Fundamentals of Mass Transfer

When a system contains two or more components whose

concentrations vary from point to point, there is natural
tendency for mass to be transferred, minimizing the
concentration differences within the system.
Mechanisms of mass transfer
Molecular Transfer ~ random molecular motion in quiescent fluid
Convective Transfer ~ transferred from surface into a moving fluid

Analogy between heat and mass transfer

Mass transfer Heat transfer
Molecular transfer Heat conduction
Convective transfer Heat convection

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Molecular Mass Transfer(Molecular Diffusion)
Fick’s law d A
j Az  D AB
dz
dx A
J Az  CD AB
dz
In vector form j A  D AB  A

J A  CD AB x A

Mass diffusivity D AB


Prandtl number Pr 

 
Schmidt number Sc  
D AB D AB
k 
Lewis number Le  
C pD AB D AB
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Mass Concentration
a) mass concentration  A 
Molecule of
the mass of A per unit volume of mixture
species A
- Total mass concentration(density)
   i
i

- mass fraction
A A
dV in multicomponent A  
muxture  i 
i

 i  1
i

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Molar Concentration
b) molar concentrationC A  ~ the number of moles of A present per unit volume
of mixture
A
CA  M A - molecular weight of A
MA

For ideal gas PAV  nA RT

n A PA
CA   PA - partial pressure of A
V RT
- Total molar concentration C   Ci
i
ntotal P
for ideal gas C 
V RT
- Mole fraction
CA CA
for liquid xA   xi  1 for gas yA   yi  1
C i C i

for ideal gas mixture

C P RT PA
yA  A  A  Dalton’s law of gas mixture
C P RT P
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Mass Average and Molar Average Velocity
a) mass average velocity
 i v i  i v i
v i
 i
  i v i v i - the absolute velocity of species i
 i  i
relative to stationary coordinate axes
i

b) molar average velocity

 Ci v i  Ci v i
V i
 i
  xi v i
 Ci C i
i

c) diffusion velocity - the velocity of a particular species relative to the mass

average or molar average velocity

vA  v vi  v and vi  V
vA
v
A species can have a diffusion velocity
vB vB  v only if gradients in the concentration exist

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Mass Diffusivity
 JA  M  1  L2
D AB     
dC A dz  L2t  M L3 1 L  t

D AB  f Temp ., Pr essure, Composition

Gases 5x10-6 ~ 10-5 m2/s

Liquids 10-10 ~ 10-9

Solids 10-14 ~ 10-10

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Molecular Mass and Molar Fluxes
Molar flux
J A  C A v A  V   CD AB xA
D AB mass diffusivity(diffusion coefficient) for component A
diffusing through component B
JA the molar flux relative to the molar average velocity

Mass flux
j A   A v A  v   D AB A

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Convective Mass and Molar Fluxes
Molar flux
J A  C A v A  V   CD AB xA
 Ci v i  Ci v i
C A v A  CD AB xA  C AV V i
 i
  xi v i
 Ci C i
i
C A v A  CD AB x A  x A  Ci v i
i
define N A  CA v A the molar flux relative to a set of stationary axes

N A  CD AB x A  x A  N i  J A  x A  N i
i i
concentration bulk motion
gradient contribution
contribution

Mass flux relative to a fixed spatial coordinate system

n A  v A  D AB  A   A v  D AB A  A  ni  j A  A  ni

i i

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Related Types of Molecular Mass Transfer
According to 2nd law of thermodynamics, system not equilibrium will tend
to move toward equilibrium with time
Driving force = chemical potential

Nernst-Einstein Relation
D AB
v A  V  u A c    c
RT
uA Mobility of component A, or the resultant velocity of
the molecule under a unit driving force
D AB
J A  C A v A  V   C A  c
RT
in homogeneous ideal solution at constant T & P

c   0  RT ln C A

J A  D AB C A Fick’s Equation

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Mass Transfer by Other Physical Conditions
~ produce a chemical potential gradient
Thermal diffusion(Soret diffusion)
Mass transfer by applying a temperature gradient to a multicomponent system
Small relative to other diffusion effects in the separation of isotopes
Pressure diffusion
Mass fluxes being induced in a mixture subjected to an external force field
Separation by sedimentation under gravity
Electrolytic precipitation due to an electrostatic force field
Magnetic separation of mineral mixtures by magnetic force
Component separation in a liquid mixtures by centrifugal force
Knudsen diffusion
If the density of the gas is low, or if the pores through which the gas
traveling are quite small
 the molecules will collide with the wall more frequently than each other
(wall xollion effect increases)
 the molecules are momentarily absorbed and than given off in the
random directions
 gas flux is reduced by the wall collisions
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Differential Equations of Mass Transfer
Conservation of Mass(overall)


A v  n dA  V dV  0
t
Conservation of Mass of Component A

nA ,x yz xx  nA ,x yz x  n A ,y zx y y  nA ,y zx y


 n A ,z xy z  z  n A ,z xy z  A xyz  rA xyz  0
t
 A
  nA   rA  0
t
Equation of Continuity for Component A
C A
 N A   RA  0
t
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 Differential
Equations of Mass
Transfer-1

In binary mixture
 A
  nA   rA  0
t

  n B  B  rB  0
t
 A   B 
  n A  n B    rA  rB   0
t
n A  n B   A v A   B v B  v

 A  B  
rA  rB

  v  0
t
Equation of Continuity for the Mixture

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 Differential
Equations of Mass
Transfer-2

n A  j A   Av

  n A    j A     Av 
 A
  nA   rA  0
t
 A
  jA      A v   rA  0
t

 A 
   A  v   A   A  v
t t
=0
D A
    j A  rA  0
Dt

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 Differential
Equations of Mass
Transfer-3

in terms of molar unit

C A
 N A   RA  0
t
C
  N B  B  RB  0
t
C A  CB 
  N A  N B    RA  RB   0
t
N A  N B  C A v A  CB v B  CV

C A  CB  C

But RA is not always –RB

for only stoichiometry reaction ( A B) RA   RB

C
  CV   RA  RB   0
t

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 Differential Equations
of Mass Transfer-4

