Mass Transfer 1 Diffusion A Molecular diffusion i

Fick's law of diffusion

The flux of molecular diffusion is proportional to the concentration gradient

dC A
FA 
dx

-ve because the direction of Diffusion is in

dC A dC A the direction of decrease of concentration
FA   D A g cm 2s R A  D A A g s
dx dx D A  FA for
dC A
 1
dx

DA  diffusion coefficient = diffusivity cm 2 s L2T 1

in gases 1 10 1 cm 2 s

D A in liquids 1 10 5 cm 2 s
in solids 1 10 7  1 1010 cm 2 s


k 
For ideal gases D     

C P
thermal diffusivity kinematic viscosity
Mass Transfer 1 Diffusion A Molecular diffusion ii

Prediction of D

In gases ( Gilliland Correlation )

0.00435T 1.5 1 1 T = temp ( K )

D A B   P = pressure ( atm )

 
2
P V A V B
1
3
1
3 MA MB V = mol. volume ( cc/gmol )
M = mol. weight
D = diffusivity ( cm 2 s )

1.5
D St . T St1.5. P T  P
  1.5   St .  
D PSt . T  T  PSt .
In liquids In mixtures

  viscosity in poise
7.7  1010 T D A mix 
1 y A
D 
  yB y
V A  mol. volume of component
 V A V 0
1 1
3 3  C  
V 0  mol. volume of liquid D AB D AC

In solids No accurate correlation

Mass Transfer 1 Diffusion A Molecular diffusion iii

Steady-state molecular diffusion

1. Equimolar counter diffusion FA   FB ( e.g Distillation )

D A B dPA
FA   
RT dx
D BA dPB
FB   
RT dx
But PA  PB  P  const
dPA dPB dP dP dP
   0  B  A
dx dx dx dx dx
D AB dPA
 FB    FA   FB
RT dx
D dP D dP
  A B  A   BA  B
RT dx RT dx
 D AB  D BA  D
D dPA
FA   
RT dx
D
FA  dx    dPA
RT
At steady state rate and area=const., FA  const.
2 2
D
FA  dx    dPA
1
RT 1

D
FA  x 2  x 1   
RT
 PA2  PA1 
 FA 
D

 PA1  PA2 
RT x 2  x1
or FA  D
C A1  C A2 
x 2  x1
Mass Transfer 1 Diffusion A Molecular diffusion iv

2. Diffusion of (A) in non-diffusing (B) FB  0 ( e.g Absorption )

liq
D dPA D dPA
FB Bulk flow   FA   
RT dx gas RT dx
D dPB D dPA
FB     
P D dPA PA RT dx RT dx
FA Bulk flow  FB Bulk flow  A    
PB RT dx PB
Bulk flow of A & B
D dPA D dPA PA
FA  FADiffusion  FA Bulk flow      
RT dx RT dx PB
D dPA  PA 
  1  
RT dx  PB 
 P  PA lg 
P  P   P  P  
A2 A1 PA1  PA2
D dPA  PA  PB   P  PA 2   P  PA2 
    ln   ln  
RT dx  PB   P  PA  P  PA
 1   1 
D dPA P  P  PA 2 
 FA     PA1  PA 2 PA  PA2
RT dx PB ln 
 P  PA    1
D dPA P  1   P  PA lg PB lg
FA    
RT dx P  PA D PA1  PA 2 P C A1  C A 2 CT C 
FA    or FA  D    T  1
CB 
D dPA RT x 2  x 1 PB lg x 2  x1 C B lg  lg 
FA  dx   P
RT P  PA
( greater than equimolar due to bulk flow )
FA  const . ( steady state + const. area )
2 2
D dPA
FA  dx   P N.B: In case of diffusion in solids, no bulk flow takes place:
1
RT 1 P  PA
 P  PA2  C A1  C A 2
D FA  D 
FA  x 2  x 1   P ln   x 2  x1
RT  P  PA
 1 
 P  PA2   C  C A2 
ln   ln  T 
D  P  PA D  CT  C A
FA  P  1  or FA  CT  1 
RT x 2  x1 RT x 2  x1
Mass Transfer 1 Diffusion A Molecular diffusion v

