobile and immobile phases tube is so fine in bore that diffusion across the entire cross-sec-
respectively. tion may be accomplished within this short time scale.
If C is the concentration (mass of solute per bulk volume of the 3. The two reactions occurring at the boundary are of different
flowing fluid) of the mobile phase and Cs is the concentration (mass orders. The reversible phase exchange is much faster than the
of solute per surface area of the boundary wall) of the immobile irreversible reaction. This ensures that local equilibrium can
phase, then at equilibrium be largely achieved over a finite number of oscillations. The rate
Cs of irreversible absorption is much slower and it is comparable
¼ a; with the advection speed down the tube.
C
4. The Peclet number is equal to or greater than order of unity:
where a is a partition coefficient having the dimension of length.
When, in general, equilibrium is not attained, the phase ex- Pe  ahus i=D P Oð1Þ:
change will take place in either forward or backward direction Under these assumptions, three distinct time scales, which gov-
according to erns the total transport process, may be defined as (Ng [17])
@C s Time scale for the radial diffusion : T 0 ¼ 2p=x ¼ Oða2 =DÞ ¼ Oðk Þ;
1
¼ kðaC  C s Þ þ Rs ;
@t 1
Time scale for advection and reactions : T 1 ¼ L=hus i ¼ OðaC Þ ¼ T 0 =;
where k is the reversible reaction rate constant and Rs is the so called Time scale for axial diffusion=dispersion : T 2 ¼ L2 =D ¼ T 0 =2 :
nonlinear reaction occurring at the boundary to be defined later.
The problem for the transport of the reactive solute can now be Thus T1 and T2 are respectively one and two order of magnitude
formulated as follows: longer than T0. Based on these time scales, we may introduce
  accordingly
@C @C @2C D @ @C
þ uðr; tÞ ¼D 2þ r þ R; 0 < r < a; ð2Þ
@t @x @x r @r @r t 0 ¼ t; t1 ¼ t; t2 ¼ 2 t;
where D is the molecular diffusion coefficient assumed to be con- which are, respectively, the fast, medium and slow time
stant. The term R on the right hand side of (2) represents the effect variables.
of nonlinear chemical reaction occurring in the bulk flow.
Two different nonlinear reactions (represented by R and Rs ) are 5. Asymptotic analysis
assumed to affect the mobile and immobile phases. The corre-
sponding reaction rates, R and Rs , are therefore prescribed accord- Let us assume that the radial diffusion is two order of magni-
ing to the power laws, tude greater than the longitudinal dispersion and one order of
magnitude greater than the advection which is again comparable
R ¼ kC n ; Rs ¼ ks C m
s ;
with the rate of irreversible reaction at the boundary as mentioned
where coefficients k and ks are the nonlinear reaction rate constants earlier. The rate of nonlinear reactions occurring in the bulk flow
for the mobile and immobile phases respectively (their units are and at the boundary are also assumed to be comparable with the
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78 S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer 54 (2011) 75–85

advection. The reactions play a significant role in the whole trans- For first order (O()), Eqs. (5)–(7) give:
port process if the time scales of the reactions and advection are  
@C 0 @C 1 @C 0 D @ @C 1
comparable. If the reactions are fast enough, they dominate and þ þu ¼ r  kC n0 ; 0 < r < a; ð18Þ
@t 1 @t0 @x r @r @r
that lead to a considerable reduction of the influences of longitudi-
nal transport mechanisms, on the contrary if the reactions are too @C 1
¼ 0; r ¼ 0; ð19Þ
slow, their contributions are negligible. Thus all the reactions pres- @r
ent in the model i.e., the irreversible reaction at the boundary and @C 1 @C s0 @C s1
D  CC 0 ¼ þ ¼ kðaC 1  C s1 Þ  ks C m
s0 ; r ¼ a: ð20Þ
the two nonlinear reactions-one in the bulk flow and the other at @r @t 1 @t 0
the boundary are comparable to each other. Averaging the Eqs. (18)–(20) w.r.t the fast time variable t0, we get
The relative significance of the terms in the transport Eq. (2) !
with the boundary conditions (3) and (4) can now be identified @C 0 @C 0 D @ @C 1
þ us ¼ r  kC n0 ; 0 < r < a; ð21Þ
as indicated below with the power of : @t 1 @x r @r @r
 
