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Chemical Engineering Mass Transfer Notes

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Lectures 1-8, T1

(original document: Dr Mark Williamson)

Photo credit: BruceBlaus (http://goo.gl/etpSOu)

Department of Chemical

Engineering

Introduction

Lecture [ 1 ]

Transport

phenomena

Fluid dynamics

transport of momentum

Heat transfer

transport of energy

transport of mass

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.

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

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 ]

A definition: Transfer of one substance through another on molecular and/or

macroscopic scales

Diffusive (molecular) 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 desorption (stripping)

fractional liquid extraction

Gas

(air)

cH 2 S

dialysis, electro-dialysis

reverse osmosis

z

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.

Lecture [ 2 ]

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 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 ]

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

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)

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 ]

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

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

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

Lecture [ 2 ]

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

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

1.0

0.718

Mole

fraction

0.282

0

-0.25

11

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

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

(1829 1901)

was a German

physiologist. In

1870 he was the

first to devise a

technique for

measuring

cardiac output.

It is the principle analytical expression of molecular diffusion transport.

13

Lecture [ 3 ]

3 common situations:

1) Pure constituent A :

Interface

at Ti,Pi

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

A,B,C = constants from lit.

T

= temperature [K]

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

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)

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

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)

(kPa.m3/mol )

(temperature-dependent)

pA =

cA=

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.

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

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)

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)

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

Both Henrys law and Raoults law assume ideal gas behaviour :

vapour

mixture

2 mol ethanol

+

1 mol methanol

liquid mixture

p(sat) ethanol

2

45 30 kPa

3

1

81 27 kPa

3

= 45 kPa

at system temperature

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

Lecture [ 3 ]

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

yA ()

y (0)

y A

NA

NA

c D AB

D AB c

y A () y A (0)

(3.8)

18

Lecture [ 3 ]

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)

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

stagnant B)

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

stagnant B)

Lecture [ 4 ]

from 0 to , instead:

(4.5)

And is known from eq. 4.4. Substituting this value of into eq. 4.5:

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 ]

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

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

stagnant B)

Lecture [ 4 ]

for

(4.8)

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

26

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