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Advanced Transport Phenomena

Lecture 6
Mass Transport: Diffusion with Chemical Reaction

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QUASI-STEADY-STATE (QS) DIFFUSION
OUTSIDE ISOLATED SPHERE
 In completely quiescent case, diffusional mass transfer
from/ to sphere occurs at a rate corresponding to Num = 2
 If Bm ≡ v wdm/D is not negligible, then:
ln 1  Bm 
Num  2
and Bm
Num ln 1  Bm 
Fm  Stefan " blowing "  2
Num,0 Bm
 Results from radial outflow due to net mass-transfer

flux across phase boundary

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QUASI-STEADY-STATE (QS) DIFFUSION
OUTSIDE ISOLATED SPHERE
 vw may be established by physically blowing fluid through
a porous solid sphere of same dia => Bm  “blowing”
parameter

 vw is negative in condensation problems, so is Bm

 Suction enhances Num

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QUASI-STEADY-STATE (QS) DIFFUSION
OUTSIDE ISOLATED SPHERE
 Pew,m  alternative blowing parameter, defined by:
 wd m,0
Pew,m 
and D

Num Pew,m
Fm  Stefan blowing   
Num ,0 exp  Pew,m   1
 Equivalent to correction factor for “phoretic suction”

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QUASI-STEADY-STATE (QS) DIFFUSION
OUTSIDE ISOLATED SPHERE
 Stefan-flow effect on Num very similar to phoresis effect,
but with one significant difference:

 Phoresis affects mass transfer of dilute species, but

not heat transfer

 Stefan flow affects both Nuh and Num in identical

fashion, hence not an analogy-breaker

 Corresponding blowing parameters:


vwd h vwd h,0
Bh  Pew,h 
 
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QUASI-STEADY-STATE (QS) DIFFUSION
OUTSIDE ISOLATED SPHERE
and
Nuh ln(1  Bh ) Pew,h
Fh  Stefan blowing    
Nuh ,0 Bh exp  Pew,h   1

 Nuh same function of Bh (or Pew,h) & Pr, as Num is of

Bm (or Pew,m) & Sc

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QS EVAPORATION RATE OF ISOLATED DROPLET

 Droplet of chemical substance A in hot gas

 Energy diffusion from hotter gas supplies latent heat

required for vaporization of droplet of size dp


 Known:
 Gas temperature, T∞
 Vapor mass fraction wA,∞
 Unknowns:
 droplet evaporation rate  m ''
  v
w w or m p   d pm 
2 ''

 Vapor/ liquid interface conditions (wA,w, Tw)

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QS EVAPORATION RATE OF ISOLATED DROPLET

 Assumptions:

 Vapor-liquid equilibrium (VLE) @ V/L interface

 Liquid is pure (wA(l) = 1), surrounding gas insoluble in it

 dp >> gas mean free path

 Forced & natural convection negligible in gas

 Variable thermophysical property effects in gas

negligible

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QS EVAPORATION RATE OF ISOLATED DROPLET

 Assumptions:

 Species A diffusion in vapor phase per Fick’s (pseudo-

binary) law

 No chemical reaction of species A in vapor phase

 Recession velocity of droplet surface negligible

compared to radial vapor velocity, vw, at V/L phase


boundary

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QS EVAPORATION RATE OF ISOLATED DROPLET

 Dimensionless “blowing” (driving force)parameters:

w A, w  w A, 
Bm 
1  w A, w
c p (T  Tw )
Bh 
LA
where wA,w = wA,eq(Tw; p)

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QS EVAPORATION RATE OF ISOLATED DROPLET

 Species A mass balance:


 mA'' ,n continuous, and, in each adjacent phase, given
by:

m  wi m  i ci  Di ,eff  gradw
''
i
''
i

 Since wA(l) = 1, in the absence of phoresis:

mA'' ,n  m'' .w A, w  j A'' ,n , w


(applying total mass balance condition mn  = 0)
''

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QS EVAPORATION RATE OF ISOLATED DROPLET

 Since m   vw , and
''

  w A  
   DA  
 w A, w  w A,  
   DA 
''
j A, n , w
  n   w dm
We can relate Bm directly to mass fractions of A as:

vwd m w A, w  w A,
Bm  
D 1  w A, w

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QS EVAPORATION RATE OF ISOLATED DROPLET