@C @C @2C D @ @C @C 1
þ u ¼ 2 D 2 þ r  kC n ; 0 < r < a; ð5Þ ¼ 0; r¼0 ð22Þ
@t @x @x r @r @r @r
@C and
¼ 0; r ¼ 0; ð6Þ
@r
@C @C s @C 1 @C s0
D   CC ¼ ¼ kðaC  C s Þ  ks C m r ¼ a: ð7Þ D  CC 0 ¼ ¼ kðaC 1  C s1 Þ  ks C m
s0 ; r ¼ a; ð23Þ
s ; @r @t 1
@r @t
To carry on the perturbation analysis, let us expand the dependent where the overbar denotes time average over one period of oscilla-
variables C and Cs in power series of the perturbed parameter : tion and us is the steady velocity component. We further take cross-
sectional average of (21) subject to the conditions (17), (22) and
Cðx; r; tÞ ¼ C 0 ðx; r; t 1 ; t2 Þ þ C 1 ðx; r; t 0 ; t 1 ; t 2 Þ (23) to obtain
þ 2 C 2 ðx; r; t 0 ; t1 ; t 2 Þ þ Oð3 Þ; ð8Þ @C 0 hus i @C 0 2C k
þ þ C 0 þ C n0 ¼ 0; ð24Þ
@t1 R @x aR R
C s ðx; tÞ ¼ C s0 ðx; t1 ; t 2 Þ þ C s1 ðx; t 0 ; t 1 ; t 2 Þ þ 2 C s2 ðx; t 0 ; t 1 ; t 2 Þ
where
þ Oð3 Þ: ð9Þ
2a
The terms Cn and Csn, (n = 1, 2, 3 . . .) are purely oscillatory functions R¼1þ ;
a
of short time variable t0 as they are subject to advection due to flow
is the retardation factor.
oscillation, but oscillatory effect does not show up on the zeroth or- @C 0
Using (17) in (20) and eliminating from (18)–(20) and (24),
der (i.e., n = 0), and therefore the leading order concentrations are @t 1
we rewrite the Eqs. (18)–(20) as:
taken to be independent of the time variable t0 [17,18].     9
The nonlinear decay term in (5) and (7) can also be expanded in @C 1 hus i @C 0 2C 2ka n D @ @C 1
þ u  C0 þ C0 ¼ r ; 0 < r < a>
>
>
>
power series as: @t 0 R @x aR aR r @r @r >
>
>
>
@C 1 >
=
kC n ¼ kðC 0 þ C 1 þ 2 C 2 þ    Þn ¼ 0; r ¼ 0
@r
 kC n0 þ 2 nkC n1 3 >
0 C 1 þ Oð Þ; ð10Þ @C 1 hus i @C 0 C ka @C s1 >
>
D ¼ a þ C 0  C n0 þ >
>
>
>
@r R @x R R @t 0 >
>
ks C ms ¼ ks ðC s0 þ C s1 þ 2 C s2 þ    Þm m m
;
¼ kðaC 1  C s1 Þ  ks a C 0 þ CC 0 ; r ¼ a
 ks C m 2 m1
s0 þ  mks C s0 C s1 þ Oð Þ:
3
ð11Þ ð25Þ
For the multiple-scale asymptotic analysis, the time derivative has The structure of (25) suggests the substitutions
been expanded as:
@C 0
C 1 ¼ NðrÞ þ ReðBðrÞeixt0 Þ þ MðrÞC 0 þ EðrÞC n0 þ FðrÞC m
0 ð26Þ
@ @ @ @ @x
¼ þ þ 2 : ð12Þ
@t @t0 @t1 @t 2 and
Using the expansions (8)–(12) in Eqs. (5)–(7) and equating the coef-
@C 0
ficients of like powers of  from both sides, a system of differential C s1 ¼ N s þ ReðBs eixt0 Þ þ Ms C 0 þ Es C n0 þ F s C m
0; ð27Þ
@x
equations is obtained:
For zeroth order (O(1)) Eqs. (5)–(7) give: where the coefficients N(r), Ns; M(r), Ms; B(r), Bs; E(r), Es and F(r), Fs
  satisfy certain boundary value problems that can be obtained by
D @ @C 0
0¼ r ; 0 < r < a; ð13Þ substituting (26) and (27) into (25), and equating the coefficients
r @r @r
of analogous terms from both sides, e.g. the steady terms associated
@C 0 with @C 0
prescribes the equation for N(r) and Ns as:
¼ 0; r ¼ 0; ð14Þ @x
@r  
@C 0 D d dN hus i
D ¼ kðaC 0  C s0 Þ; r ¼ a: ð15Þ r ¼ us  ; 0<r<a ð28Þ
@r r dr dr R
Eqs. (13) and (14) obviously imply that the leading order concentra- with the boundary conditions
tion is independent of r, i.e.,
dN
C 0 ¼ C 0 ðx; t1 ; t 2 Þ: ð16Þ ¼ 0; r ¼ 0;
dr
The boundary condition (15) then gives dN hus i
C s0 ¼ aC 0 : ð17Þ D ¼ a ¼ kðaN  Ns Þ; r ¼ a:
dr R
As expected, at the leading order the mobile phase of the reactive Again equating the coefficient of C0 from both sides, M(r) and Ms are
solute is at local equilibrium with the immobile phase. obtained as:
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S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer 54 (2011) 75–85 79

