Advanced Transport Phenomena

Module 6 Lecture 25

Mass Transport: Composite Planar Slab

Dr. R. Nagarajan
Professor
Dept of Chemical Engineering
IIT Madras

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CONCENTRATION FIELDS, SURFACE MASS-
TRANSFER RATES & COEFFICIENTS
Conservation Equations:
Concentration fields are coupled by the facts that:
Homogeneous reaction rates involve many local
species
All local mass fractions must sum to unity (only N-1
equations are truly independent)
Species i mass conservation condition may be written
as:
i
div (m i'' ) ri ''' (i 1, 2,..., N ),
t
ri ''' local mass rate of production of species i
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CONCENTRATION FIELDS, SURFACE MASS-
TRANSFER RATES & COEFFICIENTS
Conservation Equations:
Since i = wi, by virtue of total mass conservation:

div(mi'' ) 0
t
and the species balance becomes:
wi
v.gradwi div ji'',diff wi ci ri '''
t
LHS proportional to (Lagrangian) rate of change of wi
following a fluid parcel
RHS wi ci is forced diffusion flux
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CONCENTRATION FIELDS, SURFACE MASS-
TRANSFER RATES & COEFFICIENTS
Conservation Equations:
PDEs for wi x, t coupled to each other, and to
PDEs governing linear momentum density v(x,t) &
temperature field, T(x,t)
All must be solved simultaneously, to ensure self-
consistency
Simplest PDE governing wA x, t is Laplace
equation:
div gradwA 0

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CONCENTRATION FIELDS, SURFACE MASS-
TRANSFER RATES & COEFFICIENTS
Conservation Equations:
Laplace eq. holds when there are no:

Transients
Flow effects
Variations in fluid properties
Homogeneous chemical reactions involving species A
Forced diffusion (phoresis) effects
In Cartesian coordinates:
2wA 2wA 2wA
2 0
x 2
y 2
z 5
 CONCENTRATION FIELDS, SURFACE MASS-
TRANSFER RATES & COEFFICIENTS
Conservation Equations:
Boundary conditions on wi x, t are of two types:
wi along each boundary surface, or
Some interrelation between flux mi'',w & wi ,w (e.g.,
via heterogeneous chemical kinetics)
Solution methods:

Numerical or analytical
Exact or approximate
Solutions could be carried over from corresponding
momentum or energy transfer problems 6
 ANALOGIES & ANALOGY-BREAKERS

Heat-Transfer Analogy Condition (HAC) applies when:

Fluid composition is spatially uniform

Boundary conditions are simple

Fluid properties are nearly constant

All volumetric heat sources, including viscous

dissipation and chemical reaction, are negligible

St , Nuh known as functions of Re, Pr, Rah, etc.

h

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 ANALOGIES & ANALOGY-BREAKERS

Corresponding temperature field:

Tw T
T x , t ; Re, Pr,...
* * *

Tw T
Under HAC, the rescaled chemical species concentration
w A, w w A
w * x* , t * ; Re, Sc,...
w A, w w A,
And corresponding coefficients, Stm and Num , will be
identical functions of resp. arguments.
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 ANALOGIES & ANALOGY-BREAKERS

MACs:
w 1)
Species A concentration is dilute ( A

w A, w specified constant along surface

Negligible forced diffusion (phoresis)

No homogeneous chemical reaction

Analogy holds even when:

Fluid flow is caused by transfer process itself (e.g.,
natural convection in a body force field)
Analogy to linear momentum transfer breaks down
due to streamwise pressure gradients 9
 ANALOGIES & ANALOGY-BREAKERS

MAC:
Schmidt number Sc / DA plays role that Pr does for
heat transfer
Mass-transfer analog of Rah is:

g bw w A, w w A, L
3
v
Ram 2
. Grm .Sc
v DA
where bw defines dependence of local fluid density on wA:

1 1
bw
w A p ,T w A p ,T
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 ANALOGIES & ANALOGY-BREAKERS

Correction Factors for Analogy-Breaking Phenomena:

Two analogy breaking mechanisms:

Phoresis

Homogeneous chemical reaction

Have no counterpart in energy equation T(x,t)

BL situation: Substance A being transported from

mainstream to wall
wA,w << wA,
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 ANALOGIES & ANALOGY-BREAKERS

Correction Factors for Analogy-Breaking Phenomena:

Phoresis toward the wall:

Distorts concentration profile

Affects wall diffusional flux, j A, w
''

Num F ( suction).Num,0
where Num,0 mass transfer coefficient without phoretic
enhancement; analogous to Nuh
F(suction) augmentation factor

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 ANALOGIES & ANALOGY-BREAKERS

Correction Factors for Analogy-Breaking Phenomena:

F(suction) is a simple function of a Peclet number
based on drift speed, -c, boundary-layer thickness,
dm,o, and diffusion coefficient, DA:
c d m ,0 c L
Pesuction
D A DNum ,0 A
or
Pesuction
c
.
1
U Stm ,0
In most cases
Pesuction
F ( suction)
1 exp( Pesuction )
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 ANALOGIES & ANALOGY-BREAKERS

