Chapter 4: Unsteady state

(transient) Mass Transfer

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

hollow fiber sustained-release

,QWKHFRUH”U”5i) at steady

state with no convection and no
chemical reactions

Diffusion equation

General solution

CsA is bounded (finite) everywhere, including r = 0 a =0

This solution does not permit any depletion of the active species
from within the core of the fiber. Hence there could be no
evaporative loss from the exterior of the fiber without a reduction
in CS in the interior. This would violate a simple mass balance.
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
Our goal: to discuss a nonsteady mass transfer process.

We must write the transient diffusion equation to get an exact solution

for this transient process. ˧ complicated equation to solve.

Instead we will use a quasi-steady analysis. It is based on the idea that

diffusion in the core might be rapid compared to diffusion in the
membrane surrounding the core. In a sense, we are assuming that the
core is well mixed.

Diffusion problem in the annular membrane surrounding the

FRUH5i ”U”5o)

General solution

Boundary conditions
1. C Am 0 at r Ro
2. C Am D C As at r Ri
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

PRODUIOX[DWU 5o

molar rate of evaporation, per unit of fiber length L,

PRODUIOX[DWU 5i

dC Am DC As Dm
NA r Ri
 Dm 
dr r Ri
Ri ln( Ri / Ro )

molar rate of evaporation, per unit of fiber length L is same

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
But in reality the interior concentration is unsteady [CsA = CsA(t)], while
the solution presented here is valid only in the steady state: CsA = constant.
In the quasi-steady approximation we assume that the rate of transfer is
given by the expression above, even in the unsteady state, if CsA changes
slowly in some sense.

To find CsA(t) we now must introduce an overall mass (actually, mole)

balance that equates the change in CsA to the evaporative loss

define a time scale

l IJ

(Cs,oA is the initial

value of CsA)

After an elapsed time T, the total

amount evaporated

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

*(1(5$/75$16,(17',))86,21
125($&7,2125,17(51$/&219(&7,21

Initial condition:

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
Mass transfer equation

5HFWDQJXODUFRRUGLQDWHV\VWHP[\]

Cylidrical coordinate system (r,Ĺ]

Spherical coordinate system (r,DŽ,Ĺ)

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

Boundary conditions
• Essential boundary condition (Dirichlet condition):

• Flux boundary condition (Neumann condition):

‡0L[HGERXQGDU\FRQGLWLRQ5RELQFRQGLWLRQ:
- condition in terms of both the variable itself and derivative of variable

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 An arbitrary volume within
which transient diffusion occurs.

For a volume of arbitrary shape, it is impossible to write a simple

and general mathematical solution to the diffusion equation with
its initial and boundary conditions. The form of the solution
depends on the type of initial and boundary conditions.
We can learn something through dimensional arguments using a
compact dimensionless format.

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

If convection is taking place between the body (the

domain V) and an exterior fluid at some known
concentration equivalent to C’A, we usually choose to
define Y with C’A as a reference concentration:

with either of these

definitions of Y,
If convection is very effective (large k), then CsA ĺ&’A, Y = 1 at time t = O.
and the surface concentration would be specified This is why we
defined Y in this way.

Y takes on the value of zero on

the surface.

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 we make each space variable dimensionless using some
characteristic length scale L. Although L is undefined at this stage,
we can say that it is a parameter with the units of length and is
UHODWHGWRWKHVL]HRIWKHERG\.

e.g.
• For a simply shaped body, L could be one of the dimensions.
• For an odd-shaped body of volume V, L could be V1/3
• the ratio of volume to surface area A :L = V/A.

,Q&DUWHVLDQFRRUGLQDWHVZHZRXOGZULWHWKH/DSODFLDQRSHUDWRUDV

Prof. Do Hyun Kim, CBE332 Heat and

d Molecular
M l l Transfer,
T Fall, 2021

dimensionless time variable

differential
ff equation
q becomes

initial condition

boundary condition

If the surface concentration CsA were specified

boundary condition:

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 dimensionless "transport number" Bi, called the Biot number

Bi « 1:

Bi » 1:

Bi vs. Sh
Non-GLPHQVLRQDOL]DWLRQ

CA = CA(x,y,z,t; DAB,L,k)

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

The upper line is the value of Y

at the center of the body.

The dashed line is the value of Y

averaged over the volume.

The lower line is the value of Y

at the surface.

