You are on page 1of 26

Mass Transfer Processes

CHE3005W - Block 2 2016


Lectures 1-8, T1

Prof Jochen Petersen


(original document: Dr Mark Williamson)
Photo credit: BruceBlaus (http://goo.gl/etpSOu)

University of Cape Town


Department of Chemical
Engineering

Introduction

Lecture [ 1 ]

Putting mass transfer in context inter-relation of transport phenomena

Transport
phenomena

Fluid dynamics

transport of momentum

Heat transfer

transport of energy

Mass transfer (diffusion)

transport of mass

All 3 transport phenomena often occur simultaneously in industrial and


environmental situations.

Situations with only mass transfer are unusual, however initially in this course we
will be considering these type of problems, to help us understand the basic
concepts.

The mathematical relationships that describe these three phenomena are very
similar. This is not surprising, since the behaviour of fluids at a molecular level (as
postulated by kinetic theory) is a major factor for all of them. In fact kinetic theory
makes very reasonable predictions about viscosity, thermal conductivity and
diffusivity.

This mathematical (and underlying molecular) commonality allows us to predict all


transport aspects of the behaviour of systems by analogy, even if we about only
one of them.
For example: If we know (or can easily measure) the heat transfer characteristics
of a system, we can use an analogy (there are several established ones) to predict
the mass transfer and/or momentum transfer behaviour of the system. This can be
very useful in situations where direct measurement of these other transport
phenomena is difficult or impossible.

Introduction

Lecture [ 1 ]

Consider glacial melt water flowing in a river with a soluble limestone bed:
Velocity
(momentum)
profile

Concentration
(mass)
profile

Temperature
(energy)
profile

water

cA

limestone

x
Newtons law
of viscosity
Fouriers law of
conduction
Ficks 1st law
of diffusion

yx

v x
y

transport of momentum

A k

T
y

transport of energy

J A D AB

c A
y

transport of mass

Measure flow rate through channel (momentum transfer)


Select an analogy between momentum and mass transfer use it to
predict the rate of dissolution of the limestone base
Select an analogy between momentum and heat transfer use it to
predict the temperature rise of the water by absorption of heat from the
limestone base

Introduction

Lecture [ 1 ]

What is mass transfer in the context of this course?


A definition: Transfer of one substance through another on molecular and/or
macroscopic scales
Diffusive (molecular) mass transfer:

Bromine diffusing through air against the effects of gravity

Convective (macroscopic) mass transfer:


Development of turbulent flow
inside a tube

radial mass
transfer mode

molecular
only

macroscopic
dominant

Introduction
Some industrial processes that are influenced by mass transfer :
Direct contact of two immiscible phases:
distillation

Lecture [ 1 ]
Magnified view of a single
gas bubble in an H2S stripper
column
Liquid
(water)

gas absorption (scrubbing)


gas desorption (stripping)
fractional liquid extraction

Phases separated by a permeable membrane:

Gas
(air)

cH 2 S

dialysis, electro-dialysis
reverse osmosis
z

Some every-day processes that are rate-limited by mass transfer :


washing drying on a line (windy day vs. still day, dry vs. humid weather)
air freshener diffusing throughout a draught-free wardrobe
tea bag brewing in a tea pot
Try sketching the boundary layer configurations and concentration profiles for
these.

Basics of molecular diffusion

Lecture [ 2 ]

Molecular diffusion compared to mechanical mixing


Consider two identical isothermal cylindrical tanks 1.5 m x 1.5 m, both initially containing a
lower layer of salt solution and an upper layer of the same volume of pure water:

One tank is agitated using a simple paddle rotating at 22 rpm, the other is not.
How long until the top surface of each tank reaches 99% of its final salt concentration?
Molecular diffusion in fluids is the dominant mechanism for mass transfer in regions
where:

the fluid is stagnant (unmixed)

the fluid flow is laminar, and mass transfer is occurring normal to the direction of
flow

there exists a fluid boundary layer (by definition unmixed), for example at a phase
interface.