N A  CD AB y A  y A  N A  N B 
or N A  CD AB y A  C AV

n A  D AB A  A n A  n B 
or n A  CD AB  A   A v
D A
    j A  rA  0
Dt
  A 
     A v   D AB  2 A  rA
 t 
If  and D AB are constant
 A    A 
  A   A   v   v   A  D AB2 A  rA   v   A   D AB2 A  rA
t t  t 
C A
 V  C A  D AB  2 C A  R A
t
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 n A  j A   v A
A    n A  rA
t


t
 
 v       g      vv


  U  21 v 2     e   v  g 
 
   

e  q    v   v  U  21 v 2 
t    

 T , A    

T
T  T    A 
 A 
T , A A T , A

 
     T  T    A   A 
  p   g      g  T  T   g  
Dv
 A  A
Dt

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Boundary Conditions
Initial Conditions at t  0, C A  C A0 or  A   A0

Boundary Conditions
Case 1) The concentration of the surface may be specified
C A  C A1 , y A  y A1 , x A  x A1 ,  A   A0 , A   A1 ,

Case 2) The mass flux at the surface may be specified

d A
j A  j A1 , N A  N A1 , j A  0( impermeable ), j A ,z surface  DAB
dz z 0

Case 3) The rate of heterogeneous chemical reaction may be specified

N A ,z surface  knC An
surface

Case 4) The species may be lost from the phase of interest by convective mass
transfer

N A ,z surface  kc C A ,surface  C A , 
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Steady State Diffusion of A through Stagnant B
Mass Balance Equation
Flowing of gas B
z  z2 SN A ,z  SN A ,z z  0
z  z

dN A ,z dN B ,z
N A z  z 0 0
dz dz
z  N B ,z  0
At z=z1, gas B is insoluble in liquid A

NA z ~ Component B is stagnant

 y A N A ,z  N B ,z 
dy A
z  z1 N A ,z  CD AB
dz
N B ,z  0
Liquid A
CD AB dy A at z  z1, y A  y A1
N A ,z  
S 1  y A dz at z  z2 , y A  y A2

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 Steady State
Diffusion of A
through Stagnant B-1
dy A
N A ,z zz dz  CD AB yy 
2 A2
1 A1
1 yA
CD AB 1  y A2 CD AB y A1  y A2 CD AB
N A, z  ln   y  y 
z2  z1 1  y A1 z2  z1 y B ,ln  z2  z1  yB,ln A1 A2

y B 2  y B1 1  y A2   1  y A1 
y B ,ln  
ln y B 2 y B1 ln 1  y A2  1  y A1 

n P P
For ideal gas C  and y A  A
V RT P
D AB P PA1  PA2
N A, z 
RT  z2  z1  PB ,ln

Steady state diffusion of one gas through a second gas

~ absorption, humidification

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Film Theory
~ a model in which the entire resistance to diffusion from the liquid surface
to the main gas stream is assumed to occur in a stagnant or laminar film of
constant thickness d.

Flowing of gas B Main fluid stream

in turbulent flow
zd
N A, z Slowly moving gas film
z0
Liquid A
D AB P PA1  PA2
N A, z 
RTd PB ,ln
kc
Convective Mass Transfer
N A, z  kc C A1  C A2   PA1  PA2 
RT
D AB P
kc  actual kc  D AB
0.5 ~1.0
PB ,ln d
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Concentration Profile
dN A ,z
0 d  CD AB dy A 
 0
dz  1  y A dz 
dz
CD AB dy A
N A ,z  
1  y A dz

If C and D AB are constant under isothermal and isobaric conditions

d  1 dy A 
 0
dz  1  y A dz 
at z  z1, y A  y A1
 ln1  y A   C1 z  C2 at z  z2 , y A  y A2
 zz   z z 
1  y A  1  y A2 
1 2 1

  
1  y A1  1  y A1 
 y B dz y B 2  y B1
yB    y B ,ln
 dz ln y B 2 y B1
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Pseudo Steady State Diffusion through a
Stagnant Gas Film
the length of the diffusion path changes a small amount over a long
period of time ~ pseudo steady state model
CD AB 1  y A2 CD AB y A1  y A2
Flowing of gas B N A ,z  ln 
z2  z1 1  y A1 z2  z1 y B ,ln
A,L dz
N A, z 
M A dt
Molar density of A in the liquid phase
 A, L dz CD AB y A1  y A2 at t  0, z  z0
N A, z 
M A dt z y B ,ln at t  t , z  zt
z  z0
z  zt  A, L y B ,ln M A  zt2  z02 
t  
CD AB  y A1  y A2   2 
Liquid A
 A, L y B ,ln M A  zt2  z02 
D AB   
C  y A1  y A2 t  2 
S
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Diffusion through a Isothermal Spherical Film

Temperature T2  T1
d 2
r N A,r   0
dr

 x A N A ,r  N B ,r 
Temperature T1 dx A
N A ,r  CD AB
dr
N B ,r  0 Since B is insoluble in liquid A

d  2 CD AB dx A 
r 0
dr  1  x A dr 
for constant temperature CD AB is constant
r1 1 r 1 r 
1

Gas film 1  x A  1  x A2  1 r 1 r 

 
1 2

r2
1  x A1  1  x A1 
4CD AB  1  x A2 
WA  4r12 N A,r  ln 
r  r1
1 r1   1 r2   1  x A1 
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 Diffusion through a Nonisothermal Spherical Film
3n 2
r 
n
D AB  r 
T2  T1  2   
Temperature
 r1  D AB,1  r1 
Temperature T1
d  2 CD AB dx A 
 r   0
dr  1  x A dr 

d  2 PD AB,1 RT1  r  dx A 
3n 2

r   0
dr  1  x A  r1  dr 
if n  2
4PD AB,1 RT 1  n 2  1  x A2 
WA  4r12 N A,r   
Gas film
r1 r  r1

1 r1 1 n 2 
 1 r2  
1 n 2  n 2
r1
ln
 1  x A1 

r2

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Diffusion with Heterogeneous Chemical Reaction
Solid catalyzed dimerization of CH3CH=CH2
Gas A Gas A & B
2A  B