 Similarly, energy conservation condition at V/L interface


leads to relation between Bh and T∞-Tw
m'' LA  qn'' , w  Fourier 
(neglecting work done by viscous stresses)

where LA  latent heat of vaporization

LA  hA Tw   hAl  Tw ; p 

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QS EVAPORATION RATE OF ISOLATED DROPLET

 Heat Flux:
  T    T  Tw 
q  Fourier    k 
''
  k. 
  n   w  dh 
n,w

 Mass Flux:
m 2
''  DA  
.ln 1  Bm 
dp
 Relating the two:

m 
'' qn  Fourier 
''

2
 k / cp 
.ln 1  Bh 
LA dp

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QS EVAPORATION RATE OF ISOLATED DROPLET

 Driving forces are related by:

1  Bh   1  Bm 
Le

where Le = DA/ [k/cp] = Lewis number


 Yields equation for Tw

 Solution yields Bh, Bm

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QS EVAPORATION RATE OF ISOLATED DROPLET

 Single droplet evaporation rate


 k   c p T  Tw  
m p  2 d p   .ln 1  
c
 p   LA 
 Equating this to
d  4  p 
d
3

  l     (overall mass balance on the entire droplet )


dt  3  2  
 
 We find that dp2 decreases linearly with time:

  g   c p T  Tw   

d d
2 2
 8    ln 1  t
  l
p p ,o
   LA 
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QS EVAPORATION RATE OF ISOLATED DROPLET

 Setting dp = 0 yields characteristic droplet lifetime:

d p2,0
tlife,vap 
   g   c p T  Tw   
8   ln 1  
  l   LA  

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STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET
 Catalyst impregnated throughout with porous pellets

 To avoid having to separate catalyst from reaction

product

 Pellets are packed into “fixed bed” through which

reactant is passed

 Volume requirement of bed set by ability of reactants to

diffuse in & products to escape

 Core accessibility determined by pellet diameter,


porosity & catalytic activity 18
STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET
 Assumptions in continuum model of catalytic pellet:

 SS diffusion & chemical reaction

 Spherical symmetry

 Perimeter-mean reactant A number density nA,w at R = Rp

 Radially-uniform properties (DA,eff, k”’eff, , …)

 First-order irreversible pseudo-homogeneous reaction

within pellet

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STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET

 SS nA(r) profile within pellet satisfies local species A


mass-balance:
0  div( j )  r
''
A
'''
A,eff

since
j''A  DA,eff gradwA
and

r '''
A,eff  k wA
'''
eff

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STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET

 Then, nA(r) satisfies:


1 d  2 dnA 
  keff nA
'''
.  r DA,eff
r dr 
2
dr 
Relevant boundary conditions:

n A  R p   n A, w
and
 dnA / dr r 0  0
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STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET

 Applying species A mass balance to a “microsphere” of

radius e, and taking the limit as e  0:

 1 e ''' 
2  eff
lim jA'' ,r  lim  . r 4 r dr 
2

e 0 e 0  4e 0 

which, for finite rA''' (o) leads to:

 dnA / dr r 0  0
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STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET
 Once nA(r) is found, catalyst utilization (or effectiveness)
factor can be calculated as:

actual reaction rate within pellet


cat 
reaction rate within pellet if nA  r   nA, w

or    
0 keff nA  r  4 r dr  A,eff  dr r  Rp   p 
Rp
dn
''' 2  D A
 4  R 2

cat  
'''
4 R 3
p  4 R 3
p

keff nA, w . keff nA, w . 
'''

3 
 3 
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STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET
 By similitude analysis:
nA  r 
c  fct  , f   fct  ; f 
n A, w R 
 p 
and, therefore:
1  dc 
cat  2    cat f 
f  d  1
where the Thiele modulus, f, is defined by:
1/2
 DA,eff 
f  R p .  ''' 
 k
 eff 
f 2 relevant Damkohler number; ratio of characteristic
diffusion time (Rp2/DA,eff) to characteristic reaction time,
(k”’ )-1 24
STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET
 c (; f) normalized reactant-concentration variable,
satisfies 2nd-order linear ODE:
1 d  2 dc 
    f 2
c
 d  d 
subject to split bc’s:
c(1)  1
 dc / d 0  0

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STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET

Solution to this two-point BVP:


sinh f 
c
 sinh(f )
or, explicitly:
nA  r  sinh f r / Rp 

n A, w  r / Rp  sinh(f )
Catalyst-effectiveness factor is explicitly given by:

3  1 1
cat  .  
f  tanh f f 
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STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET

Catalyst effectiveness factor for first-order chemical reaction in a porous solid sphere
(adapted from Weisz and Hicks (1962))
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STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET

cat  1 for f  0
cat  3 / f for f  1
 Reaction only in a thin shell near outer perimeter of
pellet
 Alternative presentation of cat : based on dependence
on   f 2

 4 3 
 r / MA/
  3 .  rA,obs / M A 
A, obs Rp 
  3
 DA,eff nA,w / Rp2  4  DA,eff nA, w Rp 

 Independent of (unknown) keff'''


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STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET

Catalyst effectiveness factor vs experimentally observable (modified) Thiele


modulus (adapted from Weisz and Hicks (1962))
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STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET

 Following additional parameters influence cat


E
Arr 
RTe
DA,eff n A,e  H 

keff Te
n  reaction order
 DA, fluid  Nu m 
Bim    . 
 D
 A,eff  2 

 k fluid  Nu h 
Bih  
 k  2
. 
 eff  
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STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET

Representative Parameter Values for Some Heterogeneous Catalytic Reactions


(after Hlavacek et al (1969)) 31
TRANSIENT MASS DIFFUSION: MASS
TRANSFER (CONCENTRATION) BOUNDARY
LAYER
 Discussion for thermal BL applies here as well

d m  4  Dt 
1/2

 Thermal BL “outruns” the MTBL:


dh   
1/2

  Le 
1/2
 
dm  D 
 D <<  (Le << 1) for most solutes in condensed phases
(especially metals)
 Ratio holds for time-averaged penetration depth in
periodic BC case as well
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CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS
 Analogies to Energy Transfer:
 When “analogy conditions” apply, heat-transfer
equations can be applied to mass-transfer by
substituting:
  D,
Pr  Sc,
Nuh  Num
Sth  Stm ,
Rah  Ram
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CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS
 Analogies to Energy Transfer:

 Mass transfer of dilute species A in straight empty tube

flow (by analogy):


w A , w  w A ,b ( z )
w A,w  w A,b (0)
 
 exp 4 m .Nu m    .F (entrance)

where

1 z
m  .  Sc  v / DA mix 
Re.Sc d w

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CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS

Nu m     0.023 Re0.8 Sc1/3  (turbulent )

and

 1  7.60 8/3 1/8 (laminar)


  m 
F (entrance)  
 1   z / d w  
2/3
(turbulent)
 

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CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS

 Analogies to Energy Transfer:

 Packed duct (by analogy):

dj A / (a ''' A0 dz )
Num,bed 
DA  wA,w  wA,b  / e / 1  e   .  d p ,eff 
Since, in the absence of significant axial dispersion:

dj A  m.dw A,b ,

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CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS
 Analogies to Energy Transfer:

 Packed duct (by analogy):

We find:
w A , w  w A ,b ( z )   Num ,bed  Rebed , Sc   z 
 exp 6(1  e ).  . 
w A, w  w A,b (0)   e Rebed .Sc  d p ,eff 
where
Num,bed Sc0.4  0.4Re1/2
bed  0.2Re 2/3
bed

if 3 ≤ Rebed ≤ 104, 0.6 ≤ Sc, 0.48 ≤ e ≤ 0.74


Quantity in square bracket = Bed Stanton number for
mass transfer, Stm,bed
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CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS

 Analogies to Energy Transfer:

 Packed duct (by analogy):

In terms of Stm,bed

w A, w  w A,b ( z )
 exp  Stm,bed a ''' z
w A, w  w A,b (0)
'''
where, as defined earlier, a (= 6(1-e)/dp) interfacial
area per unit volume of bed

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CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS
 Analogies to Energy Transfer:

 Packed duct (by analogy):

 Height of a transfer unit (HTU) is defined by:

w A , w  w A ,b ( z )  z 
 exp   
w A, w  w A,b (0)  ( HTU ) 
 HTU  bed depth characterizing exponential approach
to mass-transfer equilibrium

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CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS

 Analogies to Energy Transfer:

 Packed duct (by analogy):


In the case of single-phase fluid flow through a packed bed,
HTU = (a”’Stm,bed)-1
 Widely used in design of heterogeneous catalytic-flow
reactors and physical separators
 No chemical reaction within fluid
 Also to predict performance of fluidized-bed contactors,
using e(Rebed) correlations
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