Basics of molecular diffusion

Lecture [ 2 ]

The following equation defines the diffusivity or diffusion coefficient of constituent A in a


fluid mixture of A and B, in terms of the mole fraction gradient:

x
J A D AB c A (2.1)
z

m 2 mol 1
mol

2
3
m s
s m m

Air (B)

Water (A)

cA(sat)

JA

= molar flux (i.e. moles


per unit area normal to
the diffusion, per unit
time) relative to the
average molar velocity of
all components.
DAB = diffusivity of A in B
cA
= concentration of A
z
= direction of diffusion

JA

cA
cA()

0
0

z=

c A( ) c A( sat)

J A DAB

If the total concentration is constant, then the molar flux can be expressed as:

J A D AB
m2
mol

2
m s
s

c A
z

mol / m 3

xA

=
total molar
concentration of all
components in a particular
phase
=
mol fraction of
component A in a liquid

(2.2)

Basics of molecular diffusion

Lecture [ 2 ]

For ideal gases, equation 2.1 can be expressed in terms of mole fractions or partial
pressures, since:

yA

yA
pA
n
c

pA
P

(Daltons law)

Pa

Pa

n
P

V
RT

(Ideal gas law)

Pa
N m2
mol mol

3
3
m
m
(
J
mol

K
)

K
(
Nm
mol

K
)
K

=
mol fraction of component A in a gas
=
partial pressure of component A in a
gas
=
total number of moles
= total molar concentration in (gas) phase

R
P
T

=
universal gas
constant 8.314 J/mol.K
=
total pressure
=
temperature

1 p A

RT z

J A D AB

m2
mol

2
m s
s

m2
Pa
1



( J mol K ) K m
s

( Nm mol K ) K

N m2

P y A

(2.3)
RT z

J A D AB
m2
mol

2
m s
s

m2

Pa



( J mol K ) K m
s


N m2

( Nm mol K ) K m

Basics of molecular diffusion

Lecture [ 2 ]

Two different molal fluxes J and N


In a system that is initially non-uniform, all constituents must diffuse to achieve uniformity.
Analysis of these systems requires the definition of two different fluxes:
J

is defined as the molar flux (i.e. moles per unit area normal to the diffusion, per unit
time) relative to the average molar velocity of all components

is defined as the molar flux (i.e. moles per unit area normal to the diffusion, per unit
time) relative to a fixed location in space

An analogy is a fish swimming upstream for an anglers (stationary) juicy worm:

is analogous to how well the fish can swim (its velocity relative to the stream)

is analogous to the fishs speed-of-approach to the worm (a function of the speed of


the river current and the fishs ability to swim).

J is characteristic of the
nature of the constituents
N is more useful for design of
processing equipment

Basics of molecular diffusion

Lecture [ 2 ]

Experiment to demonstrate the difference between J and N


Consider the 0.2 x 0.2 m cross-section box shown below, initially separated into two
sections by partition P, a clear film across the top to prevent evaporation, and balanced
on a narrow block.
Section I initially contains 10 kg water (constituent A),
section II initially contains 10 kg ethanol (constituent B).
Section I

Section II

H2O (A)

EtOH (B)

0.25 m

0.317 m

0.2 m

The concentration profiles along the box are initially as follows:

1.0

Mole
fraction

0
-0.25

0.317

10

Basics of molecular diffusion

Lecture [ 2 ]

What is the situation some time after the partition, P, is carefully removed?
H2O (A)

EtOH (B)

1.0
NB
Mole
fraction
NA

0
-0.25

0.317

0.317

What is the final situation?