N B , z   12 N A, z

CD dx A Sphere with coating

N A, z   1 AB of catalytic material
1 2 x A dz xA0
Z=0
A Edge of hypothetical
Z xA Stagnant gas film
d  1 dx A 
 1   0 xB
dz  1  2 x A dz  B
Z=d
 2 ln1  12 x A   C1 z  C2  2 ln K1 z  2 ln K 2  Catalytic surface

at z  0, x A  x A0
at z  d, x A  0 2CD AB  1 
Irreversible and instantaneous rxn N A, z  ln 1 
d  1  2 x A0 
1  12 x A   1  12 x A0 1 z d 
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Diffusion with Slow Heterogeneous Chemical Reaction
2A  B
CD AB dx A
N B , z   12 N A, z N A, z  
1 12 x A dz
d  1 dx A 
 1   0  2 ln1  12 x A   C1 z  C2
dz  1  2 x A dz 

at z  0, x A  x A0

at z  d, x A 
N A, z
N A, z  k1C A  assume pseudo 1st order rxn
k1C
zd

1  12 x A   1  1 N Az  1  12 x A0 1 z d 

 2 k1C 
2CD AB d  1 
N A, z  ln 1  k1 large
1  D AB k1d  1  2 x A0 

Da  k1d D AB Damkohler No.: the effect of the surface reaction on the

overall diffusion reaction process
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Diffusion with Homogeneous Chemical Reaction
A  B  AB
First order reaction

N A, z z S  N A , z z  z
S  k1C A Sz  0

dN A, z
 k1C A  0
dz
dC A
N A, z  D AB
dz
d 2C A at z  0, C A  C A0
D AB  k1C A  0
dz 2 at z  L, N A, z  0or dC A dz  0

  C A C A0 ζ z L   k1L2 D AB Thiele modulus

d 2 at   0,   1
  2
0
d 2 at   1, d d  0

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 Diffusion with
Homogeneous
Chemical Reaction-1
  C1 cosh   C2 sinh ζ

cosh  cosh   sinh  sinh ζ cosh1   

 
cosh  cosh 


C A cosh k1 L2 D AB 1   z L 


C A0 cosh k1 L2 D AB

0 C A C A0 dz tanh 
L
C A,avg
 
C A0 L
0 dz 

dC A C D 
N A, z z 0
 D AB   A0 AB  tanh 
dz z 0  L 

Sogang University
Gas Absorption with Chemical Reaction
in an Agitated Tank

effect of chemical reaction rate on the

rate of gas absorption in an agitated
tank
Liquid B
Surface area Example) The absorption of SO2 or
of the bubble H2S in aqueous NaOH solutions
is S

Semiquantative understanding can

Volume of liquid Gas A in be obtained by the analysis of a
phase is V relatively simple model

Sogang University
 Gas Absorption with
Chemical Reaction
in an Agitated Tank-1

Assumptions:
1) Each gas bubble is surrounded by a stagnant liquid film of thickness d, which is
small relative to the bubble diameter
2) A Quasi-steady state concentration profile quickly established in the liquid film
after the bubble is formed
3) The gas A is only sparingly soluble gas in the liquid, so that we can neglect the
convection term.
4) The liquid outside the stagnant film is at a concentration CAd, which changes so
slowly with respect to time that it can be considered constant.

Gas in Liquid film Main body of liquid

bubble
Without reaction

CAd
Liquid-gas With reaction
interface
Z=0 Z=d
Sogang University
 Gas Absorption with
Chemical Reaction
in an Agitated Tank-2
d 2C A
D AB 2
 k1C A  0
dz
  C1 cosh   C2 sinh ζ at z  0, C A  C A0
at z  d, C A  C Ad

  C A C A0 ζ z d   k1d 2 D AB

C A sinh  cosh   B  cosh  sinh ζ 


C A0 sinh 
dC A
Assumption (d) - SD AB  Vk1C Ad
dz z d

1
B
cosh   V Sd sinh 
The total rate of absorption with chemical reaction
 N A,z z 0 d   1 
N   cosh   
C A0D AB sinh   cosh   V Sd sinh  
Sogang University
 Gas Absorption with
Chemical Reaction
in an Agitated Tank-3

Chemical rxn is fast enough to keep

the bulk of the solution almost solute
free, but slow enough to have little
effect on solute transport in the film

for very slow reactions, for large value of , dimensionless surface

the liquid is nearly mass flux increases rapidly with  and
saturated with dissolved gas becomes nearly independent of V/Sd.
Sogang University
Diffusion and Chemical Reaction inside a Porous
Catalyst
We make no attempt to describe the diffusion inside the
tortuous void passages in the pellet. Instead, we describe the
“averaged diffusion” of the reactant ~ effective diffusivity

N A,r r 4r 2  N A,r r  r

4 r  r  
2
R A 4 r 2
r  0

r 2
N A,r  
 r 2 N A,r  d 2
r N A,r   r 2 RA
lim r  r r
 r RA
2
dr
 0
r r

Sogang University
 Diffusion and Chemical
Reaction inside a
Porous Catalyst-1
dC A
N A  -D A effective diffusivity
dr depends on P, T
1 d  2 dC A  and pore structure
DA 2 r    RA
r dr  dr 
First order chemical reaction,
a is the available catalytic surface per unit volume

1 d  2 dC A  at r  R , C A  C AR
DA r   k1aC A
r dr 
2
dr  at r  0, C A  finite

d 2 f  k1a 
 f r 
CA 1
2
   f
C AR r dr  DA 

C A C1 ka C ka
 cosh 1 r  2 sinh 1 r
C AR r DA r DA

C A  R  sinh k1a D A r
 
C AR  r  sinh k1a D A R

Sogang University
 Diffusion and Chemical
Reaction inside a
Porous Catalyst-2
dC A
WA  4R 2 N A,R  4R 2D A
dr r R

 k1a k1a 

WA  4RD AC AR 1  R coth R
 D A D A 

If the catalytically active surface were all exposed to the stream, then the
species A would not have to diffuse through the pores to a reaction site.

