Part I

1
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1. Introduction to Mass Transfer

and Diffusion
2. Molecular Diffusion in Gasses
3. Molecular Diffusion in Liquids
4. Molecular Diffusion in Biological
Solutions and Gels
5. Molecular Diffusion in Solids
6. Unsteady State Diffusion
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Part
I

Part
II

7. Convection Mass Transfer

Coefficients
8. Mass Transfer Coefficients
for various geometries
9. Mass Transfer to Suspensions
of Small Particles

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Part
II

Part
III

1. Introduction to Mass Transfer and

Diffusion
1.1 Ficks law for molecular diffusion

2. Molecular Diffusion in Gasses

2.1 Equimolar counterdiffusion in gases

2.2 General case for diffusion of gases A
& B plus convection
2.3 Special case for A diffusing through
stagnant, nondiffusing B

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2.4 Diffusion through a varying crosssectional area

2.5 Diffusion coefficient for gases

3. Molecular Diffusion in Liquids

3.1 Introduction
3.2 Equation for diffusion in liquids
3.3 Diffusion coefficients for liquids
3.4 Prediction of diffusivities in liquids

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 Mass transfer occurs:

Water evaporates
into still air.

Sugar dissolves &

diffuses to the
surrounding solution.
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 Mass transfer occurs:

Liquid-liquid
extraction
Crystallization
Distillation

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Drying

Adsorption

 Molecular diffusion (transport):

the transfer or movement of
individual molecules through a fluid
by means of the random, individual
movements of the molecules.

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Low
concentration

High
concentration
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Figure 6.1-1:
Schematic
diagram of
molecular
diffusion
process.
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 Consider:
the diffusion of molecules when the
whole bulk fluid is not moving but is
stationary.
due to a concentration gradient.
The Ficks law equation:

J
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*
AZ

cDAB

Total concentration
of A &B (kg mol/m3)

dxA
dz

The mole fraction of

A in mixture of A & B
Distance, m

The molecular diffusivity of

the molecule A in B, m2/s

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 If c is constant, then cA=cxA,

cdxA = d(cxA)=dcA
For constant total concentration:

*
AZ

DAB

dcA
dz

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Example 6.1-1

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Example 6.1-1

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Example 6.1-1

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2.1 Equimolar Counterdiffusion in Gases

Two gases A & B at constant total
pressure P in two large chambers
connected by a tube where molecular
diffusion at steady state is occurring.
Figure 6.2-1:
Equimolar
counterdiffusion
of gases A and B
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 Stirring in each chamber keeps the

concentrations in each chamber uniform.
The partial pressure pA1>pA2 and pB2>pB1.
Molecules of A diffuse to the right and
B to the left.
Since the total pressure P is constant
throughout, the net moles of A
diffusing to the right must equal to the
net moles of B to the left.

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 This means that

*
A

*
B

Writing Ficks law for B for constant c,

*
B

DBA

dcB
dz

Now since P=pA+pB = constant, then

cA

cB

Differentiating both sides, dc

dc=0,
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dc A

dc A

dc B
dc B
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 Equating the equations,

*
A

Finally,

DAB

dcA
dz

DAB

*
B

DBA

( )DBA

dcB
dz

Molecular
diffusivity

This shows that for a binary gas

mixture of A & B,
the diffusivity coefficient DAB for A
diffusing into B is the same as DBA
for B diffusing into A.
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Example 6.2-1

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Example 6.2-1

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 The diffusion flux J*A occurred because

of the concentration gradient.
The rate at which moles of A passed a
fixed point to the right (positive flux).
This flux can be converted:
*
A

J ( kg mol A / s.m ) v AD c A

m kgmol A
3
s
m

where vAD is the diffusion velocity of A

(m/s).
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 Consider when the whole fluid is moving

in bulk or convective flow to the right.
The molar average velocity of the whole
fluid relative to a stationary point is vM
m/s.
Component A is still diffusing to the
right, but now its diffusion velocity,
vAd is measured relative to the moving
fluid.
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 To a stationary observer A is moving

faster than the bulk of the phase, since
its diffusion velocity vAd is added to that
of the bulk phase vM.
The velocity of A relative to the
stationary point is the sum of the
diffusion velocity & the average or
convective velocity:

vA

v Ad

vM

Where vA velocity of A relative to a

stationary point.
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vA
vAd

vM

Multiplying by cA,

c Av A

NA
(kgmol A/s,m2)

c Av Ad

c Av M

J*A

Let N be the total convective flux:

N
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cv M

NA

NB

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 So,

NA

*
A

cA
NA
c

Since J*A is Ficks law,

NA
NB
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dxA
cDAB
dz
dxB
cDBA
dz

NB
Equimolar
counterdiffusion

cA
N A NB
c
cB
N A NB
c

NA = -NB
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 In the evaporation of a pure liquid (e.g.

benzene (A) at the bottom of a narrow
tube, where a large amount of inert or
nondiffusing air (B) is passed over the top.
Figure 6.2-2a:
Diffusion of A
through stagnant,
nondiffusing B: (a)
benzene
evaporating into air
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 The benzene vapor (A) diffuses through

the air (B) in the tube.
The boundary at the liquid surface at
point 1 is impermeable to air, since air is
insoluble in benzene liquid.
Air (B) cannot diffuse into or away from
the surface.
At point 2 the partial pressure pA2=0,
since a large volume of air is passing by.
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 In the absorption of NH3 (A) vapor which

is in air (B) by water.
The water surface is impermeable to
the air, since air is only very slightly
soluble in water.
Figure 6.2-2:
Diffusion of A through
stagnant, nondiffusing
B. (b) ammonia in air
being absorbed into
water.
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 thus, since B cannot diffuse, NB = 0.

NA

cDAB

dxA
dz

cA
NA
c

Convective flux of A

Keeping the total pressure P constant,

substituting
P
c
p
x
P
A
A
RT

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cA
c

pA
P

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 Then,

NA

pA
NA 1
P
z2

N A dz
z1

NA
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DAB dpA
RT dz

pA
NA
P

DAB dp A
RT dz

DAB
RT

pA 2

dpA
1 pA P
p A1

DAB P
P
ln
RT z2 z1
P

pA 2
pA1
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 A log mean value of the inert B is defined:

pB1

pA1

pB1

pA1

Then, PBM
NA

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pA 2

pB 2

pB 2 pB1
ln pB 2 pB1

pB 2

pA 2

pA1 pA 2
ln P pA 2 P pA1

DAB P
pA1
RT z2 z1 pBM

pA 2
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EXAMPLE 6.2-2

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EXAMPLE 6.2-2

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EXAMPLE 6.2-3

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EXAMPLE 6.2-3

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 So far, the cross-sectional area A m2

through which the diffusion occurs has
been constant with varying distance z.
In some situations the area A may vary.

NA

NA
A

kg moles of A / s

At steady state, N A will be constant

but not A for a varying area.
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2.4.1 Diffusion from a sphere

The evaporation of a drop of liquid, the
evaporation of a ball of naphthalene, and
the diffusion of nutrients to a sphere-like
microorganism in a liquid.
Figure 6.2-3a:
A sphere of fixed
radius, r1 (m) in
an infinite gas
medium.
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NA

NA
A

NA
2
4r

Since this is a case of A diffusing through

stagnant, nondiffusing B:

NA

NA
2
4r

DAB
dpA
RT 1 pA P dr

Note that dr was substituted for dz.

Integrating between r1 and some point r2
a large distance away:
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NA
4
NA 1
4 r1

r2

dr
2
r
r1
1
r2

DAB
RT

pA 2

p A1

dpA
dr
1 pA P

DAB P P pA 2
ln
RT
P pA1

r2>>r1, 1/r20.

NA
2
4r1
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NA1

DAB pA1 pA 2
RTr1 pBM
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 If pA1 is small compared to P (a dilute gas

phase), pBMP,
2r1=D1 (diameter),
cA1=pA1/RT

N A1

2DAB
c A1 c A 2
D1

This equation can be used for liquids,

where DAB is the diffusivity of A in the
liquid.
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Example 6.2-4

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Example 6.2-4

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 If the sphere is evaporating, the radius r

of the sphere decreases slowly with time.
The time it takes for the sphere to
evaporate completely can be derived by
assuming pseudo-steady state and by
equating the diffusion flux equation,
where r is now a variable, to the moles
of solid A evaporated per dt time and per
unit area as calculated from a material
balance.
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Density of
the sphere

tF

Original
sphere radius

2
A 1

p r RTpBM
2M ADAB P pA1 pA 2

Molecular
weight
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2.5.1 Experimental determination of

diffusion coefficients
To evaporate a pure liquid un a narrow
tube with a gas passed over the top (see
Fig 6.2-2a).
The fall in liquid level is measured with
time and the diffusivity calculated:

DAB

2
A 1

p r RTpBM
2M At F P pA1 pA 2
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 The common method is the two-bulb

method (N1).

Figure 6.2-4:
Diffusivity
measurement of
gases by the
two-bulb
method.
Pure gas A is added to V1 and pure B to V2
at the same pressures.
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 The valve is opened, diffusion proceeds

for a given time, and then the valve is
closed and the mixed contents of each
chamber are sampled separately.
Assumptions:
Neglecting the capillary volume &
assuming each bulb is always of a
uniform concentration.

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Quasi-steady-state diffusion in the

Concentration Concentration
capillary,
of A in V1 at
time t

of A in V2 at
time t

*
A

DAB

dc
dz

DAB c 2
L

c1

The rate of diffusion of A going to V2 is

equal to the rate of accumulation in V2:

AJ
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*
A

DAB c 2 c1 A
L

dc2
V2
dt
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 The average value cav at equilibrium can

be calculated by a material balance from
the starting composition c10 and c20 at
t=0:

V1 V2 cav

0
1 1

Vc

0
2 2

Vc

A similar balance at time t gives,

V1 V2 cav
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V1c1 V2c 2
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 Rearranging & integrating between t=0 &

t=t,

cav
cav

c2
0
c2

exp

DAB V1 V2
L A V2V1

if c2 is obtained by sampling at t, DAB

can be calculated.

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 Some typical data are given in Table 6.21, Perry & Green (1984) and Reid et al.,
(1938).

Table 6.2-1: Diffusivity coefficient of gases at

101.32 kPa Pressure

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 The diffusivity of a binary gas mixture in

the dilute gas region, that is, at low
pressure near atmospheric, can be
predicted using the kinetics theory of
collision with another molecule, which
implies that
momentum is
conserved.

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 The final relation for predicting the

diffusivity of a binary gas pair of A & B
molecules is:
7

DAB

1.8583x10 T
2
P AB D ,AB

Average
collision
diameter
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3/ 2

1
MA

1
MB

1/ 2

A collision integral based on

the Lennard-Jones
potential
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 The above equation is relatively

complicated to use (AB is not available
or are difficult to estimate).
7

DAB

1.75

1.00x10 T 1 M A 1 MB
1/ 3
1/ 3 2
p A
B

1/ 2

Sum of structural
volume increments

Note: DAB 1/P, DAB T1.75,

DAB T1.75/P
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Table 6.2-2: Atomic diffusion volumes for use

with Fuller et al., method.

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Example 6.2-5

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Example 6.2-5

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3.1 Introduction
Diffusion of solutes in liquids is
important in many industrial processes:

Solvent
extraction
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Gas
absorption Distillation

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 Diffusion in liquids also occurs in nature:

Oxygeneration of
rivers and lakes by
the air
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Diffusion of
water in blood
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 It should be apparent that the rate of

molecular diffusion in liquids is
considerably slower than in gases.
The molecules of the diffusing solute
A will collide with molecules of liquid B
more often and diffuse more slowly
than in gasses.
The diffusion coefficient in a gas will
be on the order of magnitude of about
105 times greater than in a liquid.
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 The flux in a gas is being only 100 times

faster,
since the concentrations in liquids are
considerably higher than in gases.
Since the molecules in a liquid are
packed together much more closely
than in gases, the density & resistance
to diffusion in a liquid are much greater.
the attractive forces between
molecules play important role in
diffusion.
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 Diffusion of liquids: the diffusivities are

often dependent on the concentration of
the diffusing components.