1.0
0.718
Mole
fraction
0.282
0
-0.25

11

Basics of molecular diffusion


Now compare the initial and final situations:
H2O (A)
10,000 g

EtOH (B)
10,000 g

0.25 m
Section I
Initially
H2O 10 ,000 g
EtOH
0g

Lecture [ 2 ]

0.317 m
Section II
0g
10,000 g

Finally
H2O 10,000 x 0.25/(0.25+0.317) g
10,000 x 0.317/(0.25+0.317) g
EtOH 10,000 x 0.25/(0.25+0.317) g
10,000 x 0.317/(0.25+0.317) g
-------------------------------------------------------------------------------total: 8,820 g
total: 11,180 g

5,590 g H2O
4,410 g EtOH
1180g

12

Ficks 1st Law

Lecture [ 3 ]

Quantitative analysis of diffusion systems

So we see that there are possibly two contributions to these type of mass transfer
systems. Considering the instantaneous transport of component A:

xA

Bulk fluid transport of A :

NA

cA
c A cB

N x A N A N B

mol
mol

2
2
m s
m s

c
N A N B A (3.1)
c

mol m

3
mol m
3

Diffusion transport of A:

J A D AB
m2
mol


2
m s
s

c A
z (3.2)
mol m 3

The total molar flux of component A relative to a fixed point in space is then given by
adding equations 3.1 and 3.2:

c A
cA
D AB
z
c

mol
mol

2
2
m s
m s

N A N A N B

mol m 3
m2

3
mol m
s

or in terms of mole fractions:

mol m 3

(3.3)

x A
z (3.4)

N A N A N B x A D AB c

cA
cB

=
overall/net molar flux
of all constituents in system
relative to a fixed position
=
mol fraction of
component A in a liquid
=
molar flux of
constituent A relative to a
fixed position
= concentration of A
= concentration of B

z
= direction of diffusion
DAB = binary diffusivity of A in B
c

=
total molar
concentration of all
components

Adolf Eugen Fick


(1829 1901)
was a German
physiologist. In
1870 he was the
first to devise a
technique for
measuring
cardiac output.

This is Ficks first law for a binary mixture.


It is the principle analytical expression of molecular diffusion transport.

13

Common boundary conditions for molecular diffusion

Lecture [ 3 ]

Thermodynamic equilibrium (i.e. saturation) at a phase interface


3 common situations:
1) Pure constituent A :

Interface
at Ti,Pi

= pA(sat) (for a gas)


or
= cA(sat) (for a liquid)
Phase II

Phase I
pure
liquid
constituent
A

Fluid mixture.
concentration
profile of A
required here
pA= f(z)

z=0
Antoines equation:
The saturated vapour pressure, p sat , of a vapour in another gas (or gas mixture e.g.
air) may be estimated from the temperature T :

ln p A ( sat ) A

B
TC

pA(sat) = satn. vap. pres. (kPa)


A,B,C = constants from lit.
T
= temperature [K]

Note: the experimentally determined coefficients A, B, C are sometimes reported in the


literature with:
- different units, often T (C) pA(sat) (mm Hg)
- log10 rather than ln in the correlation.
In this case the equation to be used is:

log 10 p A ( sat )

B*
A
T C*
*

14

Common boundary conditions for molecular diffusion


2) Liquid mixture of constituents A and B :

Lecture [ 3 ]

pA = f(pA(sat), xA)
Phase II
(laminar layer)

Phase I
liquid mixture
known ratio of
constituents A
and B
cA
cB

Gas mixture of A
and B.
partial pressure
profiles required here
pA=f(z)
pB=f(z)

A
B

z=0

z=0

Phase II
(laminar layer)

3) Constituent A slightly soluble in liquid B:


Phase I
liquid
constituent
B
low conc. A
cA
well mixed

Interface
at Ti Pi

Fluid mixture.
concentration
profile of A
required here
pA=f(z)
=pA(sat) (for a gas)
or
cA(sat) (for a liquid)

15

Common boundary conditions for molecular diffusion

Lecture [ 3 ]