WAR ,0  
4
3

R3 a  k1C AR 

 2  coth   1
WAR 3
Effective factor A 
WAR ,0 
  k1a D A Thiele modulus
For nonspherical catalyst particles
 Vp  A 
1
3 coth 3  1
Rnonsph  3  32
 Sp 
 
WAR  V p ak1C AR A 
  k1a D A V p S p  generalized
modulus
Sogang University
 Diffusion and Chemical
Reaction inside a
Porous Catalyst-3

Sogang University
Textbook p567

Diffusion in a Multi-Component System

Liquid water(species 1) is evaporating into air, regarded as a binary mixture of
nitrogen(2) and oxygen(3) at a given T & P.

dN  ,z
0   1, 2, 3
dz

Maxwell Stefan equation for multicomponent diffusion in gases at low density

x x 
v  v     x N  x N     1,2,3,..., N
N N
1
x   
 1 D   1 CD 

Since species 2 and 3 are not moving, N 2 ,z  N3,z  0

dx2 N dx3 N
 1,z x2 ;  1,z x3
dz CD12 dz CD13

Sogang University
 x2 L dx2 N1,z L x3 L dx3 N1,z L
x2 
x2 CD12 z dz; x3 
x3 CD13 z dz

x2  N L  z   x3  N L  z  
 exp   1,z ;  exp   1,z 
x2 L  CD12  x3L  CD13 

 N L  z    N L  z  
x1  1  x2 L exp   1,z   x3L exp   1,z 
 CD12   CD13 

 N L  N L
At z=0 x10  1  x2 L exp   1,z   x3L exp   1,z 
 CD12   CD13 

Sogang University
 Textbook p612

Transient 1-D Diffusion of a Finite Slab

~ negligible surface resistance

C A  C A0  z  at t  0, 0  z  L
C A  CA2
 D AB CA  CAs at z  0, t  0
C As t C As t z 2
CA  CAs at z  L, t  0

CA  CAs
Let Y 
C A0 z  C A0  C A s
Y 1 at t  0, 0  z  L
Y  Y2
 D AB 2 Y 0 at z  0, t  0
z=0 z=L
t z
Y 0 at z  L, t  0

by Separation variables method

Y  z, t   Z  z Gt 
Sogang University
2005. 05. 30
 Transient 1-D
Diffusion of a
Finite Slab -1

2   nz  n 2  X L nz X D  D AB t L 2

0 Y0  z sin
2
Y   sin
2

e D
dz
L n 1  L  L

if Y0  z   Y0 ,

C A  C A s 4  1  nz   n 2  X
  sin n  1,3,5
2

e D

C A 0  C A s  n1n  L 

dC A 4D AB
C A s  C A0   cos nz en 2  X

 D AB  n  1,3,5
2

N A, z D

dz L n 1  L 

Sogang University
Transient Diffusion in a Semi-Infinite Medium
C A  C A0 at t  0, all z
C A  2C A CA  CAs at z  0, t  0
 D AB
t z 2 C A  C A0 as z  , t  0

C A  C A0  z t   t 
 f  , 2   f  2 
C A s  C A0  z1 z1  z 

Let   z 2 t , Y  C A  C A 0  C A s  C A 0  ~ Similarity Solution Technique

C A  C A0  z  C As  C A  z 
 1  erf   or  erf  
C A s  C A0  2 D AB 
t C As  C A 0 D
 2 AB 
t

2   2
erf    e d
 0

erf 0  0, erf    1

Sogang University
Textbook p613

Unsteady State Evaporation of a Liquid

Vz
Continuity equation 0
z
Vz  Vz 0 t 
Flowing of gas B

N A,z 0  N B ,z 0
In the binary system Vz 
C
N B ,z 0  0 Gas B is insoluble in Liquid A

D AB x A
N A, z Vz  
1  x A0 z z 0
z0
x A  D AB x A  x A  2 xA
   
 z  D AB z 2
Liquid A t  1  x A0 z z 0 

at t  0, xA  0
S at z  0, xA  xA0
at z   , xA  0
Sogang University
 Unsteady State
Evaporation of a
Liquid-1
x A x A0  X , Zz 4D ABt
at Z  0, X  1
d2X
 2Z  
dX
2
0 at Z   , X  0
dZ dZ

 
 x A0  Vz t D AB  
1 x A0 dX Dimensionless molar
2 1  x A0 dZ Z 0 average velocity

Y
dX
dZ

 C1 exp  Z  
2

0
Z


 

X  C1  exp  Z   d Z  C2
2

Z
0 
exp 
 Z    d Z 
2 Z 
 
exp  W 2 dW
X Z   1   1 


0 exp  Z    d Z
2




exp W dW
2

erf Z    erf 1  erf Z  

X Z   1   Textbook p616
erf  erf 1  erf Fig. 20.1-1
Sogang University
 Unsteady State

 
Evaporation of a
Liquid-2
1 x A0 dX 1 x A0 erf  2
  x A0    x A0  
2 1 x A0 dZ Z 0
 1  x A0 1  erf

1
x A0 
1   1  erf exp 2 
1

Rate of production of vapor from surface of area S

dVA N A0 S D AB
  S
dt C t
VA: the volume of A evaporation up to time t

VA  S 4D ABt
x A  2 xA 4D ABt
 D AB  VAFick  Sx A0
t z 2 
4D ABt
VA  Sx A0      x A0

Sogang University
Deviation from the Fick’s second law caused
by the nonzero molar average velocity
 Textbook p617

Gas Absorption with Rapid Reaction

Gas A is absorbed by a stationary liquid solvent S containing solute B

aA + bB products
Gas A
C A  2C A
Liquid-Vapor Interface  D AS for 0  z  z R t 
t z 2
C B  2C B
ZR
 D BS for z R t   z  
t z 2
Solute B
at t  0, C B  C B for z  0
at z  0, C A  C A0
at z  z R t , C A  CB  0
C A C B
at z  z R t ,  D AS
1 1
  D BS
a z b z
at z  , C B  C B

Sogang University
 Gas Absorption with
Rapid Reaction-1
z
for 0  z  z R t 
CA
 C1  C2erf
C A0 4D AS t
z
for z R t   z  
CB
 C3  C4erf
C B 4D BS t