3. Steady molecular diffusion through variable area

PA1  vap . press .
D dPA P
R A  FA  A      4 r 2
RT dr P  PA
2 2
dr D dPA
RA   4 P
1
r 2
RT 1 P  PA
1 1 D  P  PA 2 
R A     4 P ln  
 r1 r2  RT  P  PA
 1 
r2  , PA 2  0
1 D  P 
R A    4 P ln  
 r1  RT  P  PA
 1 
Mass Transfer 1 Diffusion A Molecular diffusion vi

Unsteady state molecular diffusion FAy

FAy  dy FAz
y y
Rate in  Rate out x

  F  FAx
  FA x   FAx  A x dx   dz  dy
  x  FA x
FA x  dx
 dC A dC A  2C A  x
  D D D dx  dz  dy
 dx dx  x 2
 FA y
 2C A F x
D dx  dy  dz FA z  A z dz
x 2 z
x

Total Rate: z
  2C A  2C A  2C A  C A
D    dx  dy  dz  t dx  dy  dz  rate of acc.
 x y 2 z 2
2

  2C A  2C A  2C A  C A
D     t
 x y 2 z 2
2

C A  f  x , y , z , t  solution by knowing boundary & initial conditions

For generation  where rA  rate of generation 

  2C A  2C A  2C A  C A
D     rA  t
 x y 2 z 2
2

For heat transfer by conduction

k
thermal diffusivity= , C A T
c p

For simple cases

 2C A C A analitical solution or numerical solution

one dim.: D 
x 2 t
Mass Transfer 1 Diffusion A Molecular diffusion vii

Special cases

1. Diffusion in solids
C A1  C A 2
FA  D
x 2  x1
No prediction method for D ( highly sensitive for concentration and temperature )

2. Diffusion through voids of porous solids

C A1  C A 2
RA  D   Aact
 x 2  x 1 act
C A1  C A 2
D  A 
 x 2  x 1 
 C A  C A2
D  1 A
 x 2  x1
C A1  C A 2 
R A  Deff  A D eff  D    0.1  0.2  D
x 2  x1 

3. Diffusion in pores
d pore  mean free path of molecules

The collision between the molecules and the wall is greater than the collision between the molecules and themselves ( Knudson diffusion )
e.g gases at low pressure
1
 T 2
D K  97rcap  2
 m s
M
 A

For d pore  mean free path of molecules apply normal diffusivity

e.g gases at high pressure and diffusion in liquids
Mass Transfer 1 Diffusion A Molecular diffusion viii

Other forms of diffusion

i) Self diffusivity
It is a measure of mobility

ii) Thermal diffusivity

Diffusion due to difference in temperature ( e.g uranium separation )
Light material is at high temperature and viceversa

iii) Pressure diffusion

Due to difference in pressure ( e.g. gas wells)

iv) Force diffusion

e.g centrifugal force
Mass Transfer 1 Diffusion B Convection i

Modified Fick's law

dC A
FA    D  E d  where Ed is eddy diffusivty = f (Re,position)
dx

But E d cannot be well predicted

FA  k g C A g  C Al   where C A g = conc. in bulk of gases

C Al = conc. at interface
k g = mass transfer coefficient ( cm/s )

k is obtained emperically or from industrial experience

k  f G ,  ,  , L , D 
where G = mass flow rate
L = diameter

Dimensional analysis
k  A  G a   b   c  Ld  D e
LT 1
  ML2T   ML   ML
1 a 3 b 1
T 
1 c
Ld  L 2T 
1 e

a b c
M 0
M
1  a c e
T T
L  L 2a 3b c d  2e
0  a b c
1  a  c  e
1  2a  3b  c  d  2e
kL  GL     
  f  , 
D      D  
x y
kL  GL    
A   
D     D 
Mass Transfer 1 Diffusion B Convection ii
Sherwood no. kL , the ratio between mass transfer coeff. And diffusion coeff.
D
Reynold's no. GL , vL , measure of turbulance
 
