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Lecture 6
Mass Transport: Diffusion with Chemical Reaction
1
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
2
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
3
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”
4
QUASI-STEADY-STATE (QS) DIFFUSION
OUTSIDE ISOLATED SPHERE
Stefan-flow effect on Num very similar to phoresis effect,
but with one significant difference:
6
QS EVAPORATION RATE OF ISOLATED DROPLET
7
QS EVAPORATION RATE OF ISOLATED DROPLET
Assumptions:
negligible
8
QS EVAPORATION RATE OF ISOLATED DROPLET
Assumptions:
binary) law
9
QS EVAPORATION RATE OF ISOLATED DROPLET
w A, w w A,
Bm
1 w A, w
c p (T Tw )
Bh
LA
where wA,w = wA,eq(Tw; p)
10
QS EVAPORATION RATE OF ISOLATED DROPLET
m wi m i ci Di ,eff gradw
''
i
''
i
11
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
12
QS EVAPORATION RATE OF ISOLATED DROPLET
13
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
14
QS EVAPORATION RATE OF ISOLATED DROPLET
1 Bh 1 Bm
Le
15
QS EVAPORATION RATE OF ISOLATED DROPLET
d p2,0
tlife,vap
g c p T Tw
8 ln 1
l LA
17
STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET
Catalyst impregnated throughout with porous pellets
product
reactant is passed
Spherical symmetry
within pellet
19
STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET
since
j''A DA,eff gradwA
and
r '''
A,eff k wA
'''
eff
20
STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET
n A R p n A, w
and
dnA / dr r 0 0
21
STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET
1 e '''
2 eff
lim jA'' ,r lim . r 4 r dr
2
e 0 e 0 4e 0
dnA / dr r 0 0
22
STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET
Once nA(r) is found, catalyst utilization (or effectiveness)
factor can be calculated as:
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
23
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
25
STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET
3 1 1
cat .
f tanh f f
26
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))
27
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
d m 4 Dt
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
32
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
33
CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS
Analogies to Energy Transfer:
where
1 z
m . Sc v / DA mix
Re.Sc d w
34
CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS
and
35
CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS
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 ,
36
CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS
Analogies to Energy Transfer:
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 Sc0.4 0.4Re1/2
bed 0.2Re 2/3
bed
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
38
CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS
Analogies to Energy Transfer:
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
39
CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS