Planar (1-D) steady-state diffusion with homogeneous 1st order reaction

Lecture [ 13 ]

A reaction occurs throughout a volume of fluid, not just at a surface.

Example: absorption of SO2 (gas A) into a solution of NaOH (constituent B), where the
reaction occurs, resulting in equi-molar counter-diffusion of A and B in the liquid
phase:
A+BC
RA = -k. cA
gas, pure A

(13.1)

CASE
1

CASE
2
cA

z=0

CASE
3
cA

R = rate of formation of A
(mol/m3s)
k = rate constant (1/s)

cA

z
liquid
soln. of B

z=
z=L

N A (zL) 0
Physical
situations and
associated
boundary
conditions

c A
z

c A z L 0

c A z 0

deep
vessel

reaction is fast
enough to
consume A
before it can
diffuse to the
base of the
vessel

( z L)

No A can
escape from
the base of
vessel at z=L

Planar (1-D) steady-state diffusion with homogeneous 1st order reaction

CASE 1

A cannot escape through base of vessel at z=L

Gas
A

z=0
z

Lecture [ 13 ]

liquid B
cA0
cA

NA (z)
z

cA0 is the concentration of

A in the liquid phase at the
surface. In practice it is not
easy to measure.

NA (z+z)
c A
0
z

z=L
mass balance on differential volume element:
IN

+ CREATED - OUT = 0

N A ( z ) R Az N A ( z z ) 0
in the limit as z0:

N A
RA 0
z
recalling Ficks 1st law:

NA NA NB

N A
k cA 0
z
cA
c A
D AB
c
z

(13.2)

(3.4)

and with the reaction inducing equi-molar counter-diffusion (i.e. NA = -NB):

N A D AB

c A
z
2

Planar (1-D) steady-state diffusion with homogeneous 1st order

reaction

Lecture [ 13 ]

Substituting this identity into equation 16.2:

c A

D
k.c A 0
AB

Assume DAB is constant with varying z:

D AB

1 x

e ex
2
1
cosh( x ) e x e x
2
sinh( x )

2c A
k.c A 0
z 2

This 2nd order differential equation has a known general solution:

c A A cosh

k
z B sinh
D AB

k
z
D AB

(13.3)

Values for A and B can be derived by using the boundary conditions:

at z=0, cA=cA0

c A 0 A cosh 0 B sinh 0

A cA0

at z=L, cA/z=0

c A

z
0

k
A sinh
D AB

k
z
D AB

k
c A 0 sinh
D AB

B c A 0

k
L
D AB

k
B cosh
D AB

k
B cosh
D AB

k
z
D AB

k
L
D AB

k
L
D AB

sinh

cosh

k
L
D AB

Planar (1-D) steady-state diffusion with homogeneous 1st order

reaction

Lecture [ 13 ]

and putting these values for A and B back into equation 13.3:

k
z
D AB

c A c A 0 cosh

cosh

cA cA0

k
L cosh
D AB

cosh

k
z sinh
D AB

cosh

cosh

cA cA0

k
L
D AB

sinh

L
D AB

c A 0 sinh

kL2
D AB

kL
D AB

cosh

k
L
D AB

k
L sinh
D AB

k
z
D AB

k
z
D AB

(13.4)

Dimensionless numbers are often used in the literature, in order to simplify these
expressions:

cA

cA
cA0

z
z modulus

Thiele
L

kL2
D AB

Equation 13.4, the concentration profile, simplifies to :

cosh 1 z

cosh

(13.5)

Planar (1-D) steady-state diffusion with homogeneous 1st order

reaction

kL2
D AB

cosh

CASE 1

cA cA0

0.1

0.2

0.3

(13.4)

cA

cA
cA0

0.4

0.5

Diffusion
controlled
0.0
0

kL
D AB

100

1
2

cosh

Gas
A

Lecture [ 13 ]

