ARTICLE 18.

Article 18.2
UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE
In Chapter 1 we began by stating Newton's law of viscosity, and
in Chapter 9 we began with Fourier's law of heat conduction. In
this chapter we start by giving Fick's law of diffusion, which
describes the movement of one chemical species A through a
binary mixture of A and В because of a concentration gradient of
A. The movement of a chemical species from a region of high
concentration to a region of low concentration can be observed
by dropping a small crystal of potassium permanganate into a
beaker of water. The KMnO4 begins to dissolve in the water, and
very near the crystal there is a dark purple, concentrated solution
of KMnO4. Because of the concentration gradient that is
established, the KMnO4 diffuses away from the crystal. The
progress of the diffusion can then be followed by observing the
growth of the dark purple region.
DIFFUSION THROUGH A STAGNANT GAS FILM
Consider the diffusion system in which liquid A is evaporating into
gas B

Gas stream of A & B

• At the liquid-gas interface,
z=z2 z=z1, the gas-phase
Gas B concentration of A is xA1

NA| z+∆z
• A stream of gas mixture A-B
∆z of concentration xA2 flows
slowly past the top of the
NA| z tube
z

z=z1

Liquid A

UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE

ASSUMPTIONS

 The liquid level is maintained at z1.

 A and В form an ideal gas mixture.
 Solubility of gas B in liquid A is negligible.
 The entire system is kept at constant temperature and pressure.
 Gas velocity at the cylinder wall will be smaller than that in the center of the
tube but for simplicity we assume that there is no dependence of the z-
component of the velocity on the radial coordinate.
 At steady state, there is a net motion of A away from the interface and the
vapor В is stationary.

UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE

EXPRESSION FOR CONC. PROFILE

 Molar flux of A in z-direction is

cDAB dxA
NAz   (1)
1  xA dz
 A steady-state mass balance over an increment ∆z of the column gives

SNAz | z  SNAz | z  z  0 (2)

 ‘S’ is the cross-sectional area of the column. Division by S∆z and taking
the limit as ∆z —» 0 gives

 NAz | z NAz | z  z  (3)

Lim    0
z 0
 z z 
UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE
Cond…
dNAz (4)
  0
dz
 Substitution of Eq.1 into Eq. 4 gives

d  cDAB dxA 
 0 (5)
dz  1  xA dz 
 For an ideal gas mixture at constant temperature and pressure ‘с’ must
be a constant and for gases “DAB” is independent of concentration.
Hence cDAB can be taken outside of the derivative to get

d  1 dxA 
 0 (6)
dz  1  xA dz 
Integrating…

 This is a second-order differential equation for the concentration profile

expressed as mole fraction of A. Integration with respect to z

d  1 dxA 
 dz  1  xA dz    0 (7)

1 dxA
  C1 (8)
1  xA dz
 A second integration then gives

 ln( 1  xA)  C1 z  C2 (9)

 Where C1 & C2 are constants of integration
APPLYING BOUNDARY CONDITIONS

 B.C. 1 : at z=z1, xA=xA1

 B.C.2 : at z=z2 xA=xA2

 Substituting B.C.1 in Eq.9

 ln( 1  x A1 )  C2
 C1 (10)
z1

 And then Substituting B.C.2 in Eq.9

 ln( 1  x A 2 )  C2
 C1 (11)
z2
 Solving Eq.10 & Eq.11 Simultaneously we get
x 
ln  B1 
(12)
C1   xB 2 
z 2  z1

 And
z1 ln xB 2  z 2 ln xB1
C2  (13)
z 2  z1

z1  xB1 
C2   ln  
  ln xB1
(14)
z2  z1   xB 2 
 Substituting C1 & C2 in Eq.9
z  z1
 1  x A   1  x A2  z 2  z1
(15)

1 x  
 1 x 

 A1   A1 

For component B.
z  z1
 xB   xB 2  z 2  z1
(16)

x  
x 

 B1   B1 
AVERAGE CONC. OF COMPONENT B

 Now we calculate the average conc. Of B in the Region between z1 & z2.
z2  xB 
xB , avg 
z1

x  dz
 B1  (17)
 z2
xB1

z1
dz
 Using Eq.16, substitute the value of xB/xB1 in above Eq.
z  z1

x  z 2  z1

  
z2

x 
B2
dz (18)
 
z1
xB , avg
 B1
z2
xB1
 z1
dz

UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE

 Substituting ζ = (z-z1) / (z2-z1) and dζ = dz , where ζ is reduced Length

 xB2 
 
1
d
  (20)
 
0
xB , avg x B1
 1
xB1
 0
d

 To calculate the new limits we put values of C1 & C2 in Eq.9 , we get

 z2  z 
ln xB   ln xB 2 
z z   ln xB1
(19)
 2 1 

UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE

Substituting B.C.1 & B.C.2 in Eq.19, we get new limits of integration as follow
 B.C. 1 : at z=z1, ζ=0
 B.C.2 : at z=z2 ζ=1

 xB2 
 
1
d
  (20)
 
0
xB , avg x B1
 1
xB1
 0
d

 1
 
  xB2   (21)
  
 
x B , avg   x B1  
  
x B1   
 ln  x B 2 


  x  

  B1  
0

UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE

 By putting limits we get the following Eq.

xB 2  x B1
x B , avg 
 xB 2  (22)
ln  
 xB1 

 The average value of xB is the Logarithmic mean, (xB)ln of the terminal

values.
RATE OF EVAPORATION

 The rate of Evaporation is obtained by using Eq.1

 cDAB dxA 
NAz | z  z1   (23)
 1  xA dz  z  z1
 For component B

 cDAB dxB 
NAz | z  z1    (24)
 xB1 dz  z  z1
 Now we calculate the value of dxB / dz by using Eq.16
 xB 2 
ln   (25)
dxB
  xB1 
dz ( z2  z1 )

 Putting Eq.25 in Eq.24 , we get

cDAB  xB 2  (26)
NAz | z  z1  ln  
( z2  z1 )  xB1 

UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE

 From Eq. 22, we can get the value

 xB 2  ( xB 2  xB1 ) (27)
ln   
 xB1  ( xB )ln

 Eq. 26 & Eq. 27 are combined to give an alternative expression for

mass-transfer rate
cDAB
NAz | z  z1  ( x A1  x A2 ) (28)
( z2  z1 )( xB ) ln
 This Expression relates mass transfer of component A to concentration
driving Force (xA1 – xA2).

UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE

MOLAR FLUX IN TERMS OF PRESSURE

 Now Using c=P/RT ; Eq.26 becomes

( pDAB / RT ) pB 2
NAz | z  z1  ln (29)
( z2  z1 ) pB1

 And Eq.28 can be written in terms of Pressure

pDAB / RT
 NAz | z  z1  ( p A1  p A2 ) (30)
( z2  z1 )( pB ) ln
 This is the final expression of molar Flux in terms of total & partial pressure.

UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE

CONCENTRATION PROFILE GRAPH

xB
1.

z2
0

xB2

xA2
xA + xB = 1

xA
xB

Z
xB1

xA1

z1
1. xA 0
0

This graph shows how conc. profile for B is distorted because of Diffusion of A.
UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE