Special cases for molecular diffusion (spherical geometry, equi-molar

counter-diffusion)

Lecture [ 5 ]

Again, consider constituent A and constituent B but now from a spherical droplet rather
than a planar surface :
droplet
radius = R1

radius = r
NA

NB
system
boundary
radius = R2
Mass balance in the volume between R1 and r: (OUT IN = 0) :

A(r)

4r 2 N A ( R1 ) 4R 1

R 12 N A ( R1 ) r 2 N A ( r )

(5.1)

Recalling Ficks 1st law (equation 3.4), expressed using mole fractions:

N A N A N B y A D AB c
m2
mol
mol

2
2
m s
m .s
s

and when

NB = - NA

y A
z

mol m 3

(5.2)

this simplifies to:

N A ( r ) D AB c

y A
r

(5.3)

Special cases for molecular diffusion (spherical geometry, equi-molar

counter-diffusion)

Lecture [ 5 ]

Combining equations 5.1 and 5.3 to eliminate N A(r) and integrating between R1 and R2:

R N A ( R1 )
2
1

R2

1
R 12 N A ( R1 )
r

R2

R1

A2
r
R N A ( R1 ) 2 D AB c y A
r
R1
y A1

y
r D AB c A
r

2
1

D AB c y A y AA12
y

1
1
N A ( R1 ) R 12
D AB c y A 2 y A1
R 2 R1
R1 R2
DAB c y A 2 y A1
R
R
1 2

N A( R1 ) R12

N A( R1 )

R2
c DAB y A 2 y A1
R2 R1 R1

If the system volume is large, R2

N A( R1 )

c DAB
y A 2 y A1
R1

(5.4)

, equation 5.4 reduces to:

(5.5)

2
mol
1 mol m

2
3

s
m .s
m m

Special cases for molecular diffusion (spherical geometry, equi-molar

counter-diffusion)

Lecture [ 5 ]

To develop an expression for the concentration profiles, consider a differential element (or
shell) some distance from the droplet:
droplet radius = R1

differential element
inside radius = r
outside radius = r+dr

NA

NB

system
boundary
radius = R2

mass balance for the differential volume : (OUT IN = 0) :

4r 2 N A ( r )
r

r 2 N A(r)
r

(5.6)

eliminating NA(r) using equation 5.3:

y A
2
r

c
.
D

0
AB

integrating:

y A
2
r

c
.
D

A 0
AB

Special cases for molecular diffusion (spherical geometry, equi-molar

counter-diffusion)

Lecture [ 5 ]

Integrating again:

A
c.D AB

r
r 2 dy A

A
1
. yA B
c.D AB r

(5.7)

Equation 5.7 can be used with the boundary conditions to create 2 simultaneous
equations for the constants A and B:

A
1

y A1 B
c D AB R 1
A
1

yA2 B
c D AB R 2
subtracting one of these equations from the other gives an expression for A:

R 1R 2
c D AB y A1 y A 2
R 2 R1

and using this expression for A with the first of the simultaneous equations to gives an
expression for B:

R2
( y y ) y A1
R 2 R 1 A1 A 2
4

Special cases for molecular diffusion (spherical geometry, equi-molar

counter-diffusion)

Lecture [5]

finally, back-substitute these expressions for A and B in equation 5.7:

R 1R 2
1
R2
. ( y A 2 y A1 ) y A
( y A 2 y A1 ) y A1
(R 2 R 1 ) r
(R 2 R 1 )
y A y A1

R 1R 2 1
1

.( y A1 y A 2 )
(R 2 R 1 ) R 1 r

(5.8)

yA
R1

NA

yA1

NB
R2

yA2
0

r
0

R1

R2

Special cases for molecular diffusion (spherical geometry, equi-molar

counter-diffusion)

y A y A1

Lecture [ 5 ]

R 1R 2 1
1
.( y A1 y A 2 )

(R 2 R 1 ) R 1 r

1.0
0.9
0.8
0.7
0.6

yA

0.5
0.4
0.3
0.2
0.1
0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

z/d=(r-R1)/(R2-R1)

Special cases for molecular diffusion (spherical geometry, equi-molar

counter-diffusion)

