Chapter 3: Steady and Quasi-

steady Mass Transfer

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

̻ Species balance equation

Species conservation equation
Diffusion equation
We do not know whether
nA is influx or efflux a
priori.
But, we can consider
efflux by taking the
component of nA·n (n is a
outward normal vector)
nA: mass flux

ȡAv

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 w w
U } 
Species balance w› h
¦ • h ˜ • GG'z G–™G ³ Uh‹}  ³ • h ˜ • GGG‹z
w› } z

rA: mass rate of production of species A per unit volume

Divide by ¨x ¨y ¨z and take a limit as ¨x, ¨y, ¨z goes to zero

wU A wn A wn A wn A Why
    rA Continuity equation
ƵUi=0?
wt wx wy wz wU i
wU A
¦ wt  ¦ ’ ˜ n  ¦ r i i 0
’ ˜ n A  rA
wt w¦ U
 ’˜¦n 0
i
i
wt
¦U U i

¦ n Uv
i

wU
 ’ ˜ ( Uv) 0
wt

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

nA UAvA ’ ˜ nA
jA U A v A  v  ’ ˜ ( j A  UZ Av)
nA j A  U Av ’ ˜ j A  ’ ˜ ( UZ Av)
* * *
nA j A  UZ Av (’ ˜ ( su ) ’s ˜ u  s’ ˜ u )
’ ˜ j A  Uv ˜ ’Z A  Z A’ ˜ ( Uv)
cf. N A J A  C Av
wU A w
UZ A  U wZ A  Z A wU U wZ A  Z A (’ ˜ ( Uv))
wt wt wt wt wt
wU wZ A
’ ˜ n A  A  rA ’ ˜ j A  Uv ˜ ’Z A  Z A’ ˜ ( Uv)  U  Z A (’ ˜ ( Uv))  rA
wt wt
§ wZ A · DZ A
U¨  v ˜ ’Z A ¸  ’ ˜ j A  rA U  ’ ˜ j A  rA 0
© wt ¹ Dt
D
: Stokes derivative or material derivative
Dt
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
wU A
’ ˜ n A  rA
wt
wU A v§Y DVVXPLQJGLOXWHVROXWLRQ
 ’ ˜ n A  rA 0
wt
Divide both sides by MwA wC A
 ’ ˜ ( DAB ’C A  C Av)  RA 0
wC A wt
 ’ ˜ N A  RA 0
wt wC A
Ÿ  DAB ’ 2C A  C A’ ˜ v  v ˜ ’C A  RA 0
N A CDAB ’x A  x A ( N A  N B ) wt
N A  NB wC A
CDAB ’x A  Cx A Ÿ  v ˜ ’C A DAB ’ 2C A  RA
C wt
 DAB ’C A  C Av *

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

Mass transfer equation

Rectangular coordinate system (x,y,z)

Cylidrical coordinate system (r,Ĺ,z)

Spherical coordinate system (r,DŽ,Ĺ)

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 Boundary conditions

• Symmetry condition (no-flux condition)

• Composition
C = 0 on the surface with rapid reaction
or C = Cbulk with complete mixing

• Interface
- vapor/liquid interface

- liquid/liquid interface

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

• Essential boundary condition (Dirichlet condition):

value of variable is specified
ex. C = 0 on the surface with rapid reaction
C = Cbulk with complete mixing
C+ = Į C-

• Flux boundary condition (Neumann condition):

value of gradient (or derivative of variable) is specified
ex. Symmetry condition ’C = 0

• Mixed boundary condition (Robin condition):

condition in terms of both the variable itself and derivative of variable

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 Ex. 3.2.1 Mass transfer controlled by external
diffusion resistance

Rdr
v=0
Steady state & no rxn
Mass transfer coefficient k
Sh = Sherwood number

Liquid concentration = CA,sat

Corresponding vapor pressure = pA,sat
Problem: steady diffusion into the gas

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

Method A

Method B

4Sr 2 N A,r constant

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
We need two boundary conditions
'RPDLQRILQWHUHVWU•5

1. At r = R+, pA=pA,sat

$WU ’

b=0, a=-RCR

mass transfer flux

Note that we ignore any motion of the interface-
there is no xA(NA,r + NB,r) term,

Rate of mass transfer

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

We often define a surface mass transfer coefficient k as the

proportionality constant between the flux and the concentration
difference between the surface and the surroundings

1. Show kR/DAB is
dimensionless
2. k = f(DAB, velocity)

2kR/DAB :dimensionless mass transfer coefficient, Sherwood number,

denoted Sh

Sh: dimensionless convective mass transfer coefficient

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 Ex. 3.2.2 Diffusion controlled by external
convection

domain of interest: R ”r ”R ĵ

we apply the boundary conditions

- Exterior fluid is not stationary

- We will represent the convective
resistance as if it were due to
diffusion through a boundary layer
of known thickness ĵ
-
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

Then,

Note that in the limit as ĵ5» 1 we recover the earlier result.

vs.

