Chapter 2

Unsteady State Molecular Diffusion

2.1 Differential Mass Balance
When the internal concentration gradient is not negligible or Bi << 1, the microscopic or
differential mass balance will yield a partial differential equation that describes the concentration
as a function of time and position. For a binary system with no chemical reaction, the unsteady
state molecular diffusion is given by

cA
= (DABcA)
t

(2.1-1)

For one-dimensional mass transfer in a slab with constant DAB and convective conditions of hm
and cA,, equation (2.1-1) is simplified to

2c A
cA
= DAB
x 2
t

(2.1-2)

hm, cA,inf

-L

hm, cA,inf

x=0

Figure 2.1-1 One-dimensional unsteady mass transfer in a slab.

Equation (2.1-2) can be solved with the following initial and boundary conditions
I. C.

t = 0, cA(x, 0) = cAi

B. C.

x = 0,

c A
x

= 0;

x = L, DAB

x =0

c A
x

= hm(cAf cA,)
x =L

In general, the concentration within the slab depends on many parameters besides time t and
position x.
cA = cA(x, t, cA,i, cA,, L, DAB, hm)

2-1

The differential equation and its boundary conditions are usually changed to the dimensionless
forms to simplify the solutions. We define the following dimensionless variables
Dimensionless concentration: * =

Dimensionless distance: x* =

c A K ' c A,
cA =KcA, + *(cA,i KcA,)
c A, i K ' c A,

x
x = L x*
L

Dimensionless time or Fourier number: t* = Fo =

DAB t
L2

t
=
Fo
L2
DAB

K is the equilibrium distribution coefficient. Substituting T, x, and t in terms of the

dimensionless quantities into equation (2.1-2) yields
(cA,i cA,)

1 2 *
1 DAB *
=
(c

c
)
A,i
A,
L2 x *2
D AB L2 Fo

*
2 *
=
Fo x *2

(2.1-3)

Similarly, the initial and boundary conditions can be transformed into dimensionless forms

*(x*, 0) = 1
*
x *
Therefore

= 0;
x* =0

*
x *

= Bim**(1, t*), where Bim =

x* =1

hm L
K ' DAB

* = f(x*, Fo, Bim)

The dimensionless concentration depends * only on x*, Fo, and Bim. The mass transfer Biot
number, Bim, denotes ratio of the internal resistance to mass transfer by diffusion to the external
resistance to mass transfer by convection. Equation (2.1-3) can be solved by the method of
separation of variables to obtain

* =

C
n =1

exp( n2 Fo) cos(nx*)

where the coefficients Cn are given by

Cn =

4 sin n
2 n + sin(2 n )

and n are the roots of the equation: n tan(n) = Bim.

2-2

(2.1-4)

Table 2.1-1 lists the Matlab program that evaluates the first ten roots of equation n tan(n) = Bim
and the dimensionless concentrations given in equation (2.1-4). The program use Newtons
method to find the roots (see Review).

Table 2.1-1 Matlab program to evaluate and plot * =

C
n =1

exp( n2 Fo) cos(nx*)

% Plot the dimensionless concentration within a slab

%
% The guess for the first root of equation z*tan(z)=Bi depends on the Biot number
%
Biot=[0 .01 .1 .2 .5 1 2 5 10 inf]';
alfa=[0 .0998 .3111 .4328 .6533 .8603 1.0769 1.3138 1.4289 1.5707];
zeta=zeros(1,10);cn=zeta;
Bi=1;
fprintf('Bi = %g, New ',Bi)
Bin=input('Bi = ');
if length(Bin)>0;Bi=Bin;end
% Obtain the guess for the first root
if Bi>10
z=alfa(10);
else
z=interp1(Biot,alfa,Bi);
end
% Newton method to solve for the first 10 roots
for i=1:10
for k=1:20
ta=tan(z);ez=(z*ta-Bi)/(ta+z*(1+ta*ta));
z=z-ez;
if abs(ez)<.00001, break, end
end
% Save the root and calculate the coefficients
zeta(i)=z;
cn(i)=4*sin(z)/(2*z+sin(2*z));
fprintf('Root # %g =%8.4f, Cn = %9.4e\n',i,z,cn(i))
% Obtain the guess for the next root
step=2.9+i/20;
if step>pi; step=pi;end
z=z+step;
end
%
% Evaluate and plot the concentrations
hold on
Fop=[.1 .5 1 2 10];
xs=-1:.05:1;
cosm=cos(cn'*xs);
for i=1:5
2-3

