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 HMT 7935 No. of Pages 12, Model 5G
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International Journal of Heat and Mass Transfer xxx (2010) xxx–xxx

1

Contents lists available at ScienceDirect

International Journal of Heat and Mass Transfer

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

2 Effects of nonlinear chemical reactions on the transport coefficients associated

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

6
a r t i c l e i n f o a b s t r a c t
8
2 1
9 Article history: The paper concerns with the determination of effective transport coefficients associated with the 22
10 Received 5 June 2009 oscillatory flow through a tube where a solute undergoes nonlinear chemical reactions both within the 23
11 Received in revised form 8 June 2010 fluid and at the boundary. Method of homogenization, a multiple-scale method of averaging, is adopted 24
12 Accepted 25 August 2010
to derive the transport equation that contains advection, diffusion and reaction. The resultant equation 25
13 Available online xxxx
shows how the transport coefficients are influenced by the rate and degree of the nonlinear chemical 26
reaction. Two different nonlinear reactions are considered at the bulk flow and the boundary. The reac- 27
14 Keywords:
tions at the boundary may be reversible and irreversible in nature. Several facts are established from the 28
15 Phase exchange
16 Homogenization
model by fixing the rate or degree of the nonlinear reactions. Results demonstrate that the reaction at the 29
17 Transport coefficient boundary is more influential than the bulk-flow reaction in determining the transport coefficients. Also 30
18 Nonlinear reaction fluid-phase reaction coefficient diminishes as the nonlinearity increases, whereas the trend is opposite 31
19 Phase partition coefficient for the nonlinear wall-phase reaction coefficient. Different controlling parameters are found to play sig- 32
20 nificant role on the transport coefficients when the ratio of wall-phase concentration to the fluid-phase 33
concentration is low. 34
Ó 2010 Published by Elsevier Ltd. 35

36
37

38 1. Introduction The phenomena of mass transport becomes more complex 59

when the transported material is chemically reactive. Knowledge 60
39 Transport of solute through a tube has always been an impor- of the transport coefficients associated with the flow of a reactive 61
40 tant topic in fluid mechanics. Due to its applications in the field species has applications as diverse as chromatographic separations 62
41 of chemical, environmental and biomedical engineering, mass in chemical engineering, the spreading of pollutants in a stream, 63
42 transport phenomena have been extensively studied during the the mixing and transport of drug and toxins in physiological sys- 64
43 past fifty years. Investigation was initiated by Taylor [1] when he tems and so on. Reactions originated from chemical or biological 65
44 published the landmark paper concerning the transport of a con- processes are very common in aqueous environment. The fluid dy- 66
45 taminant dissolved in a fluid flowing through a pipe of narrow namic behaviour of the transport coefficients can be greatly influ- 67
46 diameter. He demonstrated that an interaction between the trans- enced by the presence of chemical processes like phase exchange, 68
47 verse variations in the fluid’s velocity field and the transverse dif- partitioning, boundary uptake or chemical reactions. Transport 69
48 fusion of the solute yielded an effective downstream mixing through these processes has widely been extended to applications 70
49 mechanism for the solute. This mechanism has since been dubbed in biological or physiological transport (Davidson and Schroter [8], 71
50 ‘Taylor Dispersion’. He found an approximate analytical formula Grotberg et al. [9], Phillips and Kaye [10]). Reactions may occur in 72
51 for the transport coefficient, more particularly for the dispersion the bulk flow or at the boundary. It may be reversible or irrevers- 73
52 coefficient which is a measure of the rate at which a solute spreads ible in nature and linear or nonlinear in degree. Linear reversible or 74
53 along the flow. Since then many related studies have been sur- irreversible reactions at the boundary has received a considerable 75
54 faced. Incorporating the effect due to molecular diffusion, Aris [2] attention by the researchers such as Gupta and Gupta [11], Purn- 76
55 modified Taylor’s expression for the dispersion coefficient using ama [12], Mazumder and Das [13], Jiang and Grotberg [14], Sarkar 77
56 his method of moments. Later on Chatwin [3], Gill and Sankara- and Jayaraman [15], Mazumder and Mondal [16], Ng [17,18], Paul 78
57 subramanian [4], Smith [5], Sullivan [6], Pedley [7] and others con- and Mazumder [19] and others. 79
58 tribute significantly on this complex field. Thus prosperous literature exists on mass transport when the 80
transported substance is chemically inert or it undergoes a first or- 81
der chemical reaction either within the bulk flow or at the bound- 82

⇑ Corresponding author. Tel.: +91 3325753033. ary. But the case is different when the reactions are not linear. In 83

E-mail address: bijoy@isical.ac.in (B.S. Mazumder). spite of its biological and industrial applications, less attention 84

0017-9310/$ - see front matter Ó 2010 Published by Elsevier Ltd.

doi:10.1016/j.ijheatmasstransfer.2010.08.028

Please cite this article in press as: S. Paul, B.S. Mazumder, Effects of nonlinear chemical reactions on the transport coefficients associated with steady and
oscillatory flows through a tube, Int. J. Heat Mass Transfer (2010), doi:10.1016/j.ijheatmasstransfer.2010.08.028
 HMT 7935 No. of Pages 12, Model 5G
15 October 2010