 
D d dM 2C @hC 1 i hus ihNi @ 2 C 0 1 @C n hus ihFi @C m
r ¼ ; 0<r<a ð29Þ ¼  ðkhNi þ hus ihEiÞ 0  0
r dr dr aR @t 1 R @x 2 R @x R @x
   
with the boundary conditions 1 2ChNi @C 0 1 2nChEi n
 þ hus ihMi  khMi þ C0
dM R a @x R a
¼ 0; r ¼ 0; 2mChFi m nkhEi 2n1 mkhFi nþm1 2ChMi
dr  C0  C0  C0  C0
dM C aR R R aR
D ¼ ¼ kðaM  Ms Þ þ C; r ¼ a:
dr R
@C 1 1 @2 C0 @C n @C m
Similarly, equating the unsteady terms linked with @C 0
, we obtain hu i ¼ ðhus Ni þ Rehuw B iÞ 2 þ hus Ei 0 þ hus Fi 0
@x @x 2 @x @x @x
the following equation for the complex functions B(r) and Bs:
  @C 0
D d dB þ hus Mi
r ¼ ixB þ uw ; 0<r<a ð30Þ @x
r dr dr
@C s1 hus iNs @ 2 C 0 1 @C n hus iF s @C m
with the boundary conditions, ¼ 2
 ðkNs þ hus iEs Þ 0  0
@t1 R @x R @x R @x
dB    
¼ 0; r ¼ 0; 1 2 CN s @C 0 1 2nCEs n
dr  þ hus iM s  kM s þ C0
R a @x R a
dB
D ¼ ixBs ¼ kðaB  Bs Þ; r ¼ a: 2mCF s m nkEs 2n1 mkF s mþn1 2CM s
dr  C0  C  C0  C0
aR R 0 R aR
Equating the coefficient of C0n, we have the following equation for
E(r) and Es:
  @C n0
D d dE 2ka nC n1
0 hC 1 i ¼ hNi þ nhMiC n0 þ nhEiC 2n1
0 þ nhFiC nþm1
0 ;
r ¼ ð31Þ @x
r dr dr aR
where * denotes the complex conjugate.
with the boundary conditions
Substitution of these terms in (38) produces
dE
¼ 0; r ¼ 0;
dr @C 0 @2C0 @C n @C m @C 0
 D0eff þ f01 0 þ f02 0 þ f03 þ v1 0C n0 þ v02 C m
dE ka @t 2 @x 2 @x @x @x 0
D ¼ ¼ kðaE  Es Þ; r ¼ a:
dr R þ v03 C 2n1 þ v04 C mþn1 þ v05 C 0 ¼ 0 ð39Þ
0 0
Finally the coefficient of C0m produces the following equation for
F(r) and Fs: with
 
D d dF   
r ¼0 ð32Þ D 1 hus i hus i 1
r dr dr D0eff ¼ þ N  us þ 2N s 2  Rehuw B0 i;
R R R aR 2R
  
with the boundary conditions 2k 1 hus i 2hus iEs
f01 ¼ 2 ðahNi  Ns Þ  E  us  ;
dF aR R R aR2
¼ 0; r ¼ 0; ð33Þ   
dr 2hus iF s 1 hus i
f02 ¼  2
 F  us ;
dF aR R R
D ¼ 0 ¼ kðaF  F s Þ  ks am ; r ¼ a: ð34Þ
dr     
1 hus i 2M s hus i 2C 2Ns 2C
For second order (O(2)), (5)–(7) give: f03 ¼  M  us  2
 2
hNi þ þ NðaÞ;
R R aR aR a aR
@C 0 @C 1 @C 2 @C 1 @ 2 C 0 D @ @C 2
þ þ þu ¼D 2 þ ðr Þ    
@t2 @t 1 @t 0 @x @x r @r @r nkhMi 2C 2nC 2Es k 2M s
nkC n1 v01 ¼ þ EðaÞ  2 hEi þ  2 hMi þ ;
 0 C1; 0 < r < a; ð35Þ R aR aR a R a
 
@C 2 2C 2mC 2F s
¼ 0; r¼0 ð36Þ v02 ¼ FðaÞ  hFi þ ;
@r aR aR2 a
and 2nk
v03 ¼ 2 ðahEi  Es Þ;
@C 2 @C s0 @C s1 @C s2 aR  
D  CC 1 ¼ þ þ nkhFi mk 2F s
@r @t 2 @t1 @t 0 v04 ¼  2 hFi þ ;
R R a
¼ kðaC 2  C s2 Þ  mks C m1
s0 C s1 ; r¼a ð37Þ  
2C hMi 4 CM s
v05 ¼ MðaÞ   :
Averaging the Eq. (35) w.r.t time followed by space subject to the aR R a2 R2
boundary conditions (36) and (37) we have:

@C 0 1 @hC 1 i 1 @C 1 2C 2 @C s1 kn n1 6. Transport coefficients

þ þ hu iþ C 1 ðaÞ þ þ C 0 hC 1 i
@t 2 R @t 1 R @x aR aR @t 1 R
D @2 C0 Finally, combining the relationships (24) and (39) and recalling
¼ : ð38Þ (12) one obtains
R @x2
Using (1), (24), (26) and (27), we find each term of (38) as follows: @C 0 @2C0 @C n @C m @C 0
 Deff 2
þ f1 0 þ f2 0 þ f3 þ v1 C n0 þ v2 C m
0
@t @x @x @x @x
@C 0
C 1 ðaÞ ¼ NðaÞ þ MðaÞC 0 þ EðaÞC n0 þ FðaÞC m
0
2n1
þ v3 C 0 mþn1
þ v4 C 0 þ v5 C 0 ¼ 0; ð40Þ
@x
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80 S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer 54 (2011) 75–85

where Eq. (40) can be written as

" #
hus i k 2C b0
@C D hus i2 a2 hus i2 a2 @ 2 C b0
f3 ¼ f03 þ ; v1 ¼ v01 þ ; v5 ¼ v05 þ  þ DTs þ DTw
R R aR @t R D D @x2
r |fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl}
and the other coefficients are equal to their dashed counterparts. s
Here Deff is the effective dispersion coefficient, fi’s (i = 1, 2, 3) bn bm b0
@C 0 @C 0 @C b n þ kc C
bm
are the effective coefficients for advective terms and vi’s (i = 1, þ hus in1 þ hus in2 þ hus in3 þ kc1 C 0 2 0
@x @x @x w x
2, . . . , 5) are the coefficients for the reaction terms. It should be t u v
mentioned here that the coefficients v1, v3 and f1 are the results b 2n1 þ kc C
þ kc3 C b mþn1 þ kc C b
0 4 0 5 0 ¼ 0; ð41Þ
of nonlinear reaction in the bulk flow while v2 and f2 signify y z s
10

the effect of nonlinear reaction at the boundary. The coupled

effect of both the reactions can be seen form v4. The linear where
 
irreversible reaction at the boundary is represented by the coeffi- 1 11 1 1 2a
^
cient v5. DTs ¼  þ 2 þ 3 ; ð42Þ
R 48 3R 8R R Da
For determination of the coefficients in (40) we need to solve
(28)–(32) subject to the respective boundary conditions which ( )
8^d6 w2 ^d2 A ½r ^  ÞJ1 ðr
^ J0 ðg ^  J 0 ðr
^Þ  g ^ ÞJ1 ðg
^  Þ Ar
^ J1 ðg ^ J 1 ðr
^Þ  g ^Þ
produces DTw ¼ Re  i ;
ScR 2ðSc2  1ÞjJ0 ðr ^ Þj2 ðSc  1Þg ^r
^ J 0 ðr^Þ
   