Fo=Fop(i);
theta=cn.*exp(-Fo*zeta.^2)*cosm;
plot(xs,theta)
end
grid
xlabel('x*');ylabel('Theta*')
Bi = .5
Root # 1 = 0.6533, Cn = 1.0701e+000
Root # 2 = 3.2923, Cn = -8.7276e-002
Root # 3 = 6.3616, Cn = 2.4335e-002
Root # 4 = 9.4775, Cn = -1.1056e-002
Root # 5 = 12.6060, Cn = 6.2682e-003
Root # 6 = 15.7397, Cn = -4.0264e-003
Root # 7 = 18.8760, Cn = 2.8017e-003
Root # 8 = 22.0139, Cn = -2.0609e-003
Root # 9 = 25.1526, Cn = 1.5791e-003
Root # 10 = 28.2920, Cn = -1.2483e-003
Figure 2.1-2 shows a plot of dimensionless concentration * versus dimensionless distance x* at
various Fourier number for a Biot number of 0.5.
Temperature distribution in a slab for Bi = 0.5
1
Fo=0.1
0.9
Fo=0.5
0.8

0.7

Fo=1

Theta*

0.6

0.5
Fo=2
0.4
0.3

0.2

0.1
Fo=10
0
-1

-0.8

-0.6

-0.4

-0.2

0
x*

0.2

0.4

0.6

0.8

Figure 2.1-2 Dimensionless concentration distribution at various Fourier number.

For the roots of equation n tan(n) = Bim, let
f = tan() Bim
Then

f = tan() +(1 + tan()2);

2-4

The differential conduction equation for mass transfer in the radial direction of an infinite
cylinder with radius R is

1 c A
cA
= DAB
r

r r r
t

(2.1-5)

The differential conduction equation for mass transfer in the radial direction of a sphere with
radius R is

1 2 c A
cA
= DAB 2
r
r r r
t

(2.1-6)

Equations (2.1-5) and (2.1-6) can be solved with the following initial and boundary conditions
I. C.

t = 0, cA(r, 0) = cA i

B. C.

r = 0,

c A
r

= 0;

r = R, DAB

r =0

c A
r

= hm(cAf cA,)
r=R

The solution of equation (2.1-5) for the infinite cylinder is given as

* =

C
n =1

exp( n2 Fo) J0(nx*)

(2.1-7)

where J0(nx*) is Bessel function of the first kind, order zero. The coefficient Cn are not the same
as those in a slab. The solution of equation (2.1-6) for a sphere is given as

* =

C
n =1

Since

exp( n2 Fo)

sin( n r*)
nr *

(2.1-8)

lim n cos( n r*)

sin( n r*)
=
= 1, it should be noted that at r* = 0
r* 0 n r *
r* 0
n
lim

* =

C
n =1

exp( n2 Fo)

For one-dimensional mass transfer in a semi-infinite solid as shown in Figure 2.1-3, the
differential equation is the same as that in one-dimensional mass transfer in a slab

2c
cA
= DAB 2A
x
t

2-5

x
Semi-Infinite Solid

Figure 2.1-3 One-dimensional mass transfer in a semi-infinite solid.

We consider three cases with the following initial and boundary conditions

Case 1:

Case 2:

Case 3:

I. C.: cA(x, 0) = cAi

B. C.: cA(0, t) = cAs,

cA(x , t) = cAi

I. C.: cA(x, 0) = cAi

c
B. C.: DAB A
= NA0,
x x =0

cA(x , t) = cAi

I. C.: cA(x, 0) = cAi

c
B. C.: DAB A = hm(cAf cA,),
x x =0

cA(x , t) = cAi

All three cases have the same initial condition cA(x, 0) = cAi and the boundary condition at
infinity cA(x , t) = cAi. However the boundary condition at x = 0 is different for each case,
therefore the solution will be different and will be summarized in a table later.

2.2 Approximate Solutions

The summation in the series solution for transient diffusion such as equation (2.1-4) can be
terminated after the first term for Fo > 0.2. The full series solution is

* =

C
n =1

exp( n2 Fo) cos(nx*)

(2.1-4)

The first term approximation is

* = C1exp(- 12 Fo) cos(1x*)

(2.2-1)

where C1 and 1 can be obtained from Table 2.2-1 for various value of Biot number. Table 2.2-2
lists the first term approximation for a slab, an infinite cylinder, and a sphere. Table 2.2-3 lists
the solution for one-dimensional heat transfer in a semi-infinite medium for three different
boundary conditions at the surface x = 0. Table 2.2-4 shows the combination of one-dimensional
solutions to obtain the multi-dimensional results.
2-6

Table 2.2-1 Coefficients used in the one-term approximation to the series

solutions for transient one-dimensional conduction or diffusion

Bim
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.1
0.15
0.2
0.25
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
20.0
30.0
40.0
50.0
100.0
500.0
1000.0

PLANE WALL
C1
1(rad)
0.0998
0.1410
0.1732
0.1987
0.2217
0.2425
0.2615
0.2791
0.2956
0.3111
0.3779
0.4328
0.4801
0.5218
0.5932
0.6533
0.7051
0.7506
0.7910
0.8274
0.8603
1.0769
1.1925
1.2646
1.3138
1.3496
1.3766
1.3978
1.4149
1.4289
1.4961
1.5202
1.5325
1.5400
1.5552
1.5677
1.5692
1.5708

1.0017
1.0033
1.0049
1.0066
1.0082
1.0098
1.0114
1.0130
1.0145
1.0160
1.0237
1.0311
1.0382
1.0450
1.0580
1.0701
1.0814
1.0919
1.1016
1.1107
1.1191
1.1795
1.2102
1.2287
1.2402
1.2479
1.2532
1.2570
1.2598
1.2620
1.2699
1.2717
1.2723
1.2727
1.2731
1.2732
1.2732
1.2732

INFINITE CYLINDER
C1
1(rad)
0.1412
0.1995
0.2439
0.2814
0.3142
0.3438
0.3708
0.3960
0.4195
0.4417
0.5376
0.6170
0.6856
0.7465
0.8516
0.9408
1.0185
1.0873
1.1490
1.2048
1.2558
1.5995
1.7887
1.9081
1.9898
2.0490
2.0937
2.1286
2.1566
2.1795
2.2881
2.3261
2.3455
2.3572
2.3809
2.4000
2.4024
2.4048

2-7

1.0025
1.0050
1.0075
1.0099
1.0124
1.0148
1.0173
1.0197
1.0222
1.0246
1.0365
1.0483
1.0598
1.0712
1.0932
1.1143
1.1346
1.1539
1.1725
1.1902
1.2071
1.3384
1.4191
1.4698
1.5029
1.5253
1.5411
1.5526
1.5611
1.5677
1.5919
1.5973
1.5993
1.6002
1.6015
1.6020
1.6020
1.6020

SPHERE

1(rad)
0.1730
0.2445
0.2989
0.3450
0.3852
0.4217
0.4550
0.4860
0.5150
0.5423
0.6608
0.7593
0.8448
0.9208
1.0528
1.1656
1.2644
1.3525
1.4320
1.5044
1.5708
2.0288
2.2889
2.4556
2.5704
2.6537
2.7165
2.7654
2.8044
2.8363
2.9857
3.0372
3.0632
3.0788
3.1102
3.1353
3.1385
3.1416

C1
1.0030
1.0060
1.0090
1.0120
1.0149
1.0179
1.0209
1.0239
1.0268
1.0298
1.0445
1.0592
1.0737
1.0880
1.1164
1.1441
1.1713
1.1978
1.2236
1.2488
1.2732
1.4793
1.6227
1.7201
1.7870
1.8338
1.8674
1.8921
1.9106
1.9249
1.9781
1.9898
1.9942
1.9962
1.9990
2.0000
2.0000
2.0000

Table 2.2-2 Approximate solutions for diffusion and conduction (valid for Fo>0.2)
Fo =

c K ' c A,
DAB t DAB t
, 0* = C1exp(- 12 Fo)
= 2 , *= A
2
L
c A, i K ' c A,
r0

Diffusion in a slab
L is defined as the distance from the center of the slab to the surface. If one surface is insulated,
L is defined as the total thickness of the slab.
sin( 1 ) *
M
* = 0* cos(1x*) ; t = 1
0
M
1

Diffusion in an infinite cylinder

2 0*
Mt
*
*
*
= 0 J0(1r ) ;
=1
J1(1)
M
1
Diffusion in a sphere
3 0*
1
Mt
*
*
*=

sin(

r
)
;
=
1

[sin(1) 1cos(1)]
1
0
1r *
M
13
If the concentration at the surface cA,s is known KcA, will be replaced by cA,s
1 and C1 will be obtained from table at Bim =

Notation:
cA = concentration of species A in the solid at any location at any time
cA,s = concentration of species A in the solid at the surface for t > 0
cA,i = concentration of species A in the solid at any location and at t = 0
cA, = bulk concentration of species A in the fluid surrounding the solid
KcA, = cA* = concentration of species A in the solid that is in equilibrium with cA,
Mt = amount of A transferred into the solid at any given time
M = amount of A transferred into the solid as t (maximum amount transferred)
hm L
Bim =
= ratio of internal resistance to mass transfer by diffusion to external mass
K ' DAB
transfer by convection
hm = kc = mass transfer coefficient
L = L for a slab with thickness 2L or a slab with thickness L and an impermeable surface
L = ro for radial mass transfer in a cylinder or sphere with radius ro
K = equilibrium distribution coefficient
DAB = diffusivity of A in the solid

2-8

Table 2.2-3 Semi-infinite medium

Constant Surface Concentration: cA(0, t) = cA,s

c A c A, s
c
x
= erf
; NA0 = DAB A

2 D t
c A , i c A, s
x
AB

DAB ( c A, s c A ,i )

x =0

DABt

Constant Surface Flux: NA(x=0) = NA0

cA(x, t) cA,i = 2NA0

x2
t
x
N A0 x
exp
erfc

2 D t
DAB
DAB
4 DAB t
AB

The complementary error function, erfc(w), is defined as erfc(w) = 1 erf(w)

Surface Convection: DAB

c A
x

= hm(cAf cA,)
x =0

2
h x

c A c A, i
hm t
x
x
h
t
m
= erfc
exp
+
erfc
+ m

2 D t K ' DAB
2 D t
K ' DAB K ' DAB
K ' c A, c A , i
AB
AB

Notation:
cA = concentration of species A in the solid at any location at any time
cA,s = concentration of species A in the solid at the surface for t > 0
cA,i = concentration of species A in the solid at any location and at t = 0
cAf = concentration of species A in the liquid at the solid-liquid interface at any time
cA, = bulk concentration of species A in the fluid surrounding the solid
KcA, = cA* = concentration of species A in the solid that is in equilibrium with cA,
hm = kc = mass transfer coefficient
K = equilibrium distribution coefficient
DAB = diffusivity of A in the solid

2-9

Table 2.2-4 Multidimensional Effects

ro

ro
x

(r,x)

L
L

L
L

r
cA(r,x,t)

The concentration profiles for a finite cylinder and a parallelpiped can be obtained from the
concentration profiles of infinite cylinder and slabs.
[ finite cylinder ] = [ infinite cylinder ] [ slab 22L ]
[ parallelpiped ] = [ slab 2L1 ] [ slab 22L2 ] [ slab 2L3 ]
S(x, t)

P(x, t)

C(r, t)

c A ( x , t ) K ' c A,
c A, i K ' c A,
c A ( x , t ) K ' c A,
c A, i K ' c A,
c A ( r , t ) K ' c A,
c A, i K ' c A,

Semi-infinite
solid

Plane
wall

Infinite
cylinder

2-10