2 S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer xxx (2010) xxx–xxx

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

85 has been made to the effects of nonlinear reactions upon a system based on the half-life of the substances used and sometimes the 125
86 of solutes undergoing Taylor Dispersion. Established literature pro- pH of the body as well. Practically, this affects the way in which 126
87 vides no insight for the effective transport coefficients when the dosages are determined and prescribed. The rate of reactions and 127
88 nonlinearity is of the order of two or more. Though Barton [20] the various conditions under which they occur are crucial for 128
89 and Smith [21] considered the effect of second order reaction on determining certain aspects of environmental protection. 129
90 dispersion phenomena, but such limited attempts are too deficient The main objective of the present paper is to examine the influ- 130
91 considering its vast environmental and biological importance. In ence of nonlinear reactions on the transport coefficients, when the 131
92 two successive papers, Revelli and Ridolfi [22,23] have shown the flow is driven by a pressure gradient comprising steady and peri- 132
93 effect of nonlinear chemical reactions on suspended material in odic components. We present here a rigorous mathematical model 133
94 sediment-laden turbulent streams. Still there remains a lot to for the evolution of the concentration of reacting solutes that travel 134
95 know about the effect of higher order chemical reactions on solute within a fluid flowing down a pipe of circular cross-section. The 135
96 transport. intention is to provide analytical expressions for the transport 136
97 The mathematical models that describe chemical reaction coefficients and to look into the effect of nonlinear chemical reac- 137
98 kinetics provide chemists and chemical engineers with tools to tions on those coefficients. With this in view, a two dimensional 138
99 better understand and describe chemical processes such as food mathematical model is formulated to take into account advection, 139
100 decomposition, microorganism growth, stratospheric ozone diffusion and reaction. The mathematical homogenization theory 140
101 decomposition, and the complex chemistry of biological systems. (Mei et al. [24]) is adopted to take cross-sectional and time aver- 141
102 These models can also be used in the design or modification of ages of the two dimensional model, and the most general case is 142
103 chemical reactors to optimize production, more efficiently segrega- dealt with in which the reactions are nonlinear both in the bulk 143
104 tion of products, and elimination of harmful by-products. When flow and boundary. 144
105 performing catalytic cracking of heavy hydrocarbons into gasoline
106 and light gas, for example, kinetic models can be used to find the
2. Velocity distribution 145
107 temperature and pressure at which the highest yield of heavy
108 hydrocarbons into gasoline will occur. The kinetics of chemical
We consider a fully developed, axi-symmetric laminar flow of a 146
109 reactions, which determines the order of nonlinear reactions, illu-
homogeneous, incompressible viscous fluid through a pipe of ra- 147
110 minate the process by which a reaction takes place. The principal
dius a. We have used a cylindrical coordinate system in which 148
111 factor in kinetics is the rate of the reaction. Many factors, such as
the radial and axial co-ordinates are r and x respectively. The flow 149
112 concentration and temperature, influence the rate of a reaction. Gi-
is assumed to be unidirectional and so the velocity has only axial 150
113 ven the ubiquity of chemical reactions, kinetics can be applied to a
component u(r, t) which satisfies the Navier–Stokes equation as: 151
114 wide variety of practical situations. An understanding of kinetics 152
 
115 enables the precise dealing of important reaction rates in biological @u 1 @p 1 @ @u
116 and industrial fields. Chemical kinetics helps to reveal the nuances ¼ þm r ;
@t q @x r @r @r 154
117 of important rate-based processes such as metabolism. In turn, this
118 knowledge helps scientists and other professionals to determine where @p@x
is the axial pressure gradient, q is the fluid density and m is 155
119 the best course of action for one’s personal nutrition. Nonlinear the kinematic viscosity. 156
120 chemical reactions have a wide variety of application in the world The horizontal pressure gradient, which drives the flow, con- 157
121 of medicine. In addition to the ways in which the human body sists of steady and harmonically fluctuating components, 158
122 undergoes processes of respiration and metabolism, nonlinear 159
123 reactions also play a large part in the supervision of drugs. For 1 @p
 ¼ P½1 þ wReðeixt Þ;
124 example, the mechanisms for the sustained release of drugs are q @x 161

Please cite this article in press as: S. Paul, B.S. Mazumder, Effects of nonlinear chemical reactions on the transport coefficients associated with steady and
oscillatory flows through a tube, Int. J. Heat Mass Transfer (2010), doi:10.1016/j.ijheatmasstransfer.2010.08.028
 HMT 7935 No. of Pages 12, Model 5G
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S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer xxx (2010) xxx–xxx 3

162 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 227
163 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 228
164 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 229
165 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 230
166
167 following velocity profile, Ng [17]. 231

169 uðr; tÞ ¼ us ðrÞ þ Re½uw ðrÞe ixt

; ð1Þ The boundary conditions for (2) can now be formulated as: 232
233
@C
170 where the steady component (us(r)) of the velocity is, ¼ 0; r ¼ 0 ð3Þ
171  @r
 r 2 
@C @C s
173
us ðrÞ ¼ hus i 1 
a D  CC ¼ ¼ kðaC  C s Þ  ks C m
s ; r ¼ a; ð4Þ 235
@r @t
174 and its unsteady component (uw(r)) is given by where C is the irreversible absorption rate. 236
175  
Pw J ðrrÞ
uw ðrÞ ¼ i 1 0 : 4. Assumptions 237
177 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- 238
178 8m
turbation analysis: 239
179 the pipe (the angle brackets denote averaging across the tube sec-
180 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 240
181 r2 =ix/m or r = (1i)/d where d ¼ 2m=x solute into the flow so that the length scale for the longitudinal 241
spreading of the reactive species is much greater than the tube 242
182 3. Governing equation and boundary conditions radius. By this we mean that x = O(L) and r = O(a), where L is a 243
characteristic longitudinal distance for the solute transport. 244
183 We consider the transport of a chemically reactive solute along a The ratio 245
246
184 tube whose walls are made of retentive and reactive materials. It is
185 assumed that the solute is completely miscible in the fluid and
 ¼ a=L << 1 248