0.6

0.7

0.8

0.9

1.0

0.1
0.2
0.3

liquid
B

z
z
L

30
10

0.4
0.5

0.6
0.7
0.8
0.9

z=L

1
0.3

kL2
D AB

0.1
reaction
controlled

Planar (1-D) steady-state diffusion with homogeneous 1st order reaction

CASE 2

Deep vessel, so that as zL (~) cA0

Gas
A

z=0
z

Lecture [ 14 ]

liquid B
cA0
cA

NA (z)
z
NA (z+z)

z=L
mass balance on differential volume element:
IN

+ CREATED - OUT = 0

N A ( z ) R Az N A ( z z ) 0
in the limit as z0:

N A
RA 0
z
recalling Ficks 1st law:

NA NA NB

N A
k cA 0
z

(14.1)

cA
c A
D AB
c
z

(3.4)
and with the reaction inducing equi-molar counter-diffusion (i.e. NA = -NB):

N A D AB

c A
z
6

Planar (1-D) steady-state diffusion with homogeneous 1st order

reaction

Lecture [ 14 ]

c A

D
AB

k.c A 0

Assume DAB is constant with varying z:

D AB

2c A
k.c A 0
z 2

This 2nd order differential equation has a convenient general solution:

k
z B exp
D AB

c A A exp

k
z
D AB

(14.2)

Values for A and B can be derived by using the boundary conditions in equation 14.2:
at z=0, cA=cA0

cA0 A B

at z=, cA=0

A0

Using these values for A and B in equation 13.2, the concentration profile is:

cA

c A 0 . exp

kL2 z
.
D AB L

(14.3)

Planar (1-D) steady-state diffusion with homogeneous 1st order

reaction
cA

CASE 2

c A 0 . exp

Diffusion
100 controlled

Gas
A

0.0
0

0.1

kL2 z
.
D AB L

cA

cA
cA0

0.4

0.5

0.2

0.3

Lecture [ 14 ]

(14.3)

0.6

0.7

0.8

0.9

1.0

0.1
0.2
0.3

liquid
B

z
z
L

30
10

0.4
0.5
0.6

0.7

kL2
D AB

0.8
0.9

z=L

For this case, by definition, any profiles that

result in CA >0 at z=L are meaningless

Planar (1-D) steady-state diffusion with homogeneous 1st order reaction

CASE 3

reaction is fast enough to consume A before it can diffuse to z=L

Gas
A

z=0
z

Lecture [ 14 ]

liquid B
cA0
cA

NA (z)
z
NA (z+z)

z=

z=L
mass balance on differential volume element:
IN

+ CREATED - OUT = 0

N A ( z ) R Az N A ( z z ) 0
in the limit as z0:

N A
RA 0
z
recalling Ficks 1st law:

NA NA NB

N A
k cA 0
z

(14.4)

cA
c A
D AB
c
z

(3.4)
and with the reaction inducing equi-molal counter-diffusion (i.e. NA = -NB):

N A D AB

c A
z
9

Planar (1-D) steady-state diffusion with homogeneous 1st order

reaction
2c A

c A
D AB
k.c A 0
D AB
k.c A 0
2

z
z
z

Lecture [ 14 ]

This 2nd order differential equation has a known general solution:

k
z B sinh
D AB

c A A cosh

k
z
D AB

(14.5)

Values for A and B can be derived by using the boundary conditions in equation 14.5:

c A 0 A cosh 0 B sinh 0

at z=0, cA=cA0

0 cA0

at z=, cA=0

kL2
B sinh

D AB L

cosh

cosh

B c A 0

sinh

A cA0
kL2
D AB L

kL2
D AB L
cA0

kL2
kL2

tanh

D AB L
D AB L

and putting these values for A and B back into equation 14.5

c A c A0

cosh

kL
D AB

z
c A0

sinh

2
L

kL
tanh

DAB L

kL2 z
DAB L

(14.6)