Schmidt no.
  , effect of physical properties on diffusion

D D
Gas in tube: Sh  0.023Re 0.83 Sc 0.44
1
  2
1 1
Liquid on walls:Sh  0.725Re 3 Sc 3  
L 
Packed column: Gas: Sh  0.11Re Sc 0.33
0.8

2 1
Liquid: Sh  0.015Re 3 Sc 3

Physical models for convective mass transfer

Whitman film model ( or two films model )

D
k 
F
D
C  C Al  
  
Ag
F  k C A g  C Al

 C 
D
 C Al
 Ag

where   film thickness  as    k 

Penetration model ( Hegbi )
C a  2C a
D
t x 2
C a  C ab at all x at t  0
C a  C ai at x  0
C a  C ab at x  
D where t is the mean residence time of eddy at the surface
k 2
t
Film penetration ( Toor and Marchello )
Mass Transfer 2 Mass transfer analogies

Analogy between mass, heat and momentum transfer:

Fourier's law : dT k d  c pT  d  c pT 
q  k    
dx c p dx dx
Newton's law : dv  d  v  d  v 
      
dx  dx dx
Fick's law : dC A
F  D
dx
 
Pr  Sc 
 D
ideal gases 1 1
inorganic gas (R.T.P) 0.7-1.1 0.6-1.1
liquids 7 1200

Reynold's Analogy

f k h
  for high turbulence gas flow
8 v c pv

where: f = Moody friction factor

Prandtl Analogy

Chilton Colburn Analogy

2 2
f k h
  Sc 3   Pr 3 for real gases and liquids
8 v c pv
Mass Transfer 3 Mass transfer between two phases i

Mass transfer between two phases


Fag  k g Pag  Pai 
Fal  k l C ai  C al 
At steady state Fag  Fal  Fa
 
Fa  k g Pag  Pai  k l C ai  C al 
Fa
 Pag  Pai 1
kg
Fa
 C ai  C al
kl 2

At equilibrium Pa*  mC A

a) Multiply 2 by m
Fa
m  mC ai  mC al
kl
Fa
m  Pa*i  Pa*l 3
kl

Adding 1 & 3
 1 m the two phases are at equilibrium at the interface i.e the surface has no resistance to mass transfer P  Pa*i 
Fa     Pag  Pal
* ai
k k
 g l 

Pag  Pa*l
Fa 
1 m

kg kl


 k og Pag  Pa*l  where k og
1
= overall mass transfer coefficient
= overall resistance
k og
Mass Transfer 3 Mass transfer between two phases ii
For most cases the surface has no resistance except in : i) crystallization
ii) presence of surface active agent
iii) presence of a film at the interface

b) Divide 1 by m, then add the resulting equation to 2

C  C al
*

Fa 
1
ag

1 
 k ol C a*g  C al 

k L mk g

  
Fa  k g Pag  Pai  k l C ai  C al   k og  Pag  Pa*l   k ol C a*g  C al 
1 m
If  
kg kL
 two phases affect mass transfer
1 m  k 
   m is small, L is large 
kg kL  k g 
 controlled by gas phase
kL
m is very large, is small
kg
 controlled by liquid phase
Mass Transfer 3 Mass transfer between two phases iii

Increasing the rate of mass transfer

1. Increase the area

use : plates
packing
spray

2. Increase mass transfer coefficient

3. Increase the driving force

In absorption use low temperature and high pressure
Increase liquid flow rate for the same conditions
Use counter current

Decrease the rate of mass transfer

Rate of drying of ceramic materials

decrease velocity of drying gas
decrease temperature of gas
recycle of gas ( to use the heat and increase the humidity )

Decrease loses from storage of volatile materials

decrease the area
closing the tank
use a floating roof