186 undergoes nonlinear reactions with it in the bulk flow. Also at the is small enough to use as ordering parameter. 249
187 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 250
188 reactions with the wall material. As a result a portion of the solute period there can be no appreciable transport effects down the 251
189 is absorbed irreversibly by the wall material and some portion takes tube. In other words, flow oscillations are sufficiently fast and 252
190 part in a reversible phase exchange process with the flowing fluid. a large number of flow oscillations are required for the spread- 253
191 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 254
192 the boundary are termed as mobile and immobile phases tube is so fine in bore that diffusion across the entire cross-sec- 255
193 respectively. tion may be accomplished within this short time scale. 256
194 If C is the concentration (mass of solute per bulk volume of the 3. The two reactions occurring at the boundary are of different 257
195 flowing fluid) of the mobile phase and Cs is the concentration (mass orders. The reversible phase exchange is much faster than the 258
196 of solute per surface area of the boundary wall) of the immobile irreversible reaction. This ensures that local equilibrium can 259
197 phase, then at equilibrium be largely achieved over a finite number of oscillations. The rate 260
198
Cs of irreversible absorption is much slower and it is comparable 261
200 ¼ a; with the advection speed down the tube. 262
C
4. The Peclet number is equal to or greater than order of unity: 263
201 where a is a partition coefficient having the dimension of length. 264
202 When, in general, equilibrium is not attained, the phase ex- Pe  ahus i=D P Oð1Þ: 266

203 change will take place in either forward or backward direction Under these assumptions, three distinct time scales, which gov- 267
204 according to erns the total transport process, may be defined as (Ng [17]) 268
205 269
@C s 2
Time scale for the radial diffusion : T 0 ¼ 2p=x ¼ Oða =DÞ ¼ Oðk Þ;
1
207 ¼ kðaC  C s Þ þ Rs ;
@t
Time scale for advection and reactions : T 1 ¼ L=hus i ¼ OðaC1 Þ ¼ T 0 =;
208 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 : 271
209 nonlinear reaction occurring at the boundary to be defined later.
210 The problem for the transport of the reactive solute can now be Thus T1 and T2 are respectively one and two order of magnitude 272
211 formulated as follows: longer than T0. Based on these time scales, we may introduce 273
212
2   accordingly 274
@C @C @ C D @ @C 275
þ uðr; tÞ ¼D 2þ r þ R; 0 < r < a; ð2Þ 2
214 @t @x @x r @r @r t 0 ¼ t; t1 ¼ t; t2 ¼  t; 277

215 where D is the molecular diffusion coefficient assumed to be con- which are, respectively, the fast, medium and slow time 278
216 stant. The term R on the right hand side of (2) represents the effect variables. 279
217 of nonlinear chemical reaction occurring in the bulk flow. 280
218 Two different nonlinear reactions (represented by R and Rs ) are 5. Asymptotic analysis 281
219 assumed to affect the mobile and immobile phases. The corre-
220 sponding reaction rates, R and Rs , are therefore prescribed accord- Let us assume that the radial diffusion is two order of magni- 282
221 ing to the power laws, tude greater than the longitudinal dispersion and one order of 283
222
n magnitude greater than the advection which is again comparable 284
224 R ¼ kC ; Rs ¼ ks C m
s ;
with the rate of irreversible reaction at the boundary as mentioned 285
225 where coefficients k and ks are the nonlinear reaction rate constants earlier. The rate of nonlinear reactions occurring in the bulk flow 286
226 for the mobile and immobile phases respectively (their units are and at the boundary are also assumed to be comparable with the 287

Please cite this article in press as: S. Paul, B.S. Mazumder, Effects of nonlinear chemical reactions on the transport coefficients associated with steady and
oscillatory flows through a tube, Int. J. Heat Mass Transfer (2010), doi:10.1016/j.ijheatmasstransfer.2010.08.028
 HMT 7935 No. of Pages 12, Model 5G
15 October 2010

4 S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer xxx (2010) xxx–xxx

288 advection. The reactions play a significant role in the whole trans- For first order (O()), Eqs. (5)–(7) give: 347
  348
289 port process if the time scales of the reactions and advection are
@C 0 @C 1 @C 0 D @ @C 1
290 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
291 that lead to a considerable reduction of the influences of longitudi-
292 nal transport mechanisms, on the contrary if the reactions are too @C 1
¼ 0; r ¼ 0; ð19Þ
293 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
294 D  CC 0 ¼ þ ¼ kðaC 1  C s1 Þ  ks C m
s0 ; r ¼ a: ð20Þ 350
295 the two nonlinear reactions-one in the bulk flow and the other at @r @t 1 @t 0
296 the boundary are comparable to each other. Averaging the Eqs. (18)–(20) w.r.t the fast time variable t0, we get 351
297 The relative significance of the terms in the transport Eq. (2) ! 352
298 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
299 as indicated below with the power of : @t 1 @x r @r @r
300
 