The radial flux at R

and

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 where

Mass transfer coefficient

We described ĵas a boundary layer thickness. Its magnitude must

depend on the fluid dynamics external to the sphere. We will need to
learn how to estimate ĵfrom hydrodynamic parameters. Obviously we can
promote mass transfer by controlling the hydrodynamics of the system.

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

Ex. 3.2.3 Respiration of a spherical cell

average rate of consumption

Why 4›r2?
We consider a spherical particle within
which a homogeneous reaction occurs, In spherical coordinates
involving a single species A. If an
average rate of consumption of A must
be maintained, denoted by R A [mol/cm3
• s], what level of CR must be provided?

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
Assume zero-order kinetics

diffusion equation becomes

a= 0 ĸdCAldr = 0 at r =0 (a
symmetry condition) or finite CA

Since CA must be positive, we see

We use that at a fixed value of CR there is a
limiting value of
For any larger than this limiting
value, we cannot supply sufficient A
to the interior, by diffusion, to
maintain a positive CA

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

Our goal is to specify a value of CR that will provide a specified average

rate of consumption, How do we relate to CR? We must write a
material balance on species A, that states that the rate of delivery of A
to the cell exactly balances the rate of consumption

no further information obtained

But,
RAo R 2
C A (0) C R  t0
6 DAB
RAo R 2
Ÿ CR t
6 DAB
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 Ex. 3.2.4 Life support for a spherical
organisms: first-order kinetics for
respiration

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

1 d § 2 dC · k
¨ r ¸  C 0
r 2 dr © dr ¹ DAB
d § 2 dC · k 2
¨ r ¸  r C 0
dr © dr ¹ DAB
2
dC 2 d C k 2
2r r 2
 r C 0
dr dr DAB
dC d 2C k
2 r 2  rC 0
dr dr DAB
Assume y r mC to eliminate r from the coefficient
Then, C r m y
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 dC dy
mr  m 1 y  r  m
dr dr
d 2C m2  m 1 dy  m 1 dy m d y
2

2
m( m  1)r y  mr  mr r
dr dr dr dr 2
§ dy ·
2¨  mr  m 1 y  r  m ¸
© dr ¹
§  m 1 dy  m 1 dy m d y ·
2
 r ¨¨  m(m  1)r m2
y  mr  mr r ¸
2 ¸
© dr dr dr ¹
k
 rr  m y 0
DAB

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

 m 1 d2y m  m dy  m 1  m 1 k  m 1
r  ( 2 r  2 mr )  ( 2 mr  m (  m  1) r  r )y 0
dr 2 dr DAB
d2y
To eliminate r - dependence of coefficient of 2 ,  m  1 0 Ÿ m 1
dr
k 11 k k
Then, 2r 1  2r 1 0,2r 11  (1  1)r 11  r 2r  2  2r  2  
DAB DAB DAB
d2y k
We have 2  y 0
dr DAB
k
Let D 2
DAB
Then, we have
d2y
2
D 2 y 0
dr

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 We have the solution y a sinh Dr  b cosh Dr
Or
1/ 2 1/ 2
§ k · § k ·
rC a sinh ¨¨ ¸¸ r  b cosh¨¨ ¸¸ r
© DAB ¹ © DAB ¹
1ª § k · º
1/ 2 1/ 2
§ k ·
C «a sinh ¨¨ ¸¸ r  b cosh¨¨ ¸¸ r »
r« © DAB ¹ © DAB ¹ »¼
¬
To satisfy C finite at r 0 Ÿ b 0
RC R
C C R at r RŸa
sinh( k / DAB )1/ 2 R

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

diffusion rate across the surface of the sphere

Thiele modulus

Ratio of chemical reaction rate to

the diffusion rate
consumption rate = diffusion rate across the surface of the sphere

To support respiration at the specified rate RA , we must have a CR

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
Parametric dependence of CR on R, DAB, and Ĺ

For small Ĺ

1 1
coth I
tanh I § I 2 2I 5 ·
¨¨ I    ¸¸
© 3 15 ¹

CR is independent of R and DAB

it is controlled by reaction rate, not by diffusion.
Note meaning of small Ĺ

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

For large Ĺ

RA kC R /(I / 3)  kC R
at a specified , CR increases with increasing Ĺ, as expected. That is,
CR depends on k,
k even at large R.

An important feature of mathematical modeling is the examination of

the manner in which the solution depends on the physical parameters
in the problem. It is often very useful to know how certain
parameters affect the solution, especially in the limits of very large
and very small values of certain parameters. Putting the solution into a
dimensionless format aids that process.
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021