hus i 2 1 r2 ð43Þ
NðrÞ ¼ Nð0Þ þ r 1  2 ;
2D 2R 4a
 a hus ia2 a hus i
N s ¼ aNð0Þ þ a 1 þ 6 þ ; ^ ðr ^ Þ þ Scr
^ J 1 ðr Da ^d2
^ ¼ 1  iðk=xÞ Da a
a 8RD k R bJ 0
^Þ k
A¼ ; b ^; ¼
  ^
bJ ðg ^Þ þ g
^ J ðgÞ ðk=xÞ2 þ 1 x 2Sc
C 2 aa2 a 2C 0 1
MðrÞ ¼ Mð0Þ  r ; M s ¼ aMð0Þ þ  þ ;
2aRD 4D k aR
  1 ^
Pw ADJ 0 ðgrÞ  mJ 0 ðrrÞ ib n1 ¼ ka^ ð2RDa  3Da  12a
^ Da  24Þ; ð44Þ
BðrÞ ¼ 2 1 þ ; Bs ¼ BðaÞ; where 6R3
x ðm  DÞJ 0 ðraÞ x
bJ 0 ðraÞ þ mrJ 1 ðraÞ ix ixka 2^ m
A¼ ; g2 ¼  ; b¼ ; n2 ¼ ks a
^ ; ð45Þ
bJ 0 ðgaÞ þ DgJ 1 ðgaÞ D k þ ix R2
  "
ka 2 1 aa ka b 1 1    #
EðrÞ ¼ Eð0Þ þ r ; Es ¼ aEð0Þ þ þ ; 1 C 1 2
2aDR k 2D R n3 ¼ 1þ2   1 ; ð46Þ
R R 3 4R R Da
ks
FðrÞ ¼ Fð0Þ; F s ¼ aFð0Þ  am ; !
k b
^k C a^ a^ R2
c1 ¼ a^ R  2na^ 2  8n þa
^8 þ2 ; ð47Þ
2R3 Da Da b
C
where N(0), M(0), E(0) and F(0) are undetermined constants. These
undetermined constants are not required for the evaluation of Deff,
fi’s and vi’s when the reactions are linear. Even for nonlinear reac- 4m Cb
c2 ¼ ^ks ; ð48Þ
tions, they are not essential as far as the coefficients Deff, f1, f2, f3, v3 Da R2
and v5 are concerned for the terms involving those undetermined
constants in each of the expressions cancel out to zero. But these n
c3 ¼  a^ ^k2 ða^ Da þ 4Þ; ð49Þ
constants are mandatory for the determination of v1, v2 and v4. 2R3
To evaluate the undetermined constants let us take, without any
loss of generality, that 2m ^^
c4 ¼ a^ kks ; ð50Þ
R2
hC 1 ðrÞi ¼ 0;
"  #
2 Cb 2Cb1  1 1
so that c5 ¼ 1 þ 1 ð51Þ
R Da R 8R R Da
hNðrÞi ¼ hMðrÞi ¼ hEðrÞi ¼ hFðrÞi ¼ 0;
which yields and for convenience, each term of Eq. (41) is marked enclosing
2 numbers rounded by circle below the individual terms.
hus ia ð3  5RÞ aC
Nð0Þ ¼ ; Mð0Þ ¼ ; Eð0Þ Eq. (41) is the one dimensional nonlinear partial differential
24DR 4RD equation that models the concentration of the mobile phase of a
aka reacting substance which undergoes a nonlinear chemical reaction
¼ and Fð0Þ ¼ 0:
4RD both within the flow and at the boundary. The equation clearly
shows how the combined action of two different types of nonlinear
Finally when all the coefficients are determined, using the following
reactions changes the transport mechanisms to a great extend.
normalised variables
Complex interactions between the mobile phase and immobile
2
b 0 ¼ C0 ; a a b Ca
^¼ ; C
ka phase and fluid dynamic mechanisms that regulate the evolution
C ¼ ; Da ¼ ;
C ð0Þ a D D of the concentration of the reactive solute, can be accessed from
^k ¼ k C n1 ; ^ks ¼ ks am1 C m1 the Eq. (41). Recalling the relationship (17), the spatial and tempo-
k ð0Þ k ð0Þ
ral behaviour of Cs0(x, t) can also be deduced from (41).
Two special cases can be derived from the general Eq. (41). In
ba m order to underline the role of nonlinearities, let us explain these
r^ ¼ ra; g^ ¼ ga; ^d ¼ d=a; b^ ¼ ; Sc ¼ :
D D two cases separately-.
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S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer 54 (2011) 75–85 81

Case 1: There is no nonlinear reaction in the bulk flow and parameters are, among others, a b which are respectively
^ , Da and C
the boundary, i.e., the solute undergoes only linear irreversible the phase partition ratio or retention parameter, Damkohler
absorption by the wall material and reversible phase exchange number (rate of reversible reaction at the boundary) and rate of
with the flowing fluid. In this case k = ks = 0 and consequently the irreversible reaction at the boundary. The retention parameter a ^
coefficients n1, n2, c1, c2, c3 and c4 as given by the Eqs. (44), (45), is the ratio of solute mass distributed between the phase retained
(47), (48), (49) and (50) respectively vanish. So Eq. (41) reduces to by the wall and that carried by the flow. In particular, a ^ ¼ 0 for a
" # non-retentive or inert boundary. The number Da is the ratio of
b0
@C D hus i2 a2 hus i2 a2 @ 2 C b0 @Cb0
 þ DTs þ DTw þ hus in3 þ kc5 Cb 0 ¼ 0; the phase exchange rate to the diffusion rate. The order of the non-
@t R D D @x2 @x s
10 linearities m and n and corresponding rates of the reactions ^ k and
r |fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl} v
s
^
ks are also required for the determination of the coefficients. The
parameter ^
d is identified as oscillation parameter. It can be noted
ð52Þ pffiffi pffiffiffi
that ^
d ¼ K2, where K ¼ a xm is the Womersley number. Thus ^ d is re-
where DTs, DTw, n3 and c5 are as given by (42), (43), (46) and (51) lated to the reciprocal of the Womersley number. It is an important
respectively. number used to describe the unsteady nature of fluid flow in re-
The Eq. (52) coincides with the one obtained by Ng [17] in his sponse to an unsteady   pressure gradient. It is the measure of the
noteworthy analysis. 2
ratio of the time am required for viscosity to smooth out  the
Case 2: This case corresponds to when both the reactions occur- transverse variation in vorticity to the period of oscillation x1 . An-
ring at the bulk flow and at the boundary are of linear type, i.e., other way of looking at K is that, for periodic flow within a tube, it
n = m = 1. In this case the Eq. (41) reduces to a simple equation pffiffiffi
is the ratio of the tube radius a to the Stoke’s layer thickness xm .
which reads as: Let us first describe few important features of the two disper-
b0 b0 b0 sion coefficients (i.e., DTs and DTw) arising from the steady and
@C @2 C @C
 Deff þ ðn1 þ n2 þ n3 Þ þ ðc1 þ c2 þ c3 þ c4 oscillatory part of the fluid motion. These features of dispersion
@t @x2 @x
coefficients were reported by Ng [17] in detail. But for the sake
b0
þ c ÞC 5 of being self contained, some of them are reproduced in the text.
¼ 0; ð53Þ Fig. 1(a) shows the variation of the oscillatory component of the
dispersion (DTw) coefficient with the Schmidt number Sc. It is ob-
where all the coefficients are defined in (42)–(51). According to Gill served from the figure that higher value of Sc may lead to smaller
and Sankarasubramanian [4], the reaction (K0), convection (K1) and DTw, but the effect is significant only when oscillation parameter ^ d
dispersion (K2) coefficients (signs are not taking into consideration) is small and a ^ > 0. When Sc is small or ^ d is large enough, DTw no
can be identified from this model as:
K 0 ¼ c1 þ c2 þ c3 þ c4 þ c5 ; K 1 ¼ n1 þ n2 þ n3 ; K 2 ¼ Deff : ð54Þ
It should be mentioned here that K2 is affected only by the revers-
ible phase exchange up to the second order of the present analysis.
But the first two transport coefficients (K0 and K1) are affected by
both reversible and irreversible reactions. If we proceed to the next
order (i.e., third order), then only the effects of irreversible reaction
on the corresponding K2 can be found out (Ng [17]).
The nature of these coefficients will be discussed in the follow-
ing section. In real cases n1, n2 may be neglected with respect to n3
and c3, c4 with respect to other three coefficients (c1, c2, c5). How-
ever for this linear case no approximation is made. Approximations
are made only for the case where nonlinearity is concerned.
The event, when n = m, can also be considered as a subcase
resulting from the general Eq. (41). In this case the Eq. (41) reduces
to:
" #
b0
@C D hus i2 a2 hus i2 a2 @ 2 C b0 @Cbn
 þ DTs þ DTw 2
þhus iðn1 þ n2 Þ 0
@t R D D @x t u @x
r |fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl}
s

@Cb0
b n þ kðc þ c Þ C
þkðc1 þ c2 Þ C b 2n1 þ kc C b
þ hus in3 0 3 4 0 5 0 ¼ 0 ð55Þ
@x w x y z s
10
v

The coupled effect of the two nonlinear reactions can be observed

from the Eq. (55).

7. Results and discussions

In the cross sectionally averaged transport equation, the disper-

sive, advective and reactive fluxes are controlled by some effective
coefficients. These transport coefficients are essentially dependent
on the factors such as the steady and unsteady flows, cross sec-
tional geometry, partition of solute in various phases, chemical
reactions and so on which are need to be prescribed in order to Fig. 1. Variation of the oscillatory component of the dispersion coefficient (a) with
compute the coefficients. For the present problem the controlling Schmidt number Sc and (b) with oscillation parameter ^ d.
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82 S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer 54 (2011) 75–85

longer remains sensitive to Sc. Variation of DTw with ^ d can be seen

from Fig. 1(b). DTw increases monotonically with ^ d and depending
on Sc and a ^ , it becomes almost constant beyond a certain ^ d. Here
the limiting value of DTw is taken into account as Sc ? 1 because
the expression of DTw (Eq. (43)) is indeterminate at Sc = 1. The ef-
fects of the phase partitioning and kinetics on the steady and oscil-
latory dispersion components DTs and DTw are shown in Fig. 2. It is
seen that the phase exchange has quite similar effects on DTs and
DTw. The figure confirms that stronger kinetics of the phase ex-
change (a slower exchange rate or smaller Da) will give rise to a lar-
ger value of either dispersion coefficients. It is remarkable that the
dispersion coefficients increase sharply when the wall condition
just changes from inert to slightly retentive.
When the reactions are linear (i.e., n = m = 1), the reaction coef-
ficient K0 and advection/convection coefficient K1 are computed
from the expression (54). For convenience of discussion, we as-
sume X ¼ ^ ks =^
k so that X < , = , > 1 according to the reaction rate
constant for the mobile phase is greater than, equal to and less
than the corresponding value for the immobile phase. Variation
of the reaction coefficient K0 with the partition coefficient a ^ is
shown in Fig. 3(a,b,c). It is clear from the figures that unless the
rate of reversible or irreversible reaction at the boundary is strong,
the reaction coefficient decreases monotonically with a ^ . If either of
the reaction rate is fast, reaction coefficient decreases sharply for
an initial small range of a ^ to reach to a minimum value followed
by a steep rise with a ^ over the remaining range. Effect of the reac-
tion rates ^ k and ^ ks on the reaction coefficient K0 can be seen from
Fig. 3(a). The increase of reaction rates enhances the reaction coef-
ficient and for low a ^ this phenomenon is more noticeable. But irre-
versible reaction rate at the boundary seems to have quite opposite
effect on the reaction coefficient that can be seen from Fig. 3(b).
Reaction coefficient diminishes as the rate of irreversible reaction
becomes stronger. Also strong kinetics of the phase exchange leads
to decrease of the reaction coefficient. [Fig. 3(c)]. The effects are
more, when a ^ is small.
The isolated effect of the reaction rates can be seen from Fig. 4
for different a ^ . It is seen that for all a
^ , reaction coefficient K0 in-
Fig. 3. Reaction coefficient as a function of a
^ for different values of various reaction
creases as ^ ks increases (for fixed ^ k, increase of X leads to increase rates when n = m = 1.
of ^
ks ). This is not true when ^ ks remains fixed allowing ^ k to vary. Ef-
fect of ^ k is found to be negligible on the reaction coefficient. Thus
reaction at the boundary is more influential than that in the bulk
flow. As demanded earlier, large a ^ inhabits the rising process to a
great extent. It may be mentioned here that the reaction coefficient
K0 varies almost linearly with the reaction rate constants ^ k and ^
ks .
The variation of the convection coefficient K1 with the partition
coefficient a ^ is shown in Fig. 5(a,b). It is observed that, Da should be
large enough for the monotonic decrease of the convection coeffi-
cient with a ^ . Otherwise the decrease of K1 is confined within the
initial small range of a ^ and over the remaining range it shows a
keen increase [Fig. 5(a)]. The same is true when the rate of irrevers-