Correction Factors for Analogy-Breaking Phenomena:

Homogeneous reaction within BL:

wA profile distorted, diffusional flux affected

Num F reaction .Num,0

or
Stm F reaction .Stm,0

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 ANALOGIES & ANALOGY-BREAKERS

Correction Factors for Analogy-Breaking Phenomena:

F(reaction) depends on Damkohler (Hatta) number:

Dam
tdiff

m,0 / D k '''d m2,0
d 2

tchem 1/ k
'''
D A

where k relevant first-order rate constant; time-1

can be rewritten using:
L D
d m,0
Num,0 UStm,0
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 ANALOGIES & ANALOGY-BREAKERS

Correction Factors for Analogy-Breaking Phenomena:

For an irreversible reaction with wA,w << wA,

Dam 1/2 / sin( Dam)1/2 ( source)

F reaction
Dam / sinh( Dam)
1/2 1/2
(sink)

(F(reaction) 1 when Dam 0)

Reaction augmentation factors Hatta factors
F(Reaction) = dm,o / dm

If only heterogeneous reactions occur, analogy

is intact: Num = Num,0
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 QUIESCENT MEDIA

Above conditions not sufficient in nondilute systems

Mass transfer itself gives rise to convection normal to
surface, Stefan flow
vwd m w A, w w A,
Bm
D 1 w A, w
vw fluid velocity @ interface
Additional condition for neglect of convective
transport in mass transfer systems:
vwd m w A, w w A,
1
D 1 w A, w
Inevitably met in dilute systems
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 QUIESCENT MEDIA

Stefan flow becomes very important when wA,w wA,,

and wA,w 1

e.g., at surface temperatures near boiling point of

liquid fuel

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 COMPOSITE PLANAR SLAB

T continuous going from layer to layer, but not wA

Only chemical potential is continuous

Two unknown SS concentrations at each interface

Linear diffusion laws to be reformulated using a

continuous concentration variable

Applies to nonplanar composite geometries as well

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 COMPOSITE PLANAR SLAB

Mass transfer of substance A across a composite barrier: effect of piecewise

discontinuous concentration (e.g., mass fraction wA(x))
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 COMPOSITE PLANAR SLAB

Continuous composition variable = a-phase mass fraction

of solute A
Corresponding mass flux through a composite solid (or
liquid membrane)
w A overall
a

j ''
A, x
L
a

K A . w A a

l D .ka ,l
overall

A l
ka,l concentration-independent dimensionless equilibrium
solute A partition coefficients, (wA(a)/wA(l))LTCE, between
phase a and phase l (= a, b, g, d, )
dm,eff stagnant film (external) thickness (resistance)
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 COMPOSITE PLANAR SLAB

Dilute solute SS diffusional transfer between two

contacting but immiscible fluid phases a, b in
separation/ extraction devices

Modeled as through two equivalent stagnant films of

thicknesses dm,eff (a) and dm,eff (b)

In series, negligible interfacial resistance between

them

Two-film theory (Lewis and Whitman, 1924)

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 COMPOSITE PLANAR SLAB

KA(a) overall interface mass transfer coefficient

(conductance)
Satisfies additive-resistance equation
kab
1 1

K Aa D / d
(a )
D / d
(b )

A m . eff A m , eff
Overall
mass transfer -phase -phase
resistance resistance resistance

(symmetrical replacement of a and b yields KA(b))

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 COMPOSITE PLANAR SLAB

Gas absorption/ stripping:

One phase (say b) vapor phase
Kab relevant partition coefficient; inversely
proportional to Henry constant, H:

p A H .( x A ) solvent H . w A M solvent / M A
where M solvent molecular weight
pA partial pressure of species A in vapor
phase

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 COMPOSITE PLANAR SLAB

H dimensional inverse partition (distribution)

coefficient
b RT 1
kab (a )
.
M H
(if b-phase (vapor mixture) obeys perfect gas law)

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 COMPOSITE PLANAR SLAB

Addition of reagents to solvent phase a:

Reduces dm,eff (a)

Simultaneous homogeneous chemical reaction

increases liquid-phase mtcs, accelerates rate of
uptake of sparingly-soluble (large H) gases

Additive (B) in sufficient excess => pseudo-first-order

reaction ( rA linearly proportional to wA, with rate

'''

constant k)

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 COMPOSITE PLANAR SLAB

d m(a,eff) ;0
d m(a,eff)
F (reaction)
where
Dam
1/2

F reaction
tanh( Dam)1/2
and

Dam
d 2
m , eff ;0 /D (a )
A

1/ k '''

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 COMPOSITE PLANAR SLAB

When reaction is so rapid that the two reagents meet in

stoichiometric ratio at a thin reaction zone (sheet):
Distance between reaction zone & phase boundary
plays role of d m(a,eff) (a )
1 DB wB ,b
F reaction 1 . .
b DA w A,i
wB,b concentration of additive B in bulk of solvent
wA,i concentration of transferred solute A at solvent
interface
b gms of B are consumed per gram of A

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