/RZHUOLQHIRU%L ’"

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 Example A

Unsteady Diffusion Across a Membrane

A membrane test cell consists of two compartments separated by a

polymeric membrane. Membrane is permeable to olefin vapors, like
ethylene, but impermeable to aliphatic hydrocarbon vapors. The top
compartment is initially evacuated, but the lower one is filled with
ethylene gas. We measure the ethylene concentration subsequently
appearing in the vapor in the top compartment as a function of time.
We will carry out an analysis of this problem, and show that we can use
the resulting mathematical model to determine the solubility and the
diffusion coefficient of ethylene in the film.
upper compartment

membrane

lower compartment filled with ethylene gas with partial pressure po

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

p=0
] % C=0
] %
C=0
]  ]  C=Hpo
p=po
t”0 t>0

• transient problem
• one-dimensional problem
• coordinate system

I.C and B.C

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 Non-GLPHQVLRQDOL]DWLRQ

Define a modified concentration variable Y'

boundary conditions will take

a simpler form with this

dimensionless space variable Z, and a dimensionless time variable X,

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

The advantage of this non-GLPHQVLRQDOL]DWLRQLVWZRIROG

1. The equation and boundary conditions are simpler to write, and
when there are fewer parameters, we are less likely to make
errors as we write.
:LWKVRPHH[SHULHQFHZHFDQUHFRJQL]HWKDWWKHGLIIHUHQWLDO
equation and boundary conditions are in a standard form, for which
a solution has already been worked out, and we need only find that
solution in a reference somewhere, rather than developing it
ourselves. From a practical, engineering, perspective, the best way
to solve a differential equation is to find that someone else has
already solved it and copy this solution!

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 Z Z
XUY XUY

X X

WU_ WU_ time

WU] time WU]

WU[ WU[

WUY WUY

W W
TWUY W WUY WU[ WU] WU_ X XUY W WUY WU[ WU] WU_ X XUY

C/Hpo <· -C/Hpo

Consider only the transient part

Y Y c( X , Z )  Y c( X o f, Z ) Y c( X , Z )  Z
Y c Y  Y c( X o f, Z ) Y  Z

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

* Separation of variables
Y A(X)B(Z)
wY w 2 Y Ac Bcc
c
Ÿ BA AB Ÿ cc C1
wX wZ 2 A B
Ac wA wA
C1 Ÿ AC1 Ÿ C1wX Ÿ lnA C1 X  C2
A wX A
Ÿ A exp(C1 X  C2 )
Since X o f, Y 1-Z (finite), C1  0. Ÿ C1 O2
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
Bcc
C1 O2
B
Bcc  O2 B 0 ½ § Sturm - Liouville ·
° ¨ ¸
° ¨ Problem ¸
° ¨ r ( x) 1, q( x) 0, ¸
B.C. ¾ ¨ ¸
Y(X,0) A(X)B(0) 0½ ° ¨ p( x) 1, E1 E 2 0 ¸
¾ o B(0) B(1) 0° ¨¨ ¸¸
Y(X,1) A(X)B(1) 0¿ °¿ ©D O
2
¹
Sturm - Liouville Problem
d
r ( x) yc  (q( x)  Dp( x) y) 0
dx
B.C.
D1 y (a)  E1 yc(a) 0
D 2 y (b)  E 2 yc(b) 0
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

Determine Ȝ

Bcc  O2 B 0 Ÿ B C3 cos OZ  C4 sin OZ

B.C.
B (0) C3 cos O ˜ 0  C4 sin O ˜ 0 0 Ÿ C3 0
B (1) C4 sin O ˜1 0 (C4 z 0) Ÿ O nS , n 1,2,3,
Ÿ B C4 sin nSZ , n 1,2,3,
ŸY A exp(O2 X ) sin OZ
Ÿ Yn An exp(n 2S 2 X ) sin nSZ
f f
Ÿ Y(X , Z) ¦Y ¦ A
n 1
n
n 1
n exp(n 2S 2 X ) sin nSZ

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 Determine An
f
I.C. Y (0, Z ) f (Z ) 1  Z ¦ A sin nSZ
n 1
n

1 1
An 2³ f ( Z ) sin nSZ dZ 2³ (1  Z ) sin nSZ dZ
0 0

2 ³ sin nSZ dZ  ³ Z sin nSZ dZ º

ª Fourier sine series
1 1

«¬ 0 0 ¼»
­° 1 ª sin nSZ Z cos nSZ º ½°
1

2 ® >cos nSZ @0  « 2 2 
1
»¼ ¾°
°̄ nS ¬ nS nS 0¿

­ cos nS 1 cos nS ½ 2
2 ®   ¾
¯ n S n S nS ¿ nS
f
Ÿ Y(X , Z) ¦A
n 1
n exp(n 2S 2 X ) sin nSZ

2sin nSZ
f

¦
S n1 n
exp(n 2S 2 X )

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

Y c Y  Y c( X o f) Y  Z

We want the rate of transfer of ethylene into the upper compartment.

For a membrane area A, this rate is

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 At Z=1

initial condition note

Note that in this solution the time dependence appears in two places: there
is a simple linear term t, to which is added an infinite series of exponential
functions of t, in terms of the dimensionless time X = DtlB2.
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

For a long time, defined as X > 1,

the exponential terms starting with n = 1 are small compared to unity

(From a mathematical handbook)

Since

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
It would not be difficult to show that we would get this result
exactly if we carried out a quasi-steady solution to this problem.
Now we have the additional insight that the quasi-steady solution is
valid after a period of time defined by X > 1.

Take data on p(t)

˧ find values for D from the intercept and
H from the slope (assuming B is known).

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

Consider physics

Boundary condition at the upper surface: assumption that the ethylene

partial pressure in the upper compartment satisfied p= O.

With that assumption, we end up with a solution for p(t) in the upper
compartment, which is an obvious violation of the assumption that p
vanishes there.

We conclude that the solution,. (Eq. 4.2.50,or Eq. 4.2.52, or even the more
exact result, Eq. 4.2.46) might be a good approximation as long as p(t) is
very small.

What is an appropriate criterion of small p? p/po is much smaller than 1.

We can design the experimental system by making the volume of the upper
compartment so great that any ethylene, that diffuses into the volume V
is so highly diluted that p/po is small compared to unity.

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
Example B

A Dissolving Particle

The dissolution of a particle is often controlled by diffusion into the

surrounding liquid. A transient analysis can tell us how much time is
required to reach a steady rate of dissolution, following some initial
transient period. In addition, we can find the time for the particle to
"disappear" through dissolution.
We assume
a stagnant liquid is in contact with the particle. y–

transient diffusion equation in spherical ™

coordinates, with only radial diffusion

Initial and boundary conditions

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

New variable u rC Ÿ C u/r

1 w § 2 wC · 1 wC w 2C
¨r ¸ ˜ 2r  2
r wr © wr ¹ r
2 2
wr wr
wC 1 wu u

wr r wr r 2
w 2C 1 wu 1 w 2u u 1 wu
   2 
wr 2 r 2 wr r wr 2 r 3 r 2 wr
1 w § 2 wC · 2 § 1 wu u · 2 wu 1 w 2u u 1 w 2u
¨ r ¸ ¨  ¸    2
r 2 wr © wr ¹ r © r wr r 2 ¹ r 2 wr r wr 2 r3 r wr 2

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 wC 1 w 2u
D
wt r wr 2

Initial and boundary conditions become

two identical partial differential equations can have different

solutions depending on the form ofthe boundary conditions.

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

Note same condition for t=0 and r˧’

Use combination of variables method (Similarity transform)

to transform pde to ode

New variable z r  Ro

wu w 2u
D 2 u 0 at t 0 wu w 2u
wt wr D 2 u 0 at t 0
wt wz
u U o at r Ro
u U o at z 0
u 0 at r o f Same
condition u 0 at z o f

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
New varibale
z
Ș ( z o f or g (t ) o 0,K o f)
g(t)
wu wu wK wu § g c(t ) · wu c
¨ ¸z  K  g (t )
wt wK wt wK ¨© g 2 (t ) ¸¹ wK g (t )
wu wu wK wu 1
wz wK wz wK g
w 2u w § wu · w § wu · wK w § wu 1 · wK w 2u 1
¨ ¸ ¨ ¸ ¨¨ ¸¸
wz 2 wz © wz ¹ wK © wz ¹ wz wK © wK g ¹ wz wK 2 g 2

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
Introduce new variable

used

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

ERXQGDU\FRQGLWLRQDWǃ ’JLYHV
f S
³
K 2
e dK
0 2

erf(ǃ): error function

erfc(ǃ): complemenatary error function

When the results of a series of measurements are described by a

normal distribution with standard deviation ķ and expected value 0, then
erf(a/ķ¥2) is the probability that the error of a single measurement
OLHVEHWZHHQíDDQGDIRUSRVLWLYHD
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021
 molar flux N at the surface Ro

d 2
erf ( x) exp( x 2 )
dx S
wC w ª Ro § r  Ro ·º
D D «Csat ¨1  erf ¸»
wr Ro wr ¬ r © 2 Dt ¹¼ R 
o

ª 1 2
2
§ r  Ro · § 1 ·º
 DCsat Ro « 2  exp¨  ¸ ¨ ¸»
¬« r S © 2 Dt ¹ © 2 Dt ¹¼» R 
o

ª 1 2 § 1 ·º ª1 2 § 1 ·º
 DCsat Ro « 2  ¨ ¸» DCsat «  ¨ ¸»
¬ Ro S © 2 Dt ¹¼ ¬ Ro S © 2 Dt ¹¼
DCsat ª Ro º
« 1
Ro ¬ SDt »¼
Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021

vs.

steady solution (equivalent to Sh = 2, a result we derived earlier) is reached

when

or

Hence a criterion for steady dissolution is given and if values for D and
Ro were available, we would be able to estimate the transient time prior
to steady dissolution.

Prof. Do Hyun Kim, CBE332 Heat and Molecular Transfer, Fall, 2021