Fig. 4. Variation of the reaction coefficient (K0) with the ratio of the wall-phase
reaction rate to the fluid-phase reaction rate (X)(for the continuous lines ^
k is fixed
while ^ks is fixed for the dotted lines).

ible reaction becomes stronger [Fig. 5(b)]. The figure indicates that
K1 decreases with the rate Cb of irreversible reaction. But when the
phase exchange rate is very fast (i.e., Da is large), advection coeffi-
b [Fig. 6(a)]. Thus reversible and irreversible
cient increases with C
reaction processes are not independent. Effect of one can be greatly
influenced by the other. The figure also indicates that under the
Fig. 2. Variation of the steady (DTs) and unsteady (DTw) components of the
phase exchange with strong kinetics, the advection speed is af-
dispersion coefficients with the partition coefficient a
^ for different reaction rate fected by the wall absorption drastically which explains the
parameter Da. well known result that the reversible phase exchange can retard
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S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer 54 (2011) 75–85 83

conceptual point of view, as they show the variety of the links

between the reactions and transport mechanisms. However for
realistic case (i.e. n, m = O(1)), the following conditions may occur
(Revelli and Ridolfi [22]):
!
@Cbn bm
@C @Cb0
0 0
n1 ; n2 << n3
;
@x @x @x
   
c3 Cb 02n1 ; c4 Cb mþn1
0
b n; c C
<< c1 C 0
bm b
2 0 ; c5 C 0 :

As a consequence third, fourth, eighth and ninth terms (numbers

within the circles below the terms indicate its position) of the Eq.
(41) can be neglected for application purpose and the equation
can be approximated as
" #
b0
@C D hus i2 a2 hus i2 a2 @ 2 C b0
 þ DTs þ DTw
@t R D D @x2
r |fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl}
s

@Cb0
b n þ kc C
þ kc1 C bm b
þ hus in3 0 2 0 þ kc5 C 0 ¼ 0: ð56Þ
@x w x s
10
v

Fig. 5. Convection coefficient as a function of the retention parameter (a) for
different values of phase exchange rate Da and (b) for different values of irreversible
b.
reaction rate C
Furthermore, if the nonlinear reaction terms from the Eq. (56) are
omitted, the equation agrees with Ng [17].
The behaviour of the three prominent reaction coefficients (i.e.,
c1, c2 and c5), which are the functions of strength and kinetics of
the nonlinear reactions, can be seen here. The ratio X which

Fig. 6. Variation of the convection coefficient K1: (a) with the irreversible reaction
rate parameter C b when a ^ ¼ 1, (b) with the ratio of the reaction rates of the wall-
phase to the fluid-phase X when Da = 1.