10

Planar (1-D) steady-state diffusion with homogeneous 1st order

reaction

Lecture [ 14 ]

CASE 3 (for case /L = 0.8)

c A c A0

kL
D AB

cosh

Gas
A

z
c A0

sinh

2
L

kL
tanh

DAB L

100

0.0
0

0.1

cA

cA
cA0

0.4

0.5

Diffusion
controlled
0.2

0.3

0.6

0.7

kL2 z
DAB L

0.8

0.9

(14.6)

1.0

0.1
0.2
0.3

liquid
B

z
z
L

0.4
0.5
0.6
0.7

30
10
3
reaction
controlled

1
0.3
0.1

kL2
D AB

0.8
0.9

z=L

11

Planar (1-D) steady-state diffusion with homogeneous 1st order reaction

Lecture [ 14 ]

It is useful to compare the rate of absorption with reaction to that which would occur
without reaction.

c A

c A0

k
sinh

D AB

z 0

c A

N A ( z 0 ) D AB

kL2 0
c A0

D AB L

kL2

tanh D L
AB

kL2
cosh
D AB

tanh

k 0
DAB L

k
D AB

D ABc A 0
z 0

D AB

(14.7)

If there is no reaction then the flux is given by a simple linear concentration profile:

N A ( z 0 ) D AB

c A

z 0

so between z = 0 (cA=cA0) and z= (cA=0), this equation becomes:

N A ( z 0 ) D AB

c A0 0
0

D AB

c A0

(14.8)

and comparing equations 14.8 and 14.7 gives:

diffusion rate with reaction

diffusion rate without reaction

D AB

tanh

D AB

Ha

(14.9)

12

Unsteady-state diffusion

Lecture [ 15 ]

Recall that in order to develop a general expression for the concentration profiles, we
considered a differential element a small distance from the liquid interface:
laminar gas film
B

yA(0)

yB

bulk
liquid
(mixed)

bulk
gas
(mixed)

yA
yA(

z (z+dz)

0
mass balance for the differential volume between z and (z+dz): (OUT IN = 0) :

N A
0
z

(15.1)
substituting for NA assuming no net bulk flow

y A

D
.
c
.
0
AB

or......... D AB

2c A
c A
DAB
2
z z
z

(15.2)

Now, for an unsteady-state problem the mass balance becomes ACC = OUT - IN

2c A
c A
D AB
2
t
z

(15.3)

Or or3-dimensional form

2c A 2c A 2c A
c A

D AB

2
t
y 2
z 2
x

(15.4)

Transient (unsteady-state) diffusion

Lecture [ 15 ]

Transient 1-D diffusion into a semi-infinite medium through one surface

Practical examples are:

well-mixed
bulk liquid

solid

Doping of atoms into solids

to make semiconductors
http://en.wikipedia.org/wiki/
Doping_(semiconductor)

Case-hardening of steel
http://en.wikipedia.org/wiki/
Case_hardening

Absorption of O2 into the

ocean

NA
CA(s)

Elapsed
time
cA = f (z,t)

cA(0)

z=0

z=

Boundary conditions for a typical analysis could be as follows:

t<0

c A(z,t=0) = c A(0)

for all z

z=0 c

A(z=0,t)

= c A(S)

for t > 0

z= c

A(z=,t)

= c A(0)

for t > 0

Ficks 2nd law can be applied to this system:

14

Transient (unsteady-state) diffusion

2c A 2c A 2c A
c A

D AB

2
2
2
t

m2
mol

3
m s
s

mol m 3

m2

Lecture [ 15 ]

(15.4)

considering just one dimension (for simplification of presentation):

2c A
c A
D AB
2
t
z

(15.5)

the solution to equation 15.5 with these boundary conditions is:

c A ( z , t ) c A ( z ,t 0 )
c A ( z 0 ,t ) c A ( z ,t 0 )