@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 354
@t @x @x r @r @r @r
@C and 355
¼ 0; r ¼ 0; ð6Þ 356
@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
302 s ; @r @t 1 358
@r @t
303 To carry on the perturbation analysis, let us expand the dependent where the overbar denotes time average over one period of oscilla- 359
304 variables C and Cs in power series of the perturbed parameter : tion and us is the steady velocity component. We further take cross- 360
305 sectional average of (21) subject to the conditions (17), (22) and 361
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 362
363
307 þ 2 C 2 ðx; r; t 0 ; t1 ; t 2 Þ þ Oð3 Þ; ð8Þ @C 0 hus i @C 0 2C k
308 þ þ C 0 þ C n0 ¼ 0; ð24Þ 365
@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 366
310 þ Oð3 Þ: ð9Þ 367
2a
311 The terms Cn and Csn, (n = 1, 2, 3 . . .) are purely oscillatory functions R¼1þ ; 369
a
312 of short time variable t0 as they are subject to advection due to flow
is the retardation factor. 370
313 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), 371
314 der (i.e., n = 0), and therefore the leading order concentrations are @t 1
we rewrite the Eqs. (18)–(20) as: 372
315 taken to be independent of the time variable t0 [17,18].   373

9
316 The nonlinear decay term in (5) and (7) can also be expanded in @C 1
þ u  huRs i @C 0
 2aRC C 0 þ 2k a Cn ¼ D @
r @C 1
; 0 < r < a>
@t 0 @x aR 0 r @r @r >
>
317 power series as: >
>
318 @C 1 =
¼ 0; r¼0
kC n ¼ kðC 0 þ C 1 þ 2 C 2 þ    Þn @r
>
D @C 1
¼ a huRs i @C 0
þ CR C 0  kRa C n0 þ @C s1 >
>
>
 kC n0 þ 2 nkC n1 3 @r @x @t0 >
320 0 C 1 þ Oð Þ; ð10Þ m m
;
¼ kðaC 1  C s1 Þ  ks a C0 þ CC 0 ; r¼a
321
 ks C m 2
¼ ks ðC s0 þ C s1 þ  C s2 þ    Þ m ð25Þ 375
s

 ks C m 2 m1 3 The structure of (25) suggests the substitutions 376

323 s0 þ  mks C s0 C s1 þ Oð Þ: ð11Þ 377
324 For the multiple-scale asymptotic analysis, the time derivative has   @C 0
C 1 ¼ NðrÞ þ ReðBðrÞe ixt 0
Þ þ MðrÞC 0 þ EðrÞC n0 þ FðrÞC m
0 ð26Þ 379
325 been expanded as: @x
326
@ @ @ @ and 380
328
¼ þ þ 2 : ð12Þ 381
@t @t0 @t1 @t 2   @C 0
C s1 ¼ N s þ ReðBs eixt0 Þ þ Ms C 0 þ Es C n0 þ F s C m
0; ð27Þ 383
329 Using the expansions (8)–(12) in Eqs. (5)–(7) and equating the coef- @x
330 ficients of like powers of  from both sides, a system of differential where the coefficients N(r), Ns; M(r), Ms; B(r), Bs; E(r), Es and F(r), Fs 384
331 equations is obtained: satisfy certain boundary value problems that can be obtained by 385
332
333 For zeroth order (O(1)) Eqs. (5)–(7) give: substituting (26) and (27) into (25), and equating the coefficients 386
 
D @ @C 0 of analogous terms from both sides, e.g. the steady terms associated 387
0¼ r ; 0 < r < a; ð13Þ
r @r @r with @C
@x
0
prescribes the equation for N(r) and Ns as: 388
389
@C 0  
¼ 0; r ¼ 0; ð14Þ D d dN hus i
@r r ¼ us  ; 0<r<a ð28Þ
r dr dr R 391
@C 0
335 D ¼ kðaC 0  C s0 Þ; r ¼ a: ð15Þ with the boundary conditions 392
@r 393
336 Eqs. (13) and (14) obviously imply that the leading order concentra- dN
337 tion is independent of r, i.e., ¼ 0; r ¼ 0;
338 dr
340 C 0 ¼ C 0 ðx; t1 ; t 2 Þ: ð16Þ dN hus i
D ¼ a ¼ kðaN  Ns Þ; r ¼ a: 395
341 The boundary condition (15) then gives dr R
342
344 C s0 ¼ aC 0 : ð17Þ Again equating the coefficient of C0 from both sides, M(r) and Ms are 396
obtained as: 397
345 As expected, at the leading order the mobile phase of the reactive 398
346 solute is at local equilibrium with the immobile phase.