advection (Ng and Rudraiah [25]). Fig. 6(b) shows the plots of K1
with the reaction rate ratio X. In this case, a
^ has almost negligible
effect on the rate of rising of K1 with the reaction rates. Although
stronger reaction rate leads to an increase of K1, the growth rate
is not so significant. The linear variation K1 like K0 with respect
to the reaction rates is also remarkable.
As far as the case of nonlinearity is concerned, numerous non-
linear terms in the Eq. (41) indicates how the complex interaction
Fig. 7. The nonlinear bulk-flow reaction coefficient c1 as a function of a ^ : (a) for
between the mobile phase and reaction alters the evolution of the different values of n, (b) for different values of the irreversible reaction rate C b and
fluid-phase concentration. These terms are important, from a (c) for different values of Da.
 Author's personal copy
84 S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer 54 (2011) 75–85
Fig. 8. Same as Fig. 7, but for the nonlinear wall-phase reaction coefficient c2.
determines intensity of the boundary reaction over the bulk flow
reaction is an important factor for the determination of the coeffi-
cients. It is interesting to see from Eqs. (47) and (48) that the non-
linear reaction rate constants ^ k and ^ks are linearly related with
their representative coefficients (i.e., c1 and c2). Consequently the
change of the reaction rates shows a linear variation with these
coefficients, which is not true for the coefficient c5, the result of
first order irreversible reaction at the boundary. The following dis-
cussions are devoted solely for the three nonlinear reaction coeffi-
cients. Without loss of generality, we take m = n = 2.
Fig. 7 shows the behaviour of the reaction coefficient c1 which is
associated with bulk-flow reaction. It is seen that, except for a ini-
tial short range, c1 increases with a ^ over a substantiable domain
and then it becomes almost constant with respect to a ^ . When
the values of n are of O(0,1), the initial decrement of c1 immedi-
ately follows stationarity. As the degree of the reaction n increases,
the coefficient c1 is found to decrease and this development is
more focused over the transient portion, i.e., where c1 alters its
direction from lowering down to rising up with a ^ [Fig. 7(a)].
Almost no exception is found with c1 compared with the coeffi-
cients already discussed (i.e., K0 and K1) under the variation of
the parameters C b and Da. Stronger C b or weaker Da both causes
the coefficient c1 to increase with a ^ beyond a critical value before
which the coefficient decreases with a ^ [Fig. 7(b,c)].
However behaviour is something exceptional as far as the coef-
ficient c2 is concerned which is linked with the nonlinear reversible
Fig. 9. Variation of the reaction coefficients (c1, c2 and c5) with the corresponding
rates of reactions (^
k, ^ b ).
ks and C
reaction at the boundary. Fig. 8(a) shows that c2 decreases mono-
tonically with a ^ for any nonzero value of m, and the decrement is
sharp when the nonlinearity is of higher order. The monotonicity is
strict for lower range of a ^ and for large a ^ there is no significant
change. It is observed that the nonlinearity of the reaction leads
to increase the coefficient c2. It should be mentioned here that c2
becomes identically equal to zero when m = 0, i.e., the coefficient
has no longer effect on the transport process in presence of the
source term. The effects of reversible and irreversible reaction rates
(i.e., Da and C b ) on c2 can be seen from the Fig. 8(b,c). Unlike the
other coefficients, c2 is found to increase as the rate of irreversible
reaction at the boundary becomes stronger. Also stronger kinetics
of the phase exchange give rise to higher value of c2 which is pro-
nounced when a ^ is sufficiently small.
The variation of reaction coefficients (c1, c2 and c5) with respect
to the corresponding reaction rates (^ k, ^
ks and C b ) are shown in
Fig. 9(a,b,c) for different values of the retention parameter a ^ . It is
remarkable to note that depending upon the retention parameter,
the coefficient c1 may decrease with ^ k [Fig. 9(a)]. Figure shows that
large a ^ ensures the lowering of c1 with ^ k, which is not the case for
the coefficient c2. It is seen from Fig. 9(b) that for all a ^ , c2 increases
with ^ ks , though larger a^ ceases the growth rate of c2. In both cases
the variations are linear. The coefficient c5 is found to decrease
monotonically as the reaction rate C b increases [Fig. 9(c)].
 Author's personal copy
S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer 54 (2011) 75–85
8. Conclusions
The purpose of this study is to ascertain the transport coeffi-
cients associated with the unsteady flow of a reacting solute
through a circular tube with a reactive wall layer. The solute is as-
sumed to undergo nonlinear reactions both within the flowing
fluid and at the boundary. The reaction at the boundary again con-
sists of two components due to phase exchange between the flow-
ing fluid and the wall layer, which is nonlinear and a linear
irreversible component due to absorption into the wall. The moti-
vation is to explore the role of nonlinear reactions in the bulk flow
and at the boundary on the transport process, which are of funda-
mental importance in chemical and biological processes. In the ab-
sence of nonlinearity the results are in good agreement with the
existing literature.
Important feature is that as the nonlinearity of the bulk flow
reaction increases, its representative coefficient decreases while
the opposite is true for the nonlinear boundary reaction. Reversible
reaction rate kinetics as well as the rate of irreversible reaction also
exhibit opposite effect on these two transport coefficients. The
transport coefficients are largely dominated by the wall-phase
reactions compared with the fluid-phase reactions. These two
types of reactions make a coupled effect on the transport coeffi-
cients so that the influence of one may be largely affected by the
strength of the other reactions. The coefficients are found to be
greatly motivated by the kinetics of the reactions when the reten-
tive effect of the wall is slow.
Acknowledgement
The authors thank Professor Chiu-On Ng of the University of
Hong Kong for providing partial financial support from the
Research Grants Council of the Hong Kong Special Administrative
Region, China, through Project No. HKU 7156/09E during BSM’s
visit to his department. Authors wish to acknowledge the anony-
mous reviewers for their valuable suggestions for bringing the
paper into its present form.
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