CA
 1
erf z  4D AS t  for 0  z  z R t 
C A0 erf zR  4D AS t 
CB
 1
1  erf z  4D BS t  for z R t   z  
C B 1  erf zR  4D BS t 
C A C B
instead of B. C. at z  z R t ,  D AS
1 1
from B. C. at z  , C B  C B   D BS
a z b z

 aCB D BS     
1  erf  erf exp   
D BS bC A0 D AS D AS  D AS D BS 

  z R2 4t  cons tan t ZR increases as t

Sogang University
 Gas Absorption
with Rapid
Reaction-2

C A C A0 D AS
N A,z 0  D AS 
z z 0 
erf  D AS  t
The average rate of absorption up to t

1 t C A0 D AS
  N A,z 0 dt 2
N A,z 0 ,avg
t 0 erf  D AS  t

Sogang University
Gas Absorption with Rapid Reaction-2

Sogang University
Textbook p.558

Diffusion into a Falling Liquid Film(Gas Absorption)

  x 2 
y
x vz x   vmax 1    
z   d  

x=0 x=d N A,z z Wx  N A,z Wx  N A,x x Wz  N A,x Wz  0
x z  z x  x

CA0
N A,z N A,x
 0
z z x

C A
V(x) N A,z  -D AB  x A N A,z  N B ,z   C Avz x 
z
CA0
C A C A
N A,x  -D AB  x A N A,x  N B ,x   D AB
x x

C A  2C A
vz  D AB
z x 2

Sogang University
 Diffusion into a
Falling Liquid
Film(Gas
at z  0, C A  0 Absorption)-1

  x  C 2
 CA 2
vmax 1     A  D AB at x  0 , C A  C A0
  d   z x 2 C A
at x  d , 0
x
The substance A has penetrated only a short distance into the film~penetration model
at z  0, C A  0
C A  2C A
vmax  D AB at x  0, C A  C A0
z x 2
at x   , C A  0
CA
C A0
 1
2 x 4D AB z vmax

 0
exp   2 d  
CA x x
 1  erf  erfc
C A0 4D AB z vmax 4D AB z vmax

C A D ABvmax
N A,x  D AB  C A0
x 0 x x 0 z

D AB vmax L 1 4D AB vmax
WA0  0W 0LN A, x dzdy  WC A0 0 dz  WC A0
x 0
 z L
Sogang University
Gas absorption from rising bubbles

Rybczynski-Hadamard circulation

Gas bubbles rising in liquids free surface –active

agents undergo a toroidal circulation

CA 4D ABv t
N A ,x  D AB  CA0
x 0
x x 0 D

vt
t exp osure 
D

4D ABv t
For creeping flow N A ,x  CA0
x 0
3 D

Trace of surface-active agents cause a marked decrease in absorption rates from small bubbles
By preventing internal circulation
1/3
N A ,x x 0
 D AB
Sogang University
Textbook p.562

Diffusion into a Falling Liquid Film(Solid Dissolution)

gd 2   y  2  gd 2   y   y 2 
vz  1  1     2     
2   d   2   d   d  
d
At end adjacent to the wall  y d2   y d
Parabolic
Velocity vz  gd y  ay
Profile of
Fluid B
C A  2C A at z  0, C A  0
ay  D AB
y z y 2 at y  0, C A  C A0
z
at y   , C A  0
CA0 =saturation
Similarity Solution Technique
concentration
C A C A0  f  , η  ya 9D AB z 
CA=0 13

Slightly soluble d2 f 2 df at   0, f  1
 3 0
Wall made of A
d 2
d at    , f  0

Sogang University
 
f  C1  exp    d   C2
3
0  
 
  3 d  exp    d 
   
3
exp
CA
    
 3  43 
C A0
0 exp    d 
C A d C   
N A ,y  D AB  D ABC A0   A  
y  d  C A0  y  y 0
y 0
y 0

 exp   3
 D ABC A0 
   a  

13

 
D ABC A0  a 

13


 43  9 D z   43 
  AB  
y 0
 9 D AB z 
 43   0.8930
13
W L 2D AB C A0WL  a 
W A0    N A, y dzdx   
0 0 y 0  3 
7
 9D AB L 
73   43 43   1.1907
WA0  D AB L 
23

Sogang University
Textbook p.585

Diffusion, Convection and Chemical Reaction

dC A d 2C A
v0  D AB  k1C A
dz dz 2
Liquid B with
small amounts at z  0, C A  C A0
of A and C
A C at z   , C A  0
by first order

  
reaction
z
Porous plug A
CA
C A0
 
 exp  1  4k1D AB v02  1 v0 z 2D AB 
(slightly soluble
in B)

Liquid B

Sogang University
Analytical Expressions for Mass Transfer Coefficients
Mass Transfer in Falling Film on Plane surfaces

The absorption of a slightly soluble gas into a falling liquid film

4D AB vmax
WA 0  WL C A0  0  kc0,m AC A
L

kc0,m L 4  Lvmax   
  1.128Re Sc 1 2
4 Lvmax
Shm     
D AB D AB     D AB 

The dissolution of a slightly soluble solid into a falling liquid film

13
2D AB  a 
   WLC A0  0  kc0,m AC A a  gd   2vmax d
73   9D AB L 
W A0

kc0,m L 2vmax dL2 1 16  L  Lvmax    L

  Re Sc 
2
Shm   7 3  7 3      1.073 13
D AB  3   9D AB 
3  9  d    D AB  d
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 Analytical Expressions for
Mass Transfer
Coefficients-1

Mass Transfer for Flow Around Spheres

The gas absorption from a gas bubble surrounded by liquid in creeping flow
4 D AB v
N A0 ,avg  C A  0  kcm
0
C A
3 D
kc0,m D 4  Dv   
  0.6415Re Sc 1 2
4 Dv
Shm     
D AB 3 D AB 3    D AB 