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 HMT 7935 No. of Pages 12, Model 5G
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452
 
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
400 r dr dr aR @t 1 R @x 2 R @x R @x
   
401 with the boundary conditions 1 2ChNi @C 0 1 2nChEi n
402  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
aR R R aR 454
dM C
404 D ¼ ¼ kðaM  Ms Þ þ C; r ¼ a: 455
dr R
@C 1 1 @2 C0 @C n @C m
405 Similarly, equating the unsteady terms linked with we obtain @C 0
, hu i ¼ ðhus Ni þ Rehuw B iÞ 2 þ hus Ei 0 þ hus Fi 0
@x @x 2 @x @x @x
406 the following equation for the complex functions B(r) and Bs:
407
  @C 0
D d dB þ hus Mi 457
r ¼ ixB þ uw ; 0<r<a ð30Þ @x
409 r dr dr 458
@C s1 hus iNs @ 2 C 0 1 @C n0 hus iF s @C m
0
410 with the boundary conditions, ¼  ðkN s þ hu s iE s Þ 
411 @t1 R @x2 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
413 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 460
aR R 0 R aR
414 Equating the coefficient of C0n, we have the following equation for
461
415 E(r) and Es: 462
416
  @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 ; 464
r ¼ ð31Þ @x
418 r dr dr aR
where * denotes the complex conjugate. 465
419 with the boundary conditions
420 Substitution of these terms in (38) produces 466
dE 467
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

422 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 469
0 0
423 Finally the coefficient of C0m produces the following equation for
424 F(r) and Fs: with 470
425
  471
D d dF  
r ¼0 ð32Þ D 1 hus i hus i 1
427 r dr dr D0eff¼ þ N  us þ 2N s 2  Rehuw B0 i;
R R R aR 2R
 
428 with the boundary conditions 2k 1 hus i 2hus iEs
429 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 473
431 D ¼ 0 ¼ kðaF  F s Þ  ks am ; r ¼ a: ð34Þ
dr     474
2 1 hus i 2M s hus i 2C 2Ns 2C
432 For second order (O( )), (5)–(7) give: f03 ¼ M  us  2
 2
hNi þ þ NðaÞ;
433 R R aR aR a aR 476
@C 0 @C 1 @C 2 @C 1 @ 2 C 0 D @ @C 2
þ þ þu ¼D 2 þ ðr Þ     477
@t2 @t 1 @t 0 @x @x r @r @r nkhMi 2C 2nC 2Es k 2M s
0
 nkC n1 v ¼ þ EðaÞ  2 hEi þ  2 hMi þ ;
0 C1; 0 < r < a; ð35Þ
435 1
R aR aR a R a 479
436 480
 
@C 2 2C 2mC 2F s
438 ¼ 0; r¼0 ð36Þ v 0
2 ¼ FðaÞ  hFi þ ;
@r aR aR2 a
439 and 2nk
440 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
442 ¼ kðaC 2  C s2 Þ  mks C m1
s0 C s1 r¼a ð37Þ  
2C hMi 4 CM s
v05 ¼ MðaÞ   :
443 Averaging the Eq. (35) w.r.t time followed by space subject to the aR R a2 R2 482
444 boundary conditions (36) and (37) we have:
445
@C 0 1 @hC 1 i 1 @C 1 2C 2 @C s1 kn n1 6. Transport coefficients 483
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 484
447 ¼ : ð38Þ (12) one obtains 485
R @x2 486
448 Using (1), (24), (26) and (27), we find each term of (38) as follows: @C 0 @2C0 @C n @C m @C 0
449  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
451 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 488
@x

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" # 538
489 where b0
@C D hus i2 a2 hus i2 a2 @ 2 C b0
490  þ DTs þ DTw
@t R D D @x2
hus i k 2C 1 |fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl}
492 f3 ¼ f03 þ ; v1 ¼ v01 þ ; v5 ¼ v05 þ
R R aR 2

@Cbn bm
@C @Cb0
493 and the other coefficients are equal to their dashed counterparts. þ hus in1 0
þ hus in2 0
þ hus in3 b n þ kc C
þ kc1 C bm
0 2 0
494 Here Deff is the effective dispersion coefficient, fi’s (i = 1, 2, 3) @x @x @x 6 7
3 4 5
495 are the effective coefficients for advective terms and vi’s (- b 2n1 þ kc C
b mþn1 þ kc C
b
þ kc3 C 0 4 0 5 0 ¼ 0; ð41Þ
496 i = 1, 2, . . . , 5) are the coefficients for the reaction terms. It should 8 9 10 540
497 be mentioned here that the coefficients v1, v3 and f1 are the results
498 of nonlinear reaction in the bulk flow while v2 and f2 signify the where 541
542
 
499 effect of nonlinear reaction at the boundary. The coupled effect 1 11 1 1 2a
^
500 of both the reactions can be seen form v4. The linear irreversible DTs ¼  þ 2 þ 3 ; ð42Þ
R 48 3R 8R R Da 544
501 reaction at the boundary is represented by the coefficient v5.
( ) 545
502 For determination of the coefficients in (40) we need to solve
8^d6 w2 d^2 A ½r ^  ÞJ1 ðr
^ J0 ðg ^  J 0 ðr
^Þ  g ^ ÞJ1 ðg
^  Þ Ar
^ J1 ðg ^ J 1 ðr
^Þ  g ^Þ
503 (28)–(32) subject to the respective boundary conditions which DTw ¼ Re  i ;
ScR 2ðSc2  1ÞjJ0 ðr ^ Þj2 ðSc  1Þg ^r
^ J 0 ðr^Þ
504 produces
505 ð43Þ 547
   
hus i 2 1 r2 548
NðrÞ ¼ Nð0Þ þ r 1  2 ; ^ ðr
2D 2R 4a bJ ^ Þ þ Scr
^ J 1 ðr
^Þ
^¼ 1  iðk=xÞ k Da ^d2
 A¼ 0 ; b Da a
^; ¼
a hus ia2 a hus i ^ ðg
bJ ^Þ þ g
^ J ðgÞ
0 1 ðk=xÞ2 þ 1 x 2Sc 550
N s ¼ aNð0Þ þ a 1 þ 6 þ ;
a 8RD k R 551
 