Lecture [ 5 ]

How to deal with a shrinking spherical particle:

m
N A ( R1 ) A( R1 )
t
R2
N A( R1 )
c DAB y A 2 y A1 (5.4)
R2 R1 R1
4
4
( R13 ) ( R13 )
m ( V )
4
R1
3
3

3R12
t
t
t
t
3
t
Combining:

4 R12

R1
4R12
t

1
R
1 1
R2

c D AB y A 2 y A1

R1

For complete disappearance of particle, integrate from R 1,0 to R1=0

0

R1

R2
R1, 0

R12, 0
2

R1R1

R13, 0

c D AB

y A 2 y A1 t

c D AB y A 2 y A1 t

3R2

(5.5)

Special cases for molecular diffusion (spherical geometry, A through

stagnant B)
Again, consider evaporation of constituent A through non-diffusing constituent B but
now from a spherical droplet rather than a planar surface :
droplet
radius = R1
(constant)

system
boundary
radius = R2

Lecture [ 6 ]

The continuity equation has a

different form in spherical and
cylindrical coordinates, and the
flux DOES NOT stay constant in
due to the changing surface
area of the differential volume.

some general
radius = r

Mass balance in the volume between R1 and r: (OUT IN = 0) :

A(r)

4r 2 N A ( R1 ) 4R 1

R 12 N A ( R1 ) r 2 N A ( r )

(6.1)

Recalling Ficks 1st law (equation 3.4), expressed using vapour phase mole fractions:

N A N A N B y A D AB c
m2
mol
mol

2
2
m s
m .s
s

y A
z

mol m 3

(6.2)

and when NB=0 (i.e. B is non-diffusing) this simplifies to:

N A(r )

D AB c y A

(1 y A ( r ) ) r

(6.3)

Special cases for molecular diffusion (spherical geometry, A through

stagnant B)

Lecture [ 6 ]

Combining equations 6.1 and 6.3 to eliminate N A(r) and integrating between R1 and R2:

R N A ( R1 )
2
1

1
R N A ( R1 )
r
2
1

D AB c y A
r
(1 y A ( r ) ) r
2

R2

R1

R2

A2
r
y A
R N A ( R1 ) 2 D AB c
r
(1 y A ( r ) )
R1
y A1

2
1

D AB c ln 1 y A y AA12
y

1
1
N A ( R1 ) R 12
D AB c ln 1 y A 2 ln 1 y A1
R 2 R1
1 yA2
R2
N A ( R1 )
c D AB ln
(6.4)
R 2 R1 R1
1

y
A
1

If the system volume is large and stagnant, R2

N A( R1 )

1 y A2
1
c DAB ln

R1
1

y
A1

, equation 6.4 reduces to:

(6.5)

2
mol
1 mol m

2
3

s
m .s
m m

Special cases for molecular diffusion (spherical geometry, A through

stagnant B)

Lecture [ 6 ]

To develop an expression for the concentration profile, consider a differential element (or
shell) some distance from the droplet:
droplet
radius = R1

differential element
inside radius = r
outside radius = r+dr

system
boundary
radius = R2
mass balance for the differential volume : (OUT IN = 0) :

4r 2 N A ( r )
r

r 2 N A(r)
r

(6.6)

eliminating NA(r) using equation 6.3:

2
r

c.D AB y A

0
1 y A r

integrating:

2
r

c.D AB y A

A0
1 y A r

10

Special cases for molecular diffusion (spherical geometry, A through

stagnant B)

Lecture [ 6 ]

Integrating again:

A
c.D AB

r
r2

dy A
1 y A

A
1
. ln 1 y A B
c.D AB r

(6.7)

Equation 5.7 can be used with the boundary conditions to create 2 simultaneous
equations for the constant A and B: :

A
1

ln 1 y A1 B
c D AB R 1
A
1

ln 1 y A 2 B
c D AB R 2
subtracting one of these equations from the other gives an expression for A:

1 y A2
R1 R2
c D AB ln

R2 R1
1 y A1

and using this expression for A with the first of the simultaneous equations to gives an
expression for B:

1 yA2
R2
ln
ln 1 y A1
R 2 R 1 1 y A1
11

Special cases for molecular diffusion (spherical geometry, A through

stagnant B)

Lecture [ 6 ]

finally, back-substitute these expressions for A and B in equation 6.7:

1 yA2 1
1 yA2
R 1R 2
R2
. ln
. ln
ln 1 y A1
. ln 1 y A
R 2 R 1 1 y A1 r
R 2 R 1 1 y A1

1 yA

A1

ln

y A( r )

1 1

R1 r
1
1

R1 R 2

1 yA2

1 y A1

ln

1 y A2

1 1 y A1

1 y A1

1 1

R1 r
1
1

R1 R2

(6.8)

yA
R1

R2

yA1

yA2
0

r
0

R1

R2

12

Special cases for molecular diffusion (spherical geometry, A through

stagnant B)

1 yA2
y A f ( r ) 1 1 y A1

1 y A1

1 1

R1 r
1
1

R1 R 2

Lecture [ 6 ]

1.0
0.9
0.8
0.7
0.6

yA

0.5
0.4
0.3
0.2
0.1
0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

z/d=(r-R1)/(R2-R1)
13

Special cases for molecular diffusion (1-D geometry counter-diffusion, NB =

-NA)

Lecture [ 6 ]

At steady state, NB = -NA = constant

The general expression for total molar flux (equation 3.4) becomes:

c A
cA
D AB
z
c

N A N A N A

mol

2
m s

mol

2
m s

mol m 3
m2

3
s
mol m

(6.9)

mol m 3

m

or alternatively expressed as gaseous mole fractions:

y A
N A N A N A y A
D
AB
c (6.10)
z

mol

m2 s

mol

m2 s

m2
s

mol m 3
m

Integrating equation 6.1:

yA ( )
y
N A z D AB c A (6.11)
0
y A ( 0 ) 1 y 1
A

NA

1 1 y

D AB c
ln A ( ) (6.12)
1 z 1 1 y A ( 0)

m 2 s mol m 3
mol

2
m
m s

DEPARTMENT OF CHEMICAL ENGINEERING

CHE3063F

MASS TRANSFER

Version

4/3/16 08:42:18 AM

14

Special cases for molecular diffusion (1-D geometry counter-diffusion,

general case)
z

1 1 y A ( )
1
yA
1 1 1 y A ( 0 )
(6.13)
1

y
A ( 0 )

=0

NB = 0

=1

NB = - NA

= 0.5

=5

Lecture [ 6 ]

NB = -0.5 NA

NB = - 5 NA

Similar analysis for spherical

geometries:.

y A( r )

DEPARTMENT OF CHEMICAL ENGINEERING

CHE3063F

MASS TRANSFER

Version

1 1 y A2
1
1 1 1 y A1

1
1 1 y A1

4/3/16 08:42:18 AM

1 1
R r
1
11
R R
1 2

15

Measurement of molecular diffusivities the Arnold/Stefan diffusion cell

flow of inert
gas B

Assumptions:

yA(z=0)
z

NB

NA

glass
tube

yA(z=L)

liquid level
(changes with time)
L=f(t)

reservoir of
liquid A

We can model the system as diffusion

of A through non-diffusing B.
This is OK as long as:
a) the inert gas B has negligible
solubility in the liquid A
b) The liquid level changes very slowly
(pseudo-steady-state assumption no accumulation)
) yA(z=0) = 0
This is OK if there is a flow of B across
the tube opening

) yA(z=L) = yA(sat)
This is an assumption of
thermodynamic equilibrium at the liquid
surface. Evaporation of the liquid
requires heat, so the apparatus may be
immersed in a temperature bath to
a) ensure isothermal conditions
b) Allow an accurate measurement of
the cell temperature

Lecture [ T1 ]

Joseph Stefan
(1835 1893)
was a Slovenian
physicist,
mathematician
and poet who
lived in Austria.
He made the first sensible
estimate of the temperature of the
sun's surface at 5430C, as well
as measurements of the thermal
conductivity of gases. He is best
known for stating that the total
radiation from a black body is
proportional to the fourth power of
its thermodynamic temperature.