Henry's law
At a constant temperature, the amount of a given gas dissolved in a given type and
volume of liquid is directly proportional to the partial pressure of that gas in equilibrium
with that liquid. This law is applicable only if the gas is slightly soluble in the liquid, i.e.
systems with dilute liquid concentrations of the dissolved gas.

pA H AcA
HA =

(3.5)

Henrys law coefficient


(kPa.m3/mol )
(temperature-dependent)

pA =

cA=

(gaseous) partial pressure


of A at phase interface
(kPa)
(liquid) concentration of A
at phase interface
(mol/m3)

P yA HA c x A
Example: SO2 in water:

1000
c water
55600 mol / m 3
M water 18 / 1000
At 25 C, 1 atm. HSO2 = 84.4 Pa.m3/mol

p
Hc
H cx A 88.4 55600
yA A A

x A 46.3 x A
P
P
P
101300

0.6

25C

William Henry
(1775 1836)
was an English
chemist. He
invented a process
for preparing
magnesia alba in
1771 and became known as
"Magnesia" Henry. He was a
founder and afterwards president
of the Manchester Literary and
Philosophical Society.

Sometimes in the literature, HA is


expressed as the inverse of our
definition here, and with different
units..be careful!

0.5

cA k HpA

0.4

Where
kH is in mol/L.atm

0.3
0.2
0.1
0

0.004

0.008

0.012

0.016

16

Common boundary conditions for molecular diffusion


Raoults law
Uses mol fractions of species in a solution and their equilibrium partial pressures to
predict their vapour pressures in the vapour space above that solution .

p A A x A p A ( sat )

(3.6)

= activity coefficient (-)

p A ( sat ) = saturated vapour pressure of A (kPa)


pA
xA

(temperature-dependent)

Lecture [ 3 ]
Franois-Marie Raoult
(1830 - 1901)
was a French
chemist who
conducted research
into the behaviour
of solutions,
especially their
physical properties.

(temperature-dependent)

= (gaseous) partial pressure of A at phase interface (kPa)


= (liquid) mol fraction of A at phase interface (-)

Both Henrys law and Raoults law assume ideal gas behaviour :

negligible interactive forces between gas-phase molecules

negligible gas-phase molecular volumes compared to the total gas volume.

vapour
mixture

p meth x meth p sat ( meth )


2 mol ethanol
+
1 mol methanol

liquid mixture

p(sat) ethanol

2
45 30 kPa
3
1
81 27 kPa
3

p ( eth ) x ( eth ) p sat ( eth )

total vapour pressure above mixture = 57 kPa

= 45 kPa
at system temperature

p(sat) methanol = 81 kPa

There is actually no such thing as


an ideal liquid mixture - the
adhesive & cohesive forces of
attraction are often quite different.
Negative deviation can be caused
by hydrogen bonds, e.g.
CH3.CO.CH3 + CHCl3
(adhesive>cohesive=lower than
expected soln. vap pres.)
Positive deviation can also be
caused by hydrogen bonds,
e.g. CH3.CO.CH3 + CS2
(adhesive<cohesive=higher than
expected soln. vap pres.)
Near-ideal (molecularly similar
substances):
hexane and heptane
benzene and methylbenzene
propan-1-ol and propan-2-ol

17

Special cases for molecular diffusion (1-D geometry, equi-molar counterdiffusion)

Lecture [ 3 ]

For equimolecular diffusion at steady state, N A = -NB = constant


laminar gas
film
yA(0)

yA()
NA

well-mixed
bulk liquid
A+B

well-mixed
bulk gas
A+B

NB

z=0
In this case, equation 3.4 simplifies considerably to:

N A D ABc

(3.7)

y A
z

m 2 mol
mol

2
3
m s
s m m

Integration of equation 7.1:

yA ()

y (0)

y A

NA

NA
c D AB

D AB c
y A () y A (0)

(3.8)

18

Special cases for molecular diffusion (1-D geometry, equi-molar counterdiffusion)

Lecture [ 3 ]

To develop a general expression for the concentration profiles, consider 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(

