CME 301 – Mass Transfer

Lecture 2_2
2b. Differential Equations for
Steady-State Molecular
Diffusion

Dr. Chandra Mouli M.R.

Chemical Engineering Department

College of Engineering

Abu Dhabi University

 One-Dimensional (1D) Mass Transfer

• Consider a binary mixture of A and B

• There are two common cases to consider for

molecular diffusion:
1. Diffusion of A through stagnant B (vB = 0) 
(unimolecular diffusion, UMD)  NB = 0

2. Equimolar Counter Diffusion (EMCD)  NB = – NA

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 Example 1: Arnold diffusion Cell
(UMD)
 used to measure diffusion coefficients (DAB) of gases.

 It consist of a narrow tube which is partly filled with pure

liquid “A”, and is maintained at a constant temperature
and pressure.
• Gas “B” flows across the open end of the
cell and has negligible solubility in the
liquid.
• Develop an expression for the mass
transfer of vaporizing A

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Solution

Assumptions:
1. B is insoluble in A
2. A is volatile and exerts a vapor pressure
3. Gas inside tube is still
4. Liquid level inside tube is constant  z1 is constant
5. No reaction  RA = 0
6. 1D flux along z
7. Uniform cross sectional area
8. Constant T and PT in gas within the tube
9. Steady state
10. Evaporation of A is limited by the diffusion of A

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Solution (Continued)

• Differential equation of mass transfer:

–▽NA + RA = ∂cA/∂t

∂N Ax ∂N Ay ∂N Az
∇N A = + + =0
∂∇x ∂y ∂z

Similarly, for component B: dNBz/dz = 0

Since B is insoluble in A  NB|z1 = 0
 Flux of B is zero throughout the diffusion path
(Steady State)
 Component B is a stagnant gas  NB = 0 5
Solution (Continued)

Flux Equation
∂y A
N Az = −cT DAB + y A ( N Az + N Bz )
∂z
If the gas flow is
− cT DAB dy A high  A is swept
N Az =
1 − y A dz away  yA2 ~ 0
(very small)

Boundary Conditions:

1: yA= yA1 @ z=z1 2: yA= yA2 @ z = z2

z2 yA2 dy A cT DAB 1 − y A 2 
N Az ∫ dz = −cT DAB ∫ N Az = ln  
z1 y A1 1− yA z 2 − z1  1 − y A1 

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Solution (Continued)

• Recall that (yA + yB = 1)  yB changes with z

• The log-mean average concentration of component B is

defined as:

y B ,lm =
y B 2 − y B1
=
[1 − y A2 ] − [1 − y A1 ] = y A1 − y A 2
ln ( y B 2 y B1 ) ln ([1 − y A 2 ] [1 − y A1 ]) ln ([1 − y A 2 ] [1 − y A1 ])
cT DAB 1 − y A 2 
OR........ ln ([1 − y A 2 ] [1 − y A1 ]) = y A1 − y A2 N Az = ln  
z 2 − z1  1 − y A1 
y B ,lm
Therefore:
 D AB 
NA   cT ( y A 1 −=
y A 2 ) k c (c A 1 − c A 2 )
 ( z 2 − z 1 ) y B ,lm  7
 cT DAB ( y A1 − y A 2 )
N Az =
z 2 − z1 y B ,lm
This equation may also written in terms of pressure. For an ideal gas
n
c= =
P
yA =
pA DAB P ( p A1 − p A 2 )
N Az =
V RT P RT ( z 2 − z1 ) pB ,lm

The above equation also written for film model for mass transfer of
component A into a moving gas stream. If (z2-z1) is set to quale to δ.

DAB P ( p A1 − p A 2 )
N Az =
RT 𝛿𝛿 pB ,lm
Solution (Continued) − cT DAB ∂y A ∂N Az
N Az = ∇N A = =0
1 − y A ∂z ∂z
• Concentration Profiles: BC1:

∂N A z ∂  −cT D AB ∂y A  cT DAB ln (1 − y A1 ) = C1 z1 + C 2
=  =0
∂z ∂z  1 − y A ∂z  BC2:

− cT DAB ∂y A cT DAB ln (1 − y A 2 ) = C1 z 2 + C 2
Integration  = C1
1 − y A ∂z Solving for C2 from both
Separation of var.s  equations and subtracting:
∂y A C 2 = cT DAB ln (1 − y A1 ) − C1 z1
− cT DAB = C1∂z
1− yA C 2 = cT DAB ln (1 − y A 2 ) − C1 z 2
Integration 
 1 − y A2 
0 = cT DAB ln  − C1 ( z 2 − z1 )
cT DAB ln (1 − y A ) = C1 z + C 2  1 − y A1 
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 C 2 = cT DAB ln (1 − y A1 ) − C1 z1
cT DAB  1 − y A 2 
C1 = ln 
z 2 − z1  1 − y A1 
cT DAB  1 − y A 2 
C 2 = cT DAB ln (1 − y A1 ) − ln  z1
z 2 − z1  1 − y A1 

Substituting c D ln (1 − y ) = C z + C
T AB A 1 2

Constants cT DAB  1 − y A2   1 − y A2 
cT DAB ln (1 − y A ) =  z + cT DAB ln (1 − y A1 ) − T AB ln
c D
ln  z1
z 2 − z1  1 − y A1  z 2 − z1  1 − y A1 
 z − z1 
 
