Jorge H.

Snchez, UPB

Chapter 5

Differential Equations of Mass Transfer:

Steady and Unsteady State Diffusion
 Jorge H. Snchez, UPB

What is mass transfer?

Mass transfer is mass in transit as the result of a species concentration difference in a

mixture (actually, it is the chemical potential difference which causes the mass transfer)

Since molecular motion is random, there is equal probability any molecule moving to the
left or the right. Accordingly, more molecules of species A cross the plane from the left that
from the right.
 Jorge H. Snchez, UPB

Molecular and convective mass transfer

Velocities In a mixture of different chemical species, each specie moves at
different total velocity vi, therefore is important to define an average velocity of
the mixture:

Mass average velocity Molar average velocity

n n
v A v A B v B i v i v x A v A xB v B
M
xi v i
i 1 i 1

The velocity of a specie relative to the average velocity of the mixture defines its
velocity of diffusion.

vi v the diffusion velocity of species i relative to the mass-average velocity

vi v M the diffusion velocity of species i relative to the molar-average velocity

 Jorge H. Snchez, UPB

Molecular and convective mass transfer

Fluxes The flux of a given species is a vector quantity denoting the amount of the
particular species, in either mass or molar units, that passes per given increment of time
through a unit area normal to the vector.

N i ci v i

Total molar (mass) flux of species i (relative to fixed axes)
Total fluxes
ni i v i

J i ci v i v

Difusive molar flux of species i
J i ci v i v M

relative to the mass (molar) average
J
i c v v M velocity
i i
Difusive fluxes
ji i v i v

Difusive mass flux of species i
ji i v i v M

relative to the mass (molar) average
j
i i v i v M
velocity
 Jorge H. Snchez, UPB

Molecular and convective mass transfer

Therefore, from the expressions for the total flux, we have:

Ni J i ci v
total flux diffusive flux advective flux

In this way, for the different

average velocities:

N i J i ci v J iM ci v M
ni ji i v jiM i v M
 Jorge H. Snchez, UPB

Ficks law for binary mixtures of A and B

Reference velocity Mass units Molar units

jA DABA
DAB
v (A) JA A (B)
MA

vM jMA CM A DABxA (C) J MA CDABxA (D)

From equation (B)

J A DABcA Isothermal liquid solution ( constant)

From equation (D)

J MA DABcA Isobaric and isothermal gas mixture (C

constant)
 Jorge H. Snchez, UPB

Differential equation for mass transfer

For a given fixed control volume, the total mass conservation equation in integral form is
given by

t dV (v n)dS
rate of accumulation net rate of mass in
of mass

From the divergence theorem and the mean value theorem, we obtain that:

( v) 0 continuity equation
t
 Jorge H. Snchez, UPB

Now, for a component A we have (in molar units)

t c dV c (v
A A A n)dS
R dV A

rate of increase net rate of moles in rate of production

of moles of moles

As before, from the divergence theorem and the mean value theorem, we obtain that:

c A RA is the net formation rate, and occurs

N A RA 0 throughout the volume of the mixture -
t homogeneous reaction
 Jorge H. Snchez, UPB

c A
N A RA 0
t

Conservation equations for a specie in different coordinate systems.

Rectangular
ci N i , x N i , y N i , z
Ri 0
t x y z
Cylindrical
ci 1 1 N i , N i , z

t r r
rN i ,r
r

z
Ri 0

Spherical
ci 1 2 1 N i ,
2
t r r

r N i ,r
1

r sin
N i , sin
r sin
Ri 0
 Jorge H. Snchez, UPB

Special cases of chemical species conservation equation:

ci
v ci Di 2 ci Ri
t
ci
Di 2 ci Fick's second law
t
2 ci 0 Laplace equation

Conservation equations for a specie in a binary or pseudobinary mixture in different coordinate systems assuming
y Di constants.

Rectangular
ci ci ci ci 2ci 2ci 2ci
vx vy vz Di 2 2 2 Ri
t x y z x y z
Cylindrical
ci c v c c 1 ci 1 2ci 2ci
vr i i vz i Di r 2 2 Ri
t r r z r r r r 2
z
Spherical
ci ci v ci v ci 1 2 ci 1 ci 1 2ci
vr Di 2 r 2 sin Ri
t r r r sin r r r r sin r 2 sin 2 2
 Jorge H. Snchez, UPB

Boundary conditions

1. Dirichlet boundary condition: The concentration value is

given on a surface

cA (0) cA,s

2. Neumann boundary condition: The flux normal to a

surface is given

N A, s

x0 n N A RAs
0

3. Robin boundary condition: The component diffusing

throughout the material is transferred from/to the surface
by convective mass transfer

x0 n N A kc (cA,s cA, )
 Jorge H. Snchez, UPB

In many cases the concentration of a specie is discontinuous in a gas-solid or a gas-liquid

interface. We have to relate the concentration on both sides of the interface.

Evaporation and sublimation

p A (0) x A (0) p Asat Raoult's law

p A (0) p Asat Pure liquid

Solubility of gases in liquids

p A (0)
xA (0) Henry's law
H
 Jorge H. Snchez, UPB

Example
A device has been proposed that will serve as a blood oxygenator
for a heartlung bypass machine. In this process, blood (which is
mostly water, species B) containing no dissolved oxygen (O2
species A) enters the top of the chamber and then falls vertically
down as a liquid film of uniform thickness, along a surface
designed to appropriately wet blood. Contacting the liquid surface
is a 100% O2 gas phase.

Oxygen is soluble in blood, with the equilibrium solubility described by Henrys law, cA* = pA/H, where pA is the
partial pressure of oxygen (atm), H is the Henrys law constant, and cA* is the solubility concentration limit of
oxygen dissolved in blood (mmol/L) at pA. In analyzing the mass transport of dissolved oxygen into the falling
film, you may assume the following: (1) the process is dilute with respect to dissolved oxygen in the fluid; (2) the
falling liquid film has a flat velocity profile with velocity vmax; (3) the gas space always contains 100% oxygen;
(5) the width of the liquid film, W, is much larger than the length of the liquid film, L.
a) Simplify the general differential equation for O2 transfer. If your analysis suggests more than one dimension for
flux, provide a simplified flux equation for each coordinate of interest.
b) Provide one simplified differential equation in terms of the fluxes and another simplified differential equation in
terms of the oxygen concentration cA.
c) List boundary conditions associated with the oxygen mass transfer process.
 Jorge H. Snchez, UPB

Example
A catalyst particle is suspended in a gas stream of mixture A and B that is maintained at constant
concentration cA,. The core of the particle is nonporous and is coated with a catalyst. A highly porous
layer with void fraction = 0.60 surrounds the catalyst coating. The catalyst coating catalyzes the
heterogeneous reaction A B, where ks is the surface reaction rate constant. Consider a cylindrical
particle, where r = R1 represents the radial position of the catalyst coating and r = R2 represents the outer
radius of the porous layer. The length of the cylindrical particle is L. Reactant A in the surrounding fluid
diffuses through the porous layer to the catalyst surface. The reaction rate of species A at the catalyst
surface is described by RA = kscAs.

Develop equations to predict the flux of species

A at the catalyst surface r = R1, and then
compare the flux for a reaction carried out at
300 C and 1.0 atm with ks = 2.0 cm/s, DAB =
0.30 cm2/s, and 50 mole% A maintained in the
gas phase.
 Jorge H. Snchez, UPB

Example
Diffusion and heterogeneous chemical reaction consider the diffusion of oxygen to
the surface of spherical particle of coal. At the surface of the particle, oxygen gas (O2)
reacts with solid carbon (C) in the coal to form carbon dioxide (CO2) gas according to
the heterogeneous reaction C + O2 CO2. If the reaction rate is given by RO2= kcO2,
determine the total molar flow of oxygen to the surface of coal.
 Jorge H. Snchez, UPB