3.2.1 Equimolar counterdiffusion

An equation similar to gases at steady
state [NA=-NB]:

NA
Kg mol
A/s.m2
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DAB c A1 c A 2
z2 z1

DAB cav x A1 x A 2
z2 z1

Concentration of
Mole fraction of
3
m2/s A (kg mol A/m ) A at point 1.
at point 1.
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 cav defined by

cav
M av

1
M1

2
M2

Average
density of
the
solution
(kg/m3)

Average total
Average molecular weight
concentration of of the solution at point 1
A+B (kg mol/m3)
(kg mass / kg mol)

The average value of DAB may vary some

with concentration, &
the average value of c may vary with
concentration
Linear average of c is usually used.
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 A dilute solution of propionic acid (A) in a

water (B) solution being contacted with
toulene.
Only the propionic acid (A) diffuses
through the water phase (B), to the
boundary & then into the toluene phase.
The toulene-water interface is a
barrier to diffusion of B and NB = 0.
Substituting
P
A1
pBM
cav
c A1
xBM
P
RT
RT
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 For liquids at steady state:

NA

DAB cav
x A1
z2 z1 xBM

x A2

xB 2 xB1
xBM
ln( xB 2 xB1 )
Note xA1+xB1=xA2+xB2=1.0
For dilute solution, xBM is close to 1.0
c is essentially constant.

NA
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DAB c A1 c A 2
z2 z1
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Example 6.3-1

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Example 6.3-1

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3.2.3.1 Experimental determination of

diffusivities
A relatively dilute solution & a slightly
more concentrated solution are placed in
chambers on opposite sides of a porous
membrane of sintered glass (see Fig6.3-1).
Figure 6.3-1:
Diffusion cell for
determination of
diffusivity in a
liquid
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 Quasi-steady-state diffusion in the

membrane is assumed:
Concentration in the lower
chamber at a time, t
Fraction of area
of the glass open
to diffusion

NA
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Concentration in the
upper chamber

DAB

c c'

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 Combining & integrating:

Initial concentrations

ln

c0 c'0
c c'

Final concentrations

2A
DAB t
V
Cell constant

Note: For liquids, unlike gases, the

diffusivity DAB does not equal DBA.
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 Table 6.3-1: experimental diffusivity

data for binary mixtures in the liquid
phase are given.
The diffusivity values are quite small and
in the range of about 0.5x10-9 to 5x10-9
m2/s for relatively nonviscous liquids.
Diffusivities in gases are larger by a
factor of 104-105.

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Table 6.3-1:
experimental
diffusivity data
for binary
mixtures in the
liquid phase are
given.

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 The Stokes-Einstein equation was derived

for a very large spherical molecule (A)
diffusing in a liquid solvent (B) of small
molecules.
Stokes law was used to describe the
drag on the moving solute molecule.
Diffusivity,
K
2
16
m /s
9.96x10 T

DAB

Viscosity,
Pa.s or kg/m.s
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1/ 3
A

Solute molar
volume at its
normal boiling
point, m3/kgmol
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 The Wilke-Chang correlation can be used

for most general purposes, where the
solute (A) is dilute in the solvent (B).

DAB

1.173 x10

16

M B

Association
Molecular weight
parameter
of solvent B
of the
Viscosity of B,
solvent
Pa.s or kg/m.s
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1/ 2

T
0. 6
BVA

Solute molar
volume at the
boiling point
(Table 6.3-2)
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 The association parameter ():

Water
Methanol
Ethanol

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2.6
1.9
1.5

Benzene
Ether
Heptane
Unassociated
solvents

1.0
1.0
1.0
1.0

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Example 6.3-2

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Example 6.3-2

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