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Introduction
Lecture [ 1 ]
Transport
phenomena
Fluid dynamics
transport of momentum
Heat transfer
transport of energy
transport of mass
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.
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
Introduction
Lecture [ 1 ]
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
(air)
cH 2 S
dialysis, electro-dialysis
reverse osmosis
z
Lecture [ 2 ]
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 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.
Lecture [ 2 ]
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
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)
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
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
Lecture [ 2 ]
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
is analogous to how well the fish can swim (its velocity relative to the stream)
J is characteristic of the
nature of the constituents
N is more useful for design of
processing equipment
Lecture [ 2 ]
Section II
H2O (A)
EtOH (B)
0.25 m
0.317 m
0.2 m
1.0
Mole
fraction
0
-0.25
0.317
10
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
11
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
Lecture [ 3 ]
So we see that there are possibly two contributions to these type of mass transfer
systems. Considering the instantaneous transport of component A:
xA
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
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
13
Lecture [ 3 ]
Interface
at Ti,Pi
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
log 10 p A ( sat )
B*
A
T C*
*
14
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)
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
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)
pA =
cA=
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.
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
p A A x A p A ( sat )
(3.6)
(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)
Both Henrys law and Raoults law assume ideal gas behaviour :
vapour
mixture
liquid mixture
p(sat) ethanol
2
45 30 kPa
3
1
81 27 kPa
3
= 45 kPa
at system temperature
17
Lecture [ 3 ]
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
yA ()
y (0)
y A
NA
NA
c D AB
D AB c
y A () y A (0)
(3.8)
18
Lecture [ 3 ]
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)
D AB .c
y A
A 0
z
integrating again:
D AB .c y A Az B 0
(3.11)
19
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)
CHE3063F
MASS TRANSFER
Version
4/3/16 08:42:17 AM
20
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
CHE3063F
MASS TRANSFER
Version
4/3/16 08:42:17 AM
21
Lecture [ 4 ]
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
Lecture [ 4 ]
23
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
Lecture [ 4 ]
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
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
Lecture [ 4 ]
26