Example
Homogeneous diffusion with chemical reaction a gas is dissolved in a liquid B and
diffuses through it isothermally. As A diffuses, it suffers a first order irreversible
homogeneous reaction to produce AB. Determine the concentration profile of A and
molar flux at the interface liquid - gas. (DAB = 110-5 m2/s, k = 0.001,0.01,0.1,1 s-1, L =
10 cm, W = 5 cm)

RA kCA
 Jorge H. Snchez, UPB

Example
Consider the simple rotating disk process unit show in the figure for the treatment of phenol (species A) in
wastewater. The biofilm contains a microorganism rich in the enzyme peroxidase that oxidatively degrades phenol.
The concentration of species A in the bulk-fluid phase over the biofilm is constant if the fluid phase is well mixed.
However, the concentration of A within the biofilm will decrease along the depth of the biofilm z as species A is
degraded. There are no resistances to convective mass transfer across the fluid boundary layer between the bulk fluid
and the biofilm surface. Furthermore, phenol is equally soluble in both water and biofilm, and the density difference
between the biofilm and water can be neglected, so that the surface concentration of phenol in the aqueous phase
equals the surface concentration of phenol in the gel phase just inside the biofilm, that is, at z = 0, cAs= cA0.
It is desired to treat 0.1 m3/h of wastewater containing 0.1 mol/m3 of phenol. If the biofilm thickness is 2 mm, what is
the required surface area of the biofilm necessary to achieve the desired outlet concentration of 0.02 mol/m3?

The rate of degradation of phenol per

unit volume of the biofilm is described
by:

RA,max c A
RA
K A cA

RA,max 5.7 103 mol/m3 s

K A 0.3 mol/m3
DAB 2 1010 m 2 / s
 Jorge H. Snchez, UPB

Effect of the Thiele number () on reactant concentration

for steady diffusion
 Jorge H. Snchez, UPB

Unsteady-state molecular diffusion

The time-dependent equations are simple to derive from the general differential equations of mass transfer.

c A A
N A RA 0 or n A rA 0
t t
The solution to the resulting partial differential equation is generally difficult, involving relative advanced
mathematics techniques.

Pseudo-steady-state diffusion

In many mass-transfer operations, one of

the boundaries may move with time. If
the length of the diffusion path changes a
small amount over a long period of time,
a pseudo-steady state diffusion model
may be used.
 Jorge H. Snchez, UPB

Example
Consider the timed drug-release pill illustrated below. The pill is ingested into the stomach. The pill is a slab, 0.36 cm
per side, that has an array of 16 cylindrical pores in it. Each pore is 0.4 mm in diameter and 2.0 mm deep. Pure solid
drug A is loaded into each pore to a depth of 1.2 mm, which provides a total initial drug loading of 2.65 mg in all of
the pores. The density of the solid drug A is 1.10 g/cm3. The drug dissolves into the fluid inside the stomach, which
approximates the properties of water (component B). The maximum solubility of drug A in water is 210-4 gmol/cm3
(i.e., not very soluble) and the diffusion coefficient of the drug is 210-5 cm2/s at body temperature of 37 C. The
molecular weight of the drug is 120 g/mol.

a. Starting with the general differential equation for mass

transfer and Ficks flux equation, develop a simple model,
in final integrated form, for predicting the flux of the drug
from one pore. You may assume that the diffusion process
is pseudo-steady state, the stomach fluid serves as an
infinite sink for the drug so that cA = 0, and the drug does
not chemically degrade inside the pore.
b. From your model, determine the initial total transfer rate
of the drug from the whole pill, WA, to the body when each
0.2 cm pore is filled to a depth of 0.12 cm with solid drug.
c. How many hours will it take for all of the drug to be
released?
 Jorge H. Snchez, UPB

Example
The formation of a silicon oxide (SiO2) thin film on a silicon (Si) wafer surface is an important step in
the fabrication of solid-state microelectronic devices. A thin film of SiO2 serves as a dielectric insulator
to isolate various devices being formed on the wafer. In one common process, silicon is oxidized by
exposure to oxygen (O2) gas at temperatures above 700 C.

Molecular O2 dissolves into de SiO2 solid, diffuses through the SiO2 film, and then reacts with Si at the
Si/SiO2 interface, as shown in figure. Assuming that the diffusion of O2 through the SiO2 film limits the
oxidation process, develop a model to predict the thickness of the SiO2 layer () as a function of time at
1000 C. The density of solid SiO2 is 2.27 g/cm3, and the molecular weight of SiO2 is 60 g/mol. The
molecular diffusion coefficient of O2 in SiO2 is 2.7 10-9 cm2/s at 1000 C, and the maximum
solubility of O2 in SiO2 is 9.6 10-8 mol O2/cm3 solid at 1000 C and 1 atm O2 partial pressure.
 Jorge H. Snchez, UPB

Example (cont.)
The figure compares the predicted film thickness vs. time to process data provided by Hess*

*D. W. Hess, Chem. Eng. Educ., 24, 34 (1990)

 Jorge H. Snchez, UPB

Transient diffusion (Analytical solution) Most solutions to these equations have been
limited to situations involving simple geometries and boundary conditions, and a constant
diffusion coefficient.

Many solutions are for one-dimensional mass transfer as defined by Ficks second law of
diffusion (no bulk motion contribution, v = 0, and no chemical reaction)*

cA ( x,0) cA,0 c A 2cA

DAB 2
t x

c A, , kc c A, , kc
cA ( x,0) cA,0
c
A 0
x x0

D cA kc cA ( L, t ) cA,
AB x
x L

*J. Crank, The mathematics of diffusion, Oxford, 1975

 Jorge H. Snchez, UPB

Plane Wall

c A c A , 4sin n
D t x
exp n2 AB
2
cos n ,
c A,0 c A, n 1
2 n sin(2 n ) L L

where n tan n Bi

Sphere

c A c A ,
4 sin( n ) n cos( n ) R
c A,0 c A,

n 1
2 n sin(2 n )

nr
exp
2 DAB t r
n 2 sin n ,
R R

where 1 n cot( n ) Bi

kc L
For mass transfer the Biot number is defined as Bi
DAB
 Jorge H. Snchez, UPB

Unsteady-state diffusion in a semi-infinite medium

cA,s c A 2cA
DAB 2
t x

c A (0, x) c A,0

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

c A c A,0 x
erfc
c A, s c A,0 2 D t
AB

cA,0
N A, s
DAB
t
c A, s c A,0
 Jorge H. Snchez, UPB

Example
One way to deliver a timed dosage of a drug within the human body is to ingest a capsule and allow it to settle in the
gastrointestinal system. Once inside the body, the capsule slowly releases the drug by a diffusion-limited process. A
suitable drug carrier is a spherical bead of a nontoxic gelatinous material that can pass through the gastrointestinal
system without disintegrating.

Consider a limiting case where the resistance mass transfer of the drug through the liquid boundary layer surrounding
the capsule surface to the bulk fluid is negligible. Furthermore, assume that the drug is immediately consumed or
swept away once it reaches the bulk solution. It is desired to design a spherical capsule for the timed release of the
drug commonly called Dramamine, which is used to treat motion sickness. A conservative total dosage for one
capsule is 10 mg, where 50% of the drug must be released to the body within 3 h. Determine the size of the bead and
the initial concentration in the bead necessary to achieve this dosage. The diffusion coefficient of Dramamine in the
gel matrix is 3 10-7 cm2/s at 37C. The solubility limit of Dramamine in the gel is 100 mg/cm3, whereas the
solubility in water is only 3 mg/cm3.
 Jorge H. Snchez, UPB

Example
A cylinder of clay, 30 cm long and 10 cm in diameter to be dried in a stream of dry
air. The initial uniform composition is 14 wt%, and the final center composition
desired will be 7 wt%. Under the specified drying conditions, the drying will be
controlled by the internal diffusion of liquid water to the surface. The diffusivity of
water through the clay is estimated to be 1.310-8 m2/s. The surface moisture
content will remain constant throughout the process at 3 wt%. Determine the
drying time required.