2 D ABt

1 erf

(15.6)

the mass flux of A into the solid (as a function of time) is found using Ficks 1 st law at
location z=0, simplified for dilute solutions or uni-molecular diffusion:

N A ( z 0 ,t )

c A
DAB

(15.7)

1
erf ( x )
exp 2 d

z 0

dcA/dz can be derived by differentiating (15.6). First re-arrange :

c A( z ,t ) c A ( z ,t 0 ) c A( z 0,t ) c A ( z ,t 0 ) 1 erf

2 D ABt

15

Transient (unsteady-state) diffusion

c A( z ,t ) c A( z ,t 0 ) c A( z 0,t ) c A( z ,t 0) 1 erf

2 DABt

Lecture [ 15 ]

erf ( x ) 2 e x
x

differentiating :

c A( z ,t )
z

0 c A ( z 0 ,t ) c A ( z ,t 0 )

simplifying for z=0 :

c A( z 0 ,t )
z

c A( z 0,t )
z

c A ( z 0 ,t ) c A ( z , t 0 )

c A ( z 0 , t ) c A ( z ,t 0 )

z2
2
1

exp

4
D
t
2 DABt
AB

02
2
1

exp
4
D
t
2 DABt

AB

exp 0 1

1
DABt

substituting in (22.3):

c A

N A( z 0,t ) DAB

z 0

D AB
c A ( z 0 , t ) c A ( z ,t 0 )
t

D AB
c A( S ) c A( 0 )
t

The cumulative mass flux of A into the solid (as a function of time) is found by
integrating this expression over time:
t

WA ( t ) N A ( z 0 ) t 2
0

D AB t
c A (S) c A ( 0 )

16

Transient (unsteady-state) diffusion

Lecture [ 15 ]

Transient 1-D diffusion into a flat plate from both surfaces

Fluid CAs

z
2a

x
2b

2c

This special case is representative of many industrial applications. Consider a

parallel rectangular block as shown above, immersed in a fast-flowing fluid. Equation
21.11 must again be solved, but with different boundary conditions:

2c A 2c A 2c A
c A
D AB

2
2
t

y
z 2

m2
mol

3
m s
s

mol m 3

m2

(15.4)

For one dimension, the solution is obtained using Laplace transforms:

c A ( z ,t ) c A (0)
c A (s ) c A ( 0)

2n 1
4 1
1
exp

n 0 2n 1
2

and if c A(0) = 0 (a common industrial situation):

c A ( z,t )
c A (s)

2n 1
4 1
1
exp

n 0 2n 1
2

D AB t
z

cos
2
n

a 2
2a

D AB t
z

cos
2
n

a 2
2a

17

Transient (unsteady-state) diffusion

c A ( z,t )
c A (s )

Lecture [ 15]

2n 1
4 1
1
exp

n 0 2n 1
2

D AB t
z

cos
2
n

a 2
2a

DAB = 0.00001 m2/s

a = 0.1 m
1.0
0.9
0.8
0.7

CA(z,t)
CA(S)

600
s

0.6
0.5

200 s

0.4

60 s

20 s

0.6

0.7

0.3
0.2
0.1
0.0
0.0

0.1

0.2

0.3

0.4

0.5

z/a

0.8

0.9

1.0

18

Transient (unsteady-state) diffusion

Lecture [ 15 ]

z
z=a
cA

-z

cA(t=0)

cAs

The flux at one of the surfaces is obtained by differentiating this equation, and using Ficks
1st law for uni-molecular diffusion:

c A
N A ( z a ) t D AB

z a

2D ABc A (S)
a

D ABt 2
exp 2m 1

4a 2
m 0

The total number of moles transferred as a function of time (per unit interfacial area) is:

W A(t )

8c A( S ) a
2

2
n 0 2 n 1

DABt 2
2

exp

2
n

4
a

Many other special cases and useful geometries have been analysed in the literature.
Analytical solutions are available from standard texts such as:
Crank, J. Mathematics of Diffusion.

19