 1 − y A   z − z1   1 − y A 2   1 − y A2   z 2 − z1 
ln  =   ln  = ln 
 1 − y A1   z2 − z1   1 − y A1   1 − y A1 
 z − z1   z − z1 
   
1 − y A  1 − y A2  −  1 − y A2  −
 2 1
y A = 1 − (1 − y A1 )
 2 1
z z z z
=   
1 − y A1  1 − y A1   1 − y A1 
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Example 2: Equimolar Counter Diffusion (EMCD)

• Assumptions: NB
z2

1. Steady state (constant flux)

z1
2. Uniform Cross sectional area
NA
3. 1D flux (along z)
4. Constant T and PT  constant cT
5. No gas phase chemical reaction  RA = 0
6. Binary mixture of A and B
7. DAB is constant

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Solution (Continued)

• Differential equation of mass transfer:

–▽NA + RA = ∂cA/∂t

∂N Ax ∂N Ay ∂N Az
∇N A = + + =0
∂x ∂y ∂z

Similarly, for component B: dNBz/dz = 0

Since EMCD  NB = - NA

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Solution (Continued)

Flux Equation

∂y A
N Az = −cT DAB + y A (N Az + N Bz )
∂z

∂y A
N Az = −cT DAB
∂z

Boundary Conditions:
1: yA= yA1 @ z=z1 2: yA= yA2 @ z = z2

N Az ∫
z = z2
∂z = −cT DAB ∫
yA2
∂y A
N Az =
cT DAB
[ y A1 − y A2 ]
z = z1 y A1 z 2 − z1

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Solution (Continued) ∂y A ∂N Az
N Az = −cT DAB ∇N A = =0
∂z ∂z

• Concentration Profiles:
BC1:
∂N Az ∂  ∂y A  y A1 = C1 z1 + C 2
=  − cT DAB =0 BC2:
∂z ∂z  ∂z 
y A 2 = C1 z 2 + C 2
∂y A
Integration  = C1 Solving for C2 from both
∂z equations:
Separation of var.s 
C 2 = y A1 − C1 z1
∂y A = C1∂z
= y A 2 − C1 z 2
Integration 
0 = ( y A 2 − y A1 ) − C1 ( z 2 − z1 )
y A = C1 z + C 2

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 y A 2 − y A1
C1 =
z 2 − z1
y A 2 − y A1
C 2 = y A1 − z1
z 2 − z1
y A = C1 z + C 2
Substituting Constants
y A 2 − y A1 y A 2 − y A1
yA = z + y A1 − z1
z 2 − z1 z 2 − z1
y A 2 − y A1
⇒ y A − y A1 = (z − z1 )
z 2 − z1
y A − y A1 y A 2 − y A1
=
z − z1 z 2 − z1
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Excel Spreadsheet

$c$2 = 0.9 z1 = 0
$c$3 = 0 z2 = 1

EMCD UMD
(z-z1)/(z2-z1) z yA -yA1)/(yA2-y yB yA yA1)/(yA2-y yB 1
0 0 0.9 0 0.1 0.9 0 0.1 0.9 EMCD
0.1 0.1 0.81 0.1 0.19 0.874107 0.028769 0.125893

(yA-yA1)/(yA2-yA1)
0.8
0.2 0.2 0.72 0.2 0.28 0.841511 0.064988 0.158489 UMD
0.7
0.3 0.3 0.63 0.3 0.37 0.800474 0.110585 0.199526 0.6
0.4 0.4 0.54 0.4 0.46 0.748811 0.167987 0.251189
0.5
0.5 0.5 0.45 0.5 0.55 0.683772 0.240253 0.316228
0.4
0.6 0.6 0.36 0.6 0.64 0.601893 0.33123 0.398107
0.3
0.7 0.7 0.27 0.7 0.73 0.498813 0.445764 0.501187
0.2
0.8 0.8 0.18 0.8 0.82 0.369043 0.589953 0.630957
0.1
0.9 0.9 0.09 0.9 0.91 0.205672 0.771476 0.794328
1 1 0 1 1 0 1 1 0
0 0.5 1
(z-z1)/(z2-z1)

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Film Concept for Molecular Mass Transfer

cA (and yA) =
constant in bulk gas
Flow of gas B
Flow of gas B
z = δ, yAδ
NA
Liquid A δ Slowly moving
gas film z = 0, yA0
Liquid A

Assume that concentration gradient

is contained in the gas film  δ is the
resistance to molecular diffusion

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Generalization of Mass Transfer Forms

EMCD UMD
cT D AB
N Az [ y A 0 − y Aδ ]
=N Az
D AB
cT [ y A 0 − y A δ ]
δ δ .y B ,lm

N Az k c0cT [ y A 0 − y A δ ]
= N Az k c cT [ y A 0 − y A δ ]
=

kc0 and kc = film mass transfer coefficients for EMCD and

UMD, respectively 0
kc = kc . y B ,lm

• If yA is very small  yB ~ 1  yB,lm ~ 1

• At low concentrations of A, UMD ~ EMCD

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