C aa2 a 2C 1
MðrÞ ¼ Mð0Þ  2
r ; M s ¼ aMð0Þ þ  þ ; n1 ¼ 3 ^ka
^ ð2RDa  3Da  12a
^ Da  24Þ; ð44Þ 553
2aRD 4D k aR 6R
  554
Pw ADJ 0 ðgrÞ  mJ 0 ðrrÞ ib
BðrÞ ¼ 2 1 þ ; Bs ¼ BðaÞ; where 2^ m
x ðm  DÞJ 0 ðraÞ x n2 ¼ ks a
^ ; ð45Þ
R2 556
bJ ðraÞ þ mrJ 1 ðraÞ ix ixka
A¼ 0 ; g2 ¼  ; b ¼  ; " 557
bJ 0 ðgaÞ þ DgJ 1 ðgaÞ D k þ ix b 1 1    #
  1 C 1 2
ka 2 1 aa ka n3 ¼ 1þ2   1 ; ð46Þ
EðrÞ ¼ Eð0Þ þ r ; Es ¼ aEð0Þ þ þ ; R R 3 4R R Da 559
2aDR k 2D R
! 560
ks
507 FðrÞ ¼ Fð0Þ; F s ¼ aFð0Þ  am ; b
^k C R2
a^ a^
k c1 ¼ ^2
a^ R  2na  8n þ a^  8 þ 2 ; ð47Þ
2R3 Da Da b
C 562
508 where N(0), M(0), E(0) and F(0) are undetermined constants. These 563
509 undetermined constants are not required for the evaluation of Deff, 4m Cb
c2 ¼ ^ks ; ð48Þ
510 fi’s and vi’s when the reactions are linear. Even for nonlinear reac- Da R2 565
511 tions, they are not essential as far as the coefficients Deff, f1, f2, f3, v3 566
512 and v5 are concerned for the terms involving those undetermined n
513 constants in each of the expressions cancel out to zero. But these
c3 ¼  3
a^ ^k2 ða^ Da þ 4Þ; ð49Þ 568
2R
514 constants are mandatory for the determination of v1, v2 and v4. 569
515 To evaluate the undetermined constants let us take, without any 2m
516 loss of generality, that
c4 ¼ 2 a^ k^^ks ; ð50Þ 571
R
" 572
517
b b1   #
519 hC 1 ðrÞi ¼ 0; 2 C 2C 1 1
c5 ¼ 1 þ 1 ð51Þ
R Da R 8R R Da 574
520 so that
521 and for convenience, each term of Eq. (41) is marked enclosing 575
523 hNðrÞi ¼ hMðrÞi ¼ hEðrÞi ¼ hFðrÞi ¼ 0; numbers rounded by circle below the individual terms. 576
524
525 which yields Eq. (41) is the one dimensional nonlinear partial differential 577
hus ia2 ð3  5RÞ aC equation that models the concentration of the mobile phase of a 578
Nð0Þ ¼ ; Mð0Þ ¼ ; Eð0Þ reacting substance which undergoes a nonlinear chemical reaction 579
24DR 4RD
aka both within the flow and at the boundary. The equation clearly 580
527 ¼ and Fð0Þ ¼ 0: shows how the combined action of two different types of nonlinear 581
4RD
reactions changes the transport mechanisms to a great extend. 582
Complex interactions between the mobile phase and immobile 583
528 Finally when all the coefficients are determined, using the following
phase and fluid dynamic mechanisms that regulate the evolution 584
529
530 normalised variables
of the concentration of the reactive solute, can be accessed from 585
2
b 0 ¼ C0 ; a a b Ca
^¼ ; C
ka the Eq. (41). Recalling the relationship (17), the spatial and tempo- 586
C ¼ ; Da ¼ ;
C ð0Þ a D D ral behaviour of Cs0(x, t) can also be deduced from (41). 587
^k ¼ k C n1 ; ^ks ¼ ks am1 C m1 Two special cases can be derived from the general Eq. (41). In 588
532 k ð0Þ k ð0Þ
order to underline the role of nonlinearities, let us explain these 589
534 two cases separately-. 590
533
ba m
536 r^ ¼ ra; g^ ¼ ga; ^d ¼ d=a; b^ ¼ ; Sc ¼ : Case 1: There is no nonlinear reaction in the bulk flow and the 591
D D boundary, i.e., the solute undergoes only linear irreversible absorp- 592
537 Eq. (40) can be written as tion by the wall material and reversible phase exchange with the 593

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594 flowing fluid. In this case k = ks = 0 and consequently the coeffi- versible reaction at the boundary. The retention parameter a ^ is 648
595 cients n1, n2, c1, c2, c3 and c4 as given by the Eqs. (44), (45), (47), the ratio of solute mass distributed between the phase retained 649
596 (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 650
597 " # non-retentive or inert boundary. The number Da is the ratio of 651
@Cb0 D hus i2 a2 hus i2 a2 @ 2 C b0 @Cb0
 þ DTs þ DTw þ hus in3 b 0 ¼ 0;
þ kc5 C the phase exchange rate to the diffusion rate. The order of the non- 652
@t R D D @x2 @x 10 linearities m and n and corresponding rates of the reactions ^ k and 653
1 |fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl} 5
2
^
ks are also required for the determination of the coefficients. The 654
599 ð52Þ parameter ^
d is identified as oscillation parameter. It can be noted 655
pffiffi pffiffiffi
that ^
d ¼ K2, where K ¼ a xm is the Womersley number. Thus ^ d is re- 656
600 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 657
601 respectively. number used to describe the unsteady nature of fluid flow in re- 658
602 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 659
603 noteworthy analysis. 2
ratio of the time am required for viscosity to smooth out the 660
604 Case 2: This case corresponds to when both the reactions occur-

transverse variation in vorticity to the period of oscillation x1 . An- 661

605 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 662
606 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 . 663
607 which reads as: Let us first describe few important features of the two disper- 664
608
b0 b0 b0 sion coefficients (i.e., DTs and DTw) arising from the steady and 665
@C @2 C @C
 Deff 2
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 666
@t @x @x
coefficients were reported by Ng [17] in detail. But for the sake 667
b0
þ c ÞC 5 of being self contained, some of them are reproduced in the text. 668

610 ¼ 0; ð53Þ Fig. 1(a) shows the variation of the oscillatory component of the 669
dispersion (DTw) coefficient with the Schmidt number Sc. It is ob- 670
611 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 671
612 and Sankarasubramanian [4], the reaction (K0), convection (K1) and DTw, but the effect is significant only when oscillation parameter ^ d 672
613 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 673
614 can be identified from this model as: longer remains sensitive to Sc. Variation of DTw with ^ d can be seen 674
615
from Fig. 1(b). DTw increases monotonically with ^ d and depending 675
617 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
618 It should be mentioned here that K2 is affected only by the revers-
619 ible phase exchange up to the second order of the present analysis.
620 But the first two transport coefficients (K0 and K1) are affected by
621 both reversible and irreversible reactions. If we proceed to the next
622 order (i.e., third order), then only the effects of irreversible reaction
623 on the corresponding K2 can be found out (Ng [17]).
624 The nature of these coefficients will be discussed in the follow-
625 ing section. In real cases n1, n2 may be neglected with respect to n3
626 and c3, c4 with respect to other three coefficients (c1, c2, c5). How-
627 ever for this linear case no approximation is made. Approximations
628 are made only for the case where nonlinearity is concerned.
629 The event, when n = m, can also be considered as a subcase
630 resulting from the general Eq. (41). In this case the Eq. (41) reduces
631 to:
632 " #
b0
@C D hus i2 a2 hus i2 a2 @ 2 C b0 @Cbn
 þ DTs þ DTw þhus iðn1 þ n2 Þ 0
@t R D D @x2 3 4 @x
1 |fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl}
2

@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
634
@x 6 7 8 9 10
5

635 The coupled effect of the two nonlinear reactions can be observed
636 from the Eq. (55).

637 7. Results and discussions

638 In the cross sectionally averaged transport equation, the disper-

639 sive, advective and reactive fluxes are controlled by some effective
640 coefficients. These transport coefficients are essentially dependent
641 on the factors such as the steady and unsteady flows, cross sec-
642 tional geometry, partition of solute in various phases, chemical
643 reactions and so on which are need to be prescribed in order to
644 compute the coefficients. For the present problem the controlling
645 parameters are, among others, a b which are respectively
^ , Da and C
646 the phase partition ratio or retention parameter, Damkohler num- Fig. 1. Variation of the oscillatory component of the dispersion coefficient (a) with
647 ber (rate of reversible reaction at the boundary) and rate of irre- Schmidt number Sc and (b) with oscillation parameter ^ d.

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8 S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer xxx (2010) xxx–xxx

676 on Sc and a ^ , it becomes almost constant beyond a certain ^ d. Here

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

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).

phase exchange rate is very fast (i.e., Da is large), advection coeffi- 726
cient increases with Cb [Fig. 6(a)]. Thus reversible and irreversible 727
reaction processes are not independent. Effect of one can be greatly 728
influenced by the other. The figure also indicates that under the 729
phase exchange with strong kinetics, the advection speed is af- 730
fected by the wall absorption drastically which explains the well 731

Fig. 2. Variation of the steady (DTs) and unsteady (DTw) components of the
known result that the reversible phase exchange can retard advec- 732
dispersion coefficients with the partition coefficient a
^ for different reaction rate tion (Ng and Rudraiah [25]). Fig. 6(b) shows the plots of K1 with the 733
parameter Da. reaction rate ratio X. In this case, a
^ has almost negligible effect on 734

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S. Paul, B.S. Mazumder / International Journal of Heat and Mass Transfer xxx (2010) xxx–xxx 9

ceptual point of view, as they show the variety of the links between 743
the reactions and transport mechanisms. However for realistic case 744
(i.e. n, m = O(1)), the following conditions may occur (Revelli and 745
Ridolfi [22]): 746
! 747
@Cbn bm
@C @Cb0
0 0
n1 ; n2 << n3 ;
@x @x @x
   
c3 Cb 02n1 ; c4 Cb mþn1
0 << c1 Cb n; c C
0
bm b
2 0 ; c5 C 0 : 749

As a consequence third, fourth, eighth and ninth terms (numbers 750

within the circles below the terms indicate its position) of the Eq. 751
(41) can be neglected for application purpose and the equation 752
can be approximated as 753
" # 754
b0
@C D hus i2 a2 hus i2 a2 @ 2 C b0
 þ DTs þ DTw
@t R D D @x2
1 |fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl}
2

@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 6 7 10 756
5

Furthermore, if the nonlinear reaction terms from the Eq. (56) are 757
omitted, the equation agrees with Ng [17]. 758
The behaviour of the three prominent reaction coefficients (i.e., 759
Fig. 5. Convection coefficient as a function of the retention parameter (a) for c1, c2 and c5), which are the functions of strength and kinetics of 760
different values of phase exchange rate Da and (b) for different values of irreversible the nonlinear reactions, can be seen here. The ratio X which deter- 761
b.
reaction rate C

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.