0
z (z+dz)

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

N A
0
z

(3.9)
using equation 3.7 to substitute for NA in equation 3.9 :

y A

D
.
c
.
0
AB

or.........

y A
D
.
c
.
0
AB

(3.10)

integrating equation 7.4 :

D AB .c

y A
A 0
z

integrating again:

D AB .c y A Az B 0

(3.11)

19

Special cases for molecular diffusion (1-D geometry, equi-molar counterdiffusion)

Lecture [ 3 ]

using the boundary conditions in this equation generates two simultaneous equations:

D AB c y A ( 0 ) B 0
D AB c y A ( ) A B 0
these simultaneous equations can be solved for A and B :

D AB c
y A ( 0) y A ( )

B D AB c y A ( 0 )

and then these values for A and B can be back-substituted into equation 3.11:

z
D AB c y A D AB c y A ( 0 ) y A ( ) D AB c y A ( 0 ) 0

y A y A (0) y A (0) y A ( )

(3.12)

DEPARTMENT OF CHEMICAL ENGINEERING

CHE3063F

MASS TRANSFER

Version

4/3/16 08:42:17 AM

20

Special cases for molecular diffusion (1-D geometry, equi-molar counterdiffusion)

Lecture [ 3 ]

y A y A (0) y A (0) y A ( )

1.0
0.9
0.8
0.7
0.6

yA

0.5
0.4
0.3
0.2
0.1
0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

z/d

DEPARTMENT OF CHEMICAL ENGINEERING

CHE3063F

MASS TRANSFER

Version

4/3/16 08:42:17 AM

21

Special cases for molecular diffusion (1-D geometry, A through


stagnant B)

Lecture [ 4 ]

laminar gas film

bulk
liquid
(mixed) yA(0)

yB

y B
0
z
y A
0
z

yA
H2O (A)

z=0

bulk
gas
(mixed)
H2O (A)

z+dz

yA()

To develop a general expression for the concentration profiles, first consider the continuity
equation at pseudo-steady-state, no reaction:

N A(z)
z

(4.1)

Then derive an expression for NA, using a version of equation 3.4 expressed as
gaseous mole fractions with NB=0

N A N A N B y A DAB c

y A
z

N A 1 y A D AB c

y A
z

(4.2)

N A ( z ) z

D AB c
y A
1 yA

(4.3)

Since NA is not a function of z (eq. 4.3), we can integrate eq. 4.3 from 0 to :

(4.4)

22

Special cases for molecular diffusion (1-D geometry, A through


stagnant B)

Lecture [ 4 ]

If we were interested in the concentration profile , we can integrate eq. 4.3


from 0 to , instead:
(4.5)
And is known from eq. 4.4. Substituting this value of into eq. 4.5:

23

Special cases for molecular diffusion (1-D geometry, A through stagnant B)

1 y A ()

y A 1 1 y A ( 0 )

Lecture [ 4 ]

1 y A ( 0)

1.0
0.9
0.8
0.7
0.6

yA

0.5
0.4
0.3
0.2
0.1
0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

z/d

24

Special cases for molecular diffusion (1-D geometry, dilute A)

Lecture [ 4 ]

laminar gas film


P

bulk
liquid
(mixed) yA(0)

bulk
gas
(mixed)

yA
H2O (A)

z=0

H2O (A)

z+dz

yA()

If A is dilute (xA << 1), we can simplify the solution in eq. 4.4 by recognizing

ln(1 y ) y

for

Then substituting this into eq 4.4

y 1

(4.5)

(4.6)
(4.7)
Which we recognize to be identical to the solution of the equimolar counter diffusion
problem in eq. 3.8

25

Special cases for molecular diffusion (1-D geometry, A through


stagnant B)

Lecture [ 4 ]

If we were interested in the concentration profile , we can simply substitue z


for
(4.8)
And is known from eq. 4.7. Substituting this value of into eq. 4.8:

26