Shm  2  0 .6415 Re Sc 

12
Re  0 Shm  2
Creeping flow around a solid sphere with slightly soluble coating


32 3 2D AB 3 D AB
2
v
C  0  kc0,m C A
73 
N A0 ,avg 73 2 A
2 D

kc0,m D 32 3 Dv 32 3  Dvmax   

Shm   73 7 3  73 7 3     0.991Re Sc 1 3
D AB 2  3  D AB 2  3     D AB 

Shm  2  0 .991 Re Sc 

13
Re  0 Shm  2
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Sogang University
Blasius’s Solution
vx v y
Governing Equations  0
x y
vx vx  2vx
vx  vy  2
x y y
C A C A  2C A
vx  vy  D AB
x y y 2
vx v y C A-C As
Boundary Conditions at y  0,   0, 0
v v C A -C As
vx C A-C As
as y  ,  1, 1
v C A -C As

if Sc   1 (thermal boundary layer = hydrodynamic boundary layer)
D AB
v C  C As
f2 x 2 A
v C A  C As
y v y v x y
   Re,x
2 x 2 x  2x
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 Blasius’s Solution-1

d 2vx v  d 2 C A  C As  C A  C As 
 f 0 
df
d 0 
d  y 2 x  Re, x   0


d  y 2 x  Re, x   0
 1.328

 0.332 1 2 
 C A   C A s 
dC A
Re, x 
dy y 0  x 
C A
N Ay  kc C A s  C A     D AB
y y 0

D AB C A 0.332D AB
kc    Re,1x 2
C A s  C A  y y 0
x

kc x
Nu AB   0.332 Re,1x 2
D AB

d Nu AB , x  0.332 Re,1x 2 Sc1 3

- Pohlhausen  Sc1 3
dM
0.332
if x  x0 , C A  C A and x  x0 , C A  C A s Nu AB  Re,1x 2 Sc1 3
1   x0 x 
3 34

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Mean Nusselt Number
C A  0.332 1 2 1 3 
 C A  C A s  Re,x Sc 
y y 0  x 

kc x
 Nu x ,AB  0.332 Re,1x 2 Sc1 3
D AB

WA  k c AC A s  C A    kc C A s  C A dA
A

0.332D AB Re,1x 2 Sc1 3dA

 k cWLC A s  C A   C A s  C A 
A x

kcL
 0.664 Re,1L 2 Sc1 3
D AB

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Mass, Energy and Momentum Transfer Analogy
At steady state
d  vx  d  C  C A,s 
    A
dy  v  y 0 dy  C A,  C A,s 
y 0

 d  vx  d  C  C A,s 
if Sc  1     D AB  A
D AB dy  v  y 0 dy  C A,  C A,s 
y 0

C A  C A,s 
N A,y  kc C A,s  C A,    D AB
y y 0

 dvx w 2 dvx
kc  Cf  
v dy y 0 v2 2 v2 dy 0

kc C f h Cf
 
v 2 vC p 2

Reynolds Analogy (1) Sc=1, and (2) no form drag ~ only skin drag

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Chilton-Colburn Analogy
The Schmidt number is other than unity
Nu AB 0.332
Nu AB 
kc x
 0.332 Re, x Sc
12 13 
D AB Re, x Sc1 3 Re,1x 2
Nu AB Nu AB Cf
 Sc 23

Re, x Sc1 3 Re, x Sc 2
 kc x    D AB  2 3 kc Sc 2 3 Cf
   Sc  
 D AB  xv      v 2

Chilton-Colburn Analogy (1) 0.6<Sc<2500, and (2) laminar flow

kc 2 3 C f
jD  Sc 
v 2
Colburn j factor for mass transfer

Cf h k
jD  jH  Pr 2 3  c Sc 2 3 (1) 0.6<Pr<2500
2 vC p v (2) 0.6<Sc<100

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Mass Transfer to Non-Newtonian Fluids

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 Mass Transfer to Non-Newtonian Fluids
Mass Transfer to a Power-Law Fluid
Flowing on an Inclined Plate
fully developed flow
incompressible power-law fluid,
mass transfer rate is small
no chemical reaction
the solid surface consist of
a soluble material of length L
 2c c
D A 2  Vz ( x )
C* x z
C(x,z)  B.C. 1 at z  0 , c  co
B.C. 2 at x  0 , c  c * solubility
c
B.C. 3 at x  d, 0
x
no mass transfer
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 Mass Transfer to a Power-Law Fluid
Flowing on an Inclined Plate-1
The stress distribution in the film
 xz  g( x  d ) cos 
The mass transfer is confined to a region near the solid surface
 xz   gd cos 
c
B.C. 3 at x  d, 0  B.C. 3’ at x  , c  co
x
for power-law fluids
n 1
dV
m z  gd cos   gd cos   n
or Vz    x
dx  m 
the shear rate at the plane surface
1
 gd cos   n
w   
 m 
Sogang University
 Mass Transfer to a Power-Law Fluid
Flowing on an Inclined Plate-2
 2c c
DA 2  w x
x z
By using Laplacce transform
c( s )  0 exp( sz )(c  co )dz

 2 c( s )
DA  w xs c( s )
x 2

a form of the Bessel equation

1

 2  DA 
x  I  1 ( t )  I 1 ( t )
6
1
c( s )  (c  co )(3 ) 
* 3

o
 3   w s 
  3 3 
1

 2  w s  16
2

t     x
 3  DA 
I  1 ( t ), I 1 ( t ) the modified Bessel functions of the first kind
3 3
of order -1/3 and 1/3, respectively
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 Mass Transfer to a Power-Law Fluid
Flowing on an Inclined Plate-3

 1      s 
1
c 2 3

 (c *  co )(3 6 ) 4  w 
3

x x  0   3   DA 
1 1
c 3   
3 3

 (c *  co ) 1  w 
x x  0   3   DA z 

the average(over the length L) mass transfer coefficient

c
 DA dz 4 2 1
1 L x x  0 3 DA  w  3
3 3
ka  0   
L ( c *  co ) 2 3   L 
1

Sogang University
 Mass Transfer to Non-Newtonian Fluids
Mass Transfer to a Power-Law Fluid
in Poiseuille Flow
completely analogous to convective heat transfer in Poiseuille flow
y c  2c
Vo  DA 2
R z y
B.C. 1 at z  0 , c  co inlet concentration
B.C. 2 at y  0 , c  c * solubility
B.C. 3 at y  , c  co
B.C. 3 is valid only for the case of short contact time for which
the mass transfer, or diffusion, proceeds in the vicinity of the wall