Recalling the appropriate expression of Ficks 1 st law for NA (equation 4.2), we can create
a time-dependent version :

NA t

1 y A ( z L )
P.D AB
. ln

R.T.L( t )
1 y A ( z 0 )

(T1.1)

16

Measurement of molecular diffusivities the Arnold/Stefan diffusion cell

Lecture [ T1 ]

Rate of liquid A evaporation = rate at which vapour A leaves by diffusion

d 2
d 2
L(t )
NA
4
4

mol
1
3
2
m 2 m
m s
s

S.I. units clearly dont match, so must add terms to correct:

d 2
A
d 2
NA
L(t )

4 M A 1000
4

1
3
m
s

MA = molecular weight of A
A = liquid density of A

kg / m 3
mol
2
2 m
g / mol / g / kg m s

Now substitute for NA using Ficks 1st law, with yA(z=0) = 0:

P D AB ln 1 y A( z L ) d 2
d 2
A

L (t )

4
M
1000
R T L(t )
4

L(t )

P DAB ln 1 y A( z L )
A

t
M A 1000
R T L (t )
L
M A P D AB ln 1 y A( z L ) t
t
L L(t )L

1000

T
A
0
0

2
(t)

L2( t 0 )
2

D AB

P D AB ln 1 y A ( sat ) t

1000 A R T
500 A R T L2( t ) L2( t 0 )

M A P ln 1 y A ( sat ) t

(T1.2)

17

Correlations and typical values for molecular diffusivity

Lecture [ T1 ]

Gases

Wilke, C.R. and Lee, C.Y.:

Ind. Eng. Chem. ,47, 1253
(1953)
Hirschfelder, J.O., Bird, R.B.,
Spotz, E.L.:
Trans. ASME, 71, 921 (1949);
Chem. Rev., 44, 205 (1949)

Theoretical predictions, based on the kinetic theory of gases, suggest:

D AB

1
P

D AB T1.5

The Wilke-Lee / Hirschfelder-Bird-Spotz method for estimation of gas diffusivities of a) two

non-polar species b) one polar and one non-polar species at low densities (<10 atm) is as
follows:

rAB

A/k
[K]

H2

0.283

59.7

O2

0.347

106.7

N2

0.380

71.4

Air

0.371

78.6

CO

0.369

91.7

CO2

0.394

195.2

SO2

0.411

335.4

Typical values for DAB:

T 1 .5

1
1

M B
MA

AB

~ 10-5 m2/s

Note that this correlation is not

dimensionless!

P rAB f

1
rA rB
2

rA
[nm]

(T1.3)

A B
k k

f(kT/AB
)

with:

1
1

MA
MB

f(kT/AB
)

D AB

0.0001 1.084 0.249

kT/AB

accurate to 5%

DAB binary molecular diffusivity

[m2/s],
T
temperature [K]
P
atm. pressure [N/m2]
MA molecular mass [g/mol]
rAB collision separation [nm]
rA
molecular radius [nm]
f
collision integral, a
function of (kT/AB)
kB Boltzmann constant
/k force constant [K]
for molecular attraction
(from viscosity data)
For more values of rA , /k
refer to examination data sheet or:
Treybal, R.E. Mass Transfer
Operations, p 33.

18

Correlations and typical values for molecular diffusivity

Another commonly-used correlation for estimation of gas diffusivities is the Fuller
equation as follows:

10 3 T
D AB

1.75

1
1

M
M
A
B

P vA

13

vB

12

13 2

Lecture [ T1 ]
Note that this correlation is
not dimensionless!
DAB in [cm2/s],
T in [K]
P in [atm]

(T1.4)

Diffusion volumes (vi) for simple molecules, for use in the above equation further data is
available in Perry:

H2 7.07

Ar 16.1

D2 6.7
He 2.88
N2 17.9
O2 16.6
Air 20.1

Kr 22.8
CO 18.9
CO2 26.9
N2O 35.9
NH3 14.9

H2O 12.7
CClF
114.8
2
SF6 69.7
Cl2 37.7
Br2 67.2
SO2 41.1

(T1.5)

19