735 the rate of rising of K1 with the reaction rates. Although stronger
736 reaction rate leads to an increase of K1, the growth rate is not so
737 significant. The linear variation K1 like K0 with respect to the reac-
738 tion rates is also remarkable.
739 As far as the case of nonlinearity is concerned, numerous non-
740 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
741 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
742 fluid-phase concentration. These terms are important, from a con- (c) for different values of Da.

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Fig. 8. Same as Fig. 7, but for the nonlinear wall-phase reaction coefficient c2.
Fig. 9. Variation of the reaction coefficients (c1, c2 and c5) with the corresponding
rates of reactions (^
k, ^ b ).
ks and C
762 mines intensity of the boundary reaction over the bulk flow reac-
763 tion is an important factor for the determination of the coefficients.
764 It is interesting to see from Eqs. (47) and (48) that the nonlinear
765 reaction rate constants ^ k and ^ks are linearly related with their rep- tonically with a ^ for any nonzero value of m, and the decrement is 789
766 resentative coefficients (i.e., c1 and c2). Consequently the change of sharp when the nonlinearity is of higher order. The monotonicity is 790
767 the reaction rates shows a linear variation with these coefficients, strict for lower range of a ^ and for large a ^ there is no significant 791
768 which is not true for the coefficient c5, the result of first order irre- change. It is observed that the nonlinearity of the reaction leads 792
769 versible reaction at the boundary. The following discussions are to increase the coefficient c2. It should be mentioned here that c2 793
770 devoted solely for the three nonlinear reaction coefficients. With- becomes identically equal to zero when m = 0, i.e., the coefficient 794
771 out loss of generality, we take m = n = 2. has no longer effect on the transport process in presence of the 795
772 Fig. 7 shows the behaviour of the reaction coefficient c1 which is source term. The effects of reversible and irreversible reaction rates 796
773 associated with bulk-flow reaction. It is seen that, except for a ini- (i.e., Da and C b ) on c2 can be seen from the Fig. 8(b,c). Unlike the 797
774 tial short range, c1 increases with a ^ over a substantiable domain other coefficients, c2 is found to increase as the rate of irreversible 798
775 and then it becomes almost constant with respect to a ^ . When reaction at the boundary becomes stronger. Also stronger kinetics 799
776 the values of n are of O(0,1), the initial decrement of c1 immedi- of the phase exchange give rise to higher value of c2 which is pro- 800
777 ately follows stationarity. As the degree of the reaction n increases, nounced when a ^ is sufficiently small. 801
778 the coefficient c1 is found to decrease and this development is The variation of reaction coefficients (c1, c2 and c5) with respect 802
779 more focused over the transient portion, i.e., where c1 alters its to the corresponding reaction rates (^ k, ^
ks and C b ) are shown in 803
780 direction from lowering down to rising up with a ^ [Fig. 7(a)]. Al- Fig. 9(a,b,c) for different values of the retention parameter a ^ . It is 804
781 most no exception is found with c1 compared with the coefficients remarkable to note that depending upon the retention parameter, 805
782 already discussed (i.e., K0 and K1) under the variation of the param- the coefficient c1 may decrease with ^ k [Fig. 9(a)]. Figure shows that 806
783 eters Cb and Da. Stronger Cb or weaker Da both causes the coefficient ^ ensures the lowering of c1 with ^
large a k, which is not the case for 807
784 c1 to increase with a^ beyond a critical value before which the coef- the coefficient c2. It is seen from Fig. 9(b) that for all a ^ , c2 increases 808
785 ficient decreases with a ^ [Fig. 7(b,c)]. with ^ ks , though larger a^ ceases the growth rate of c2. In both cases 809
786 However behaviour is something exceptional as far as the coef- the variations are linear. The coefficient c5 is found to decrease 810
787 ficient c2 is concerned which is linked with the nonlinear reversible monotonically as the reaction rate C b increases [Fig. 9(c)]. 811
788 reaction at the boundary. Fig. 8(a) shows that c2 decreases mono-

Please cite this article in press as: S. Paul, B.S. Mazumder, Effects of nonlinear chemical reactions on the transport coefficients associated with steady and
oscillatory flows through a tube, Int. J. Heat Mass Transfer (2010), doi:10.1016/j.ijheatmasstransfer.2010.08.028
 HMT 7935 No. of Pages 12, Model 5G
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Please cite this article in press as: S. Paul, B.S. Mazumder, Effects of nonlinear chemical reactions on the transport coefficients associated with steady and
oscillatory flows through a tube, Int. J. Heat Mass Transfer (2010), doi:10.1016/j.ijheatmasstransfer.2010.08.028