Dimensionless variables
c * c y DA z
C ,  ,  
c *  co R V  R 2
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 Mass Transfer to a Power-Law Fluid in
Poiseuille Flow-1

The velocity profile for power-law fluids

Vz Vz 3  n1  n
1 1
 Q  1  (1   )
V  R 2 1  n1  

 dV   1 Q  1 Q
w   z    3   3 Vo  w R   3   2
 dy  y  0  n  R  n  R

1  C  2 C B.C. 1 at   0 , C  1

 3    B.C. 2 at   0 , C  0
 n    2
B.C. 3 at   , C  1
Similarity solution technique 1
 9  3
   ( )    
 3  (1 n) 
d 2C 2 dC
 3  0 C( 0 )  0 and C()  1
d 2
d
1   3
  e d

 34

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 Mass Transfer to a Power-Law Fluid in
Poiseuille Flow-2

The local mass transfer coefficient

c
 DA  k loc (cb  c*)
y y  0
cb is the bulk solute concentration in the fluid
For short contact time, cbco
local Sherwood number(Nusselt number for mass transfer)
 c 
2 R 
2k loc R  y  y  0 C
Shloc   2
DA (co  c*)    0

 1
 3   V  R
2

C    2 3  n
Shloc  2   4
  0 
    3  9 DA z

Sogang University
 Mass Transfer to a Power-Law Fluid in
Poiseuille Flow-3

average Sherwood number

 1
 3   V  R
2

Sha 
2k a R 1 L 3 3
 0 Shloc dz  4  n
DA L  3  9 DA L
1
 1 3

3  n  1
R 2 V 
Sha  1.75   Gz 3 Gz 
 4  DA L
 

R 2 V    2 RV      R    R
Gz    
  
 L  2 Re Sc  
DA L 2    D A    L

Shear thinning(as n decreases) enhances the mass transfer rate

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Concentration Distributions in Turbulent Flows
vx  vx  x , y , z   vx  x , y , z ,t  C A  C A x , y , z   CA x , y , z ,t 
C A
 v  C A  DAB 2C A  knC An
t
k1C A
C A 
 v  C A  D AB2 C A  v   C A  
t  C 2A  C 2A 
 2
k


t 
J A  vC A

D
   v  0
Dt

Dv
Dt
v 
t 
  p        g 
k1C A
 v  t 
     J A  J A    
DC A
  k2  C A  C  A 
2 2
Dt  
  

Sogang University
 Concentration
Distributions in
Turbulent Flows-1

t 
t  dC A
J A  D AB
dy

t   t 
Turbulent Prandtl Number Sc  t  1
D AB

Prandtl’s mixing length ~ normal to the direction of bulk flow

in the y direction t  dv x dC A
J A  v y  C A  l 2
dy dy

Sogang University
TRANSFER COEFFICIENTS IN ONE PHASE

the rates of mass transfer across phase boundaries to the

relevant concentration differences, mainly for binary systems
Fig. 22.1-1. Example of mass transfer across a
plane boundary: 포화 평판의 건조

Fig. 22.1-2. Two rather typical kinds of

membrane separators, classified here
according to a Peclet number, or the flow
through the membrane. The heavy line
represents the membrane, and the arrows
represent the flow along or through the
membrane.

선택적 투과막

진짜 상 경계를 가짐
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 유체역학적 물성의 급격한 변화

Fig. 22.1-3. Example of mass transfer

through a porous wall: transpiration cooling.

Fig. 22.1-4. Example of a gas-liquid contacting

device: the wetted-wall column. Two chemical
species A and B are moving from the downward-
flowing liquid stream into the upward-flowing gas
stream in a cylindrical tube

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 N

미분 면적에 정의되는 국부 전달계수 e  kT   H N 

 1

Partial molar enthalpy

J A* 0  JB* 0 , x A  xB  k xA,loc  k xB,loc

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if the heat of mixing is zero (as in ideal gas mixtures)

H A  CpA,0 T0  T o 
~
T o : reference temperature

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Partial molar enthalpy

 H 
H   
 n T ,P ,n

H kn1 , kn2 , kn3 ,   kHn1 , n2 , n3 ,  Enthalpy ~ Extensive property

By Euler Theorem H   n H Homogeneous of degree 1



 H~  ~
~
H A  H  xB   ~  H 
 x  HB  H  x A   H  H / nA  nB   H / n
~
 B n  x 
 B n
 H  H xB  H 
   HA    
nA  1  xB n; nB  xB n
 nA  nB n n  xB n

 H   H   nA   H   nB 
             H A  n   HB  n 
 xB n  nA nB  xB n  nB nA  xB n


H   n H  nAH A  nB HB 

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mass transfer coefficient

"apparent" mass transfer coefficient

The superscript 0 indicates that these quantities are applicable only for small mass-transfer
rates and small mole fractions of species A.

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TRANSFER COEFFICIENTS IN TWO PHASES

Interphase Mass Transfer

N A0 gas
 N A0 liquid
 N A0

N A0  k y0,loc  y Ab  y A0   k x0,loc x A0  x Ab 

Assuming equilibrium across the interface

y A0  f  x A0  평형곡선

N A0  K y0,loc  y Ab  y Ae   K x0,loc x Ae  x Ab 

Overall concentration difference

y Ae Gas phase composition in equilibrium with a liquid at composition x Ab

x Ae Liquid phase composition in equilibrium with a gas at composition y Ab

Sogang University
 Fig. 22.4-2. Relations among gas- and
liquid phase compositions, and the
graphical interpretations of mx, and my.

N A0  K 0y ,loc  y Ab  y Ae   K x0 ,loc  x Ae  x Ab 

K 0y ,loc the overall mass transfer coefficient "based on the gas phase’

K x0 ,loc the overall mass transfer coefficient "based on the liquid phase"

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If k x ,loc mk y ,loc  1 the mass-transport resistance of the gas phase has little effect,
0 0

and it is said that the mass transfer is liquid-phase controlled. In practice, this means that
the system design should favor liquid-phase mass transfer.

If k x ,loc mk y ,loc  1 then the mass transfer is gas-phase controlled. In a practical

0 0

situation, this means that the system design should favor gas-phase mass transfer.

If 0 .1  k x0 ,loc mk 0y ,loc  10 , roughly, one must be careful to consider the interactions

of the two phases in calculating the two-phase transfer coefficients.

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Mean two phase mass transfer coefficient

bulk concentrations in the two adjacent phase do not change significantly over
the total mass transfer surface

1
K 0x ,approx 
1 k0xm   1 mx k0ym 

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 Penetration model holds in each phase

4 D AB
k 0x ,loc  k x ,loc  cl
t exp

4 D AC
k 0y ,loc  k y ,loc  cg
t exp
Total molar concentraion in each phase

k 0x ,loc cl D AB 1
  1
mk0y ,loc cg D AC m

Only liquid phase resistance is significant

an oxygen stripper, in which
oxygen(A) from the water(B) Absorption or desorption of sparingly soluble
diffuses into the nitrogen gas(C) gases is almost always liquid phase controlled
bubbles.

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the law of conservation of mass of
chemical species  in a multicomponent
macroscopic flow system

the instantaneous the mass rate of the net rate of

total mass of  in addition of production
the system species  to the of species  by
system by mass homogeneous
transfer across and hetero-
the bounding geneous
surface reactions within
the system

in molar units

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Disposal of an unstable waste product

d
t  V w mA,tot  wA0  k1''' mA,tot t 0 mA,tot  0
dt
wA0
mA,tot 
k1'''

1  expk1''' t 

A 1  expk1''' t 
mA,tot  wt A 
A0 k1''' t
AF 1  e K
When the tank is full  K  k1''' V w  k1''' V Q
A0 K
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 d
t  V w  AV   wA0  wA  k1''' V
dt
dA
 1  K A  A0   w V t
d
 1 A  AF

A  A0 1  K 
 e 1 K  1 
AF  A0 1  K 

A0 A0
A  
1  K 1  k1''' V w 

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Binary Splitters
zF  yP  xW
F  P W
Cut  P F

z  y  1   x

Separation factor  Y  X
y x
Mole ratio Y  , X 
1 y 1 x
x y
y  or x 
1    1x     1y
Gas-liquid Splitters(equilibrium distillation)  Relative volatility

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Dirac 분리용량(separation capacity) 및 가치함수(value function)

서로 다른 분리공정의 유효성을 비교하기 위한 기준 수립

y 1  y  y- x
   1
x 1  x  x1- y

약간 농축되는 계   1 
x    1x
y   x    1x 1  x 
1    1x
Dirac 분리용량(separation capacity)
  Pv (y )  Wv (x )  Fv (z )
Binary Splitters zF  yP  xW
F  P W
Cut  P F

z  y  1   x or z - x   y - x

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 
 v (y )  1   v (x )  v (z )
F

v (y )  v (x )  y  x v x   y  x  v x   
1 2
2

v (z )  v (x )  z  x v x   z  x  v x   
1 2
2


 21  1   y  x  v (x )
2

F
x    1x 
 21  1     1 x 2 1  x  v (x )
 x    1x 1  x 
2 2
y 
1    1x F
x 2 1  x  v (x )  1
2
계의 분리용량은 실질적으로 농도에 무관하다고 가정

 21  1     1
2

F
2
d v (x ) x
v (x )  2 x  1ln
1
  2  C 1x  C 2
dx 2 x 2 1  x 
2
1  x 
x
적분 상수를 구하기 위한 조건 선택 v (x )  2 x  1ln
v (21 )  0, v (21 )  0 1  x 
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Compartmental Analysis

A complex system is treated as a network of perfect mixers, each constant

volume, connected by ducts of negligible volume, with no dispersion occurring
in the connecting ducts
d n N
Vn  Q mn m  n   V n rn
dt m 1

Q mn The volumetric flow rate of solvent flow from unit m to unit n

d 1
 Q 1  2   G
Hemodialysis during dialysis period
V1
dt
d
V 2 2  Q 1  2   D 2
dt
Initial condition t  0 1  2  0

d 2 2  Q Q D  d 2 Q D Q G
 
V   
   
dt 2  1 V 2 V 2  dt V1 V 2 2 V1 V 2
d 2 D 0
t  0 2  0 and 
dt V2
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For the recovery period

d 2 2  V1  V2  d2 QG
 Q   
dt 2
 V1V2  dt V1V2

 V V  
2 ,cf  C3 expQ 1 2
t   C4
  1 2  
V V
Gt 
2 ,pi 
V1  V2

Initial condition t  0 2  2 1  1

d2 d2 D2

 
dt dt V2

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 during dialysis period

For the recovery period

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Sogang University
Tour du Mont Blanc
Sogang University
Two or Three Dimensional Diffusion
At steady state  2C  0
Y A
CA  Cx Infinite plate in z direction
L
 2C A  2C A
 0
x 2 y 2
 2C A  0
CA  0 CA  0
at x  0 , all y, C A  0
at x  W, all y, C A  0
0 CA  0 W X at y  0 , all x, C A  0
at y  L, all x, C A  C  x 

by Separation variables method

C A  x , y   X  x Y  y 

1 d 2 X 1 d 2Y
   2

X dx 2 Y dy 2

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 Two or Three
Dimensional Heat

Conduction-1

d2X d 2Y
2
 X  0
2
and 2
 2Y  0
dx dx
General solution of temperature distribution

C A x , y    A cos x  B sin x  Cey  Dey 
at x  0, all y, C A  0 A0
at y  0, all x, C A  0 C  D

at x  W, all y, C A  0 DB sin W  0
W  n   n W
at y  0, all x, T  Ts  T1

 n 
T1   Bn sin x
n 1  L 
4T1
Bn  for n  1, 3, 5 Bn  0 for n  2, 4, 6
n

T x, y   Ts 
4T1 e 2 n1y L 2n  1x

 2n  1 sin
L
n
 n   L y Sogang University
T x, y   Ts   Bn sin
 x e
 L 