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Chapter 3

Stage and Continuous Gas-

Liquid Separation Processes

Introduction to Separations

The goal of a separations process is to purify solutions.

To do this we must cause differential transport of species or conversion of species

so that the purer mixtures can be collected. Most separations processes involve

differential transport.

Most separations processes involve differential transport. m i x e d separated Examples: Separation of blood

mixed

processes involve differential transport. m i x e d separated Examples: Separation of blood Purification of

separated

Examples:

Separation of blood Purification of drugs Purification of Au Refining of crude oil DNA testing Purification of organics Purification of water

Introduction to Separations

1.

Mixtures

Mixtures: 2 or more components

Mixture classification:

Homogeneous - single phase, gas or liquid

Air - N 2 , Ar, O 2

Dry syngas: CO/H 2 /CH 4 /CO 2

Heterogeneous - multiple, immiscible phases

Liquid + liquid, e.g. oil + water

solid + liquid

solid + gas

liquid + gas

Mixing - spontaneous, irreversible

Introduction to Separations 2. Separation Types:  Separation: Mixture  Products that differ in composition

Introduction to Separations

2. Separation Types:

Separation:

Mixture Products that differ in composition

Classification:

Force field (mechanical)

Gravity, pressure, electrical field, centrifugal force

Heterogeneous mixtures

Physical - exploit differences in physical properties

vapor pressure, solubility, molecular geometry, surface activity, freezing

point

Chemical - based on differences in reactivity

Mechanism of Separations Phase Phase  Phase contacts and component separation solute I II 
Mechanism of Separations
Phase
Phase
 Phase contacts and component separation
solute
I
II
 Necessary condition: two bulk phases are
usually only somewhat miscible in each other

Possible two phases: Gas Liquid, Gas Solid, Liquid Liquid, Liquid - Solid

Separation by phase contact is normally achieved in three steps:

1. Intimate contact of the two phases

2. Redistribution of the components between the two phases

3. Physical separation of the two phases

Although the extent of a separation is determined by thermodynamics, the rate of separations is limited by the differential rate at which the different species are moved. That is:

The Rate of Separation is limited by Mass Transport.

Processing Methods

Single-stage process

Mixing the two phases, eg. gas and liquid, together in a vessel and then separated

Multiple-stage process

P

F

1 S P
1
S
P

2

The phases are mixed in one stage, separated, and then brought into contact again

The two methods can be carried out batchwise or continuous.

Cascades is another terminology for multiple stage process. Sequences of separators can be used to achieve higher purities or to recover

more solute from a product stream.

Cascades can be configured in various ways.

Cascades

Three single section cascade configurations are:

P S 1 Countercurrent F P 2 S Crosscurrent F P 1 P 2 P
P
S
1
Countercurrent
F
P
2
S
Crosscurrent
F
P
1
P 2
P 3
P 4
S
F
P
6
2-D diamond
P
5
P
4
P 1
P 2
P 3

Experimental Gas-Liquid Equilibrium Data

Example: SO 2 air water system

1. An amount of SO 2 , air , and water are put in a closed container and shaken repeatedly at a given temperature until equilibrium is reached.

2. Samples of the gas and liquid are analyzed to determine the partial pressure p A of SO 2 (A) in the gas phase and the mole fraction x A in the liquid phase.

p A

and the mole fraction x A in the liquid phase. p A x A JUST Department

x A

Gas-Liquid Equilibrium: Henry’s Law

Applied for pressure low enough that vapor phase may be assumed as ideal gas.

For a species present as a very dilute solute in the liquid phase.

The equilibrium relationship between p A in the gas phase and x A can be expressed by a straight-line Henry’s law equation:

be expressed by a straight- line Henry’s law equation: Henry’s  Hx p A p A

Henry’s

Hx

p A

p

A

A

'

H x

P

 

x

A

y

A

A

where,

p A

H = Henry’s law constant (atm/mol fraction).

H' = Henry’s law constant (mol frac.gas/mol frac.liquid). = H/P.

X A = mole fraction of component A in liquid. ( dimension less ) Y A = mole fraction of component A in gas = p A /P. ( dimensionless )

P = total pressure (atm).

= partial pressure of component A (atm).

Example 10.2-1: Dissolved Oxygen Concentration in Water

What will to be the concentration of oxygen dissolved in water at 298 K when the solution is in equilibrium with air at 1 atm total pressure ? The Henry’s law constant is 4.38 x 10 4 atm/mol fraction.

The partial pressure p A of oxygen (A) in air is 0.21 atm.

Solution:

p

A

Hx

A

0.21=H x A = 4.38 x10 4 x A

Solving , x A = 4.80 x10 -6 mol fraction.

This means that 4.80 x10 -6 mol O 2 is dissolved in 1 mole water plus oxygen.

Single-Stage Equilibrium Contact

This is defined as one in which two different phases are brought into intimate contact with each other and then separated when equilibrium is achieved

During contact, intimate mixing occurs and various components diffuse and redistribute themselves between the two phases

Consider the two entering phases, L 0 and V 2 , of known amounts and compositions.

After

mixing

and

equilibrium,

the

two

streams V 1 and L 1 can be separated

V 1

the two streams V 1 and L 1 can be separated V 1 V 2 L

V 2

two streams V 1 and L 1 can be separated V 1 V 2 L 1
two streams V 1 and L 1 can be separated V 1 V 2 L 1
two streams V 1 and L 1 can be separated V 1 V 2 L 1

L

1

streams V 1 and L 1 can be separated V 1 V 2 L 1 L

L

0

Total mass balance:

L

0

V

2

L

1

V M

1

(1)

If three component, A, B, and C, present in the streams:

L

0

x

A0

L

0

x

C0

V y V y

2

2

A2

C2

L x L x

1

1

A1

C1

V y V y

1

1

A1

C1

Mx

= Mx

AM

CM

(2)

(3)

An equation for B is not needed since x A + x B + x C = 1.0

for B is not needed since x A + x B + x C = 1.0

Unknowns: L 1 , V 1 , x A1 , x C1 , y A1 , y C1 Other three equations are needed??

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Chapter 3-11

For Gas-liquid system

Solute A is in the gas phase V (or light phase) with inert air B

Also it is in the liquid phase L (or heavy phase) with inert water C

Assuming air is insoluble in the water phase and water does not vaporize to the gas phase

Gas phase is a binary of A-B and liquid phase is a binary of A-C.

V 1 (A-B)

of A-B and liquid phase is a binary of A-C. V 1 (A-B) V 2 (A

V 2 (A B) V 2 (A –

A
A
phase is a binary of A-C. V 1 (A-B) V 2 (A – B) A L
phase is a binary of A-C. V 1 (A-B) V 2 (A – B) A L

L 0 (A-C)

L 1 (A-C) Richer in A

 

L =L 1-x

A

V =V 1-y

A

L

L / 1-x

V=V / 1-y

A

A

A 1

1 y

A 1

where:

y

A

1

'

H x

A

1

y

If L = mole of inert water C;

A 1  y   If L ’ = mole of inert water C; V

V = moles inert air B:

'

'

'

'

'

'

L

L L

and V V V

0

1

2

1

Since A is the only component that distributes between the two phases , moles balance on solute A can be written as

L   x

'

1

A

0

x

A

0

y

  V

'

A

2

1

y

A

2

x

  L

'

A 1

1 x

A 1

  V

'

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Chapter 3-12

Example 10.3-1: Equilibrium Stage Contact for CO 2 Air-Water.

A gas mixture at 1.0 atm pressure abs containing air and CO 2 is contacted in a single-stage mixer continuously with pure water at 293 K. The two exit gas and liquid streams reach equilibrium. The inlet gas flow rate is 100 kg mol/h, with a mole fraction of CO 2 of y A2 = 0.20. The liquid flow rate entering is 300 kg mol water/h. calculate the amounts and compositions of the two outlet phases. Assume that water does nor vaporize to the gas phase.

Solution

V 1

y A1

L 0 = 300 kg mol/h x A0 = 0

Solution V 1 y A1 L 0 = 300 kg mol/h x A 0 = 0

V 2 = 100 kg mol/h y V 2 A 2 = 0.20 A2 = 0.20

L 1

x A1

1 atm

293 K

= 100 kg mol/h y A 2 = 0.20 L 1 x A1 1 atm 293
= 100 kg mol/h y A 2 = 0.20 L 1 x A1 1 atm 293

(1) The inert water flow is L’ = L 0 = 300 kg mol/h.

(2) The inert air flow V’ is obtained from,

V'= V 2 (1-y A2 )

= 100 (1-0.20)

= 80 kg mol/h .

A balance on CO 2 (A):

'

x

A

0

L

1

x

A

0

y

  V

'

A

2

1

y

A

2

'

x

  L

A 1

1

x

A 1

'

y

  V

A 1

1 y

A 1

300

 

0

1 0

  80  

0.20

1 0.20

x 1 x

 300

A 1

A 1

y 1 y

  80

A 1

A 1

(1)

The Resulting equation has two unknowns (x A1 and y A1 )

It is possible to calculate the y A1 by the use of Henry’s law because the gas and liquid are in equilibrium

y

A1

'

H x

A1

At 293 K, the Henry’s law constant H = 0.142 x 10 4 atm/mol frac. (Appendix A.3)

H' = H/P = 0.142 x 10 4 /1.0 = 0.142 x 10 4 mol frac. gas/mol frac. Liquid.

4 /1.0 = 0.142 x 10 4 mol frac. gas/mol frac. Liquid. y A 1 =

y A1 = 0.142 x 10 4 x A1

(2)

Solving equation (1) and (2) simultaneously, get x A 1 = 1.41 x 10 -

Solving equation (1) and (2) simultaneously, get x A1 = 1.41 x 10 -4 and y A1 = 0.20.

To calculate the total flow rates leaving,

L

1

'

L

1 x

A 1

V

1

'

V

1 y

A

1

300

1

1.41

10

4

300

kgmol h

/

80

1

0.20

100

kgmol h

/

In this case, since the liquid solution is so dilute, L 0 L 1 .

Graphical Representation

Cocurrent

V

1

V

2

Graphical Representation Cocurrent V 1 V 2 L 1 L 2 Total material balance: Component A

L 1

Graphical Representation Cocurrent V 1 V 2 L 1 L 2 Total material balance: Component A
Graphical Representation Cocurrent V 1 V 2 L 1 L 2 Total material balance: Component A
Graphical Representation Cocurrent V 1 V 2 L 1 L 2 Total material balance: Component A
Graphical Representation Cocurrent V 1 V 2 L 1 L 2 Total material balance: Component A

L 2

Total material balance:

Component A balance:

L L x V V y L   V L x V y

1

1

A1

1

1

2

A1

2

2

A 2

2

A 2

Again if there are inert components in both light and heavy phases such that flow rates of these inert components, i.e. L and V , remain constant, defining concentrations of solute- free basis as:

X

x

1 x

&

Y

y

1 y

Operating line: an equation obtained from material balance which relates compositions of any two passing streams together . It defines operating conditions within the

together . It defines operating conditions within the JUST Department of Chemical Engineering M a s
Component A balance becomes: L X  V Y  L X  V Y
Component A balance becomes:
L X  V Y  L X  V Y
'
'
'
'
x
x
1
1
2
2
where:
X 
A
1
,
X 
A
2
1
2
1  x
1  x
L
'
(
X  X  V Y  Y
)
'
(
)
A
1
A
2
or:
1
2
2
1
y
y
Y 
A
1
,
Y 
A
2
1
2
1  y
1  y
'
L
Y
 Y
A
1
A
2

2
1
'
V
X
 X
2
1
'
L
Equation of a straight line which passes through the points (X 1 , Y 1 ) and (X 2 , Y 2 ) with a slop of
'
V
For transfer of solute from heavy to light:
L

V
Eqm. curve
solute
Y
Operating line
X 1 > X 2
Y 2 > Y 1
Below equilibrium
curve
Y 2
-L ’ /V ’
Note that X 2e and Y 2e are the composition of the
heavy and light phases, respectively, if they
leave the stage in equilibrium
Y 1
X
X 2
X 1

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Chapter 3-17

For transfer of solute from light to heavy:

V  solute L X 1 < X 2 Y 2 < Y 1
V

solute
L
X 1 < X 2
Y 2 < Y 1

Y

Operating line

above equilibrium curve

Eqm. curve

Y 1 Y 2 X 1 X 2
Y 1
Y 2
X 1
X 2

X

there are no inert

components in the phases, operating line representing the material balance can no longer be a straight line, but becomes a

When

curve

y Eqm. curve y 2 y 1 x x 2 x 1
y
Eqm. curve
y 2
y 1
x
x 2
x 1

Countercurrent

V 1

Countercurrent V 1 V 2

V 2

Total material balance:

Component A balance:

V L V L x V y L x V y

L

0

0

A0

2

2

1

A 2

1

1

A1

1

A1

L

0

y  L x  V y L 0 0 A 0 2 2 1 A
y  L x  V y L 0 0 A 0 2 2 1 A
y  L x  V y L 0 0 A 0 2 2 1 A
y  L x  V y L 0 0 A 0 2 2 1 A

L 1

If there are inert components in the phases which do not transfer:

'

L

(

'

X X V Y Y

0

1

1

2

)

(

)

operating line equation:

'

L

'

V

For transfer of solute from heavy to light:

2

1

Y

X

Y

1

X

0

to light: 2 1 Y X  Y 1  X 0 L solute  V

L

solute



V

X 0 > X 1 Y 1 > Y 2

Operating line Below equilibrium curve

Eqm. curve Y Y 1 L ’ /V ’ Y 2 X X 1 X
Eqm. curve
Y
Y 1
L ’ /V ’
Y 2
X
X 1
X 0

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Chapter 3-19

For transfer of solute from light to heavy:

V

solute



L

Y

Eqm. curve

Y 2 L ’ /V ’ Y 1 X 0 X 1
Y 2
L ’ /V ’
Y 1
X 0
X 1

X 0 < X 1 Y 1 < Y 2

Operating line above equilibrium curve

When 
When

X

there are no inert

components in the phases, operating line representing the material balance can no longer be a straight line, but becomes a

curve

y Eqm. curve y 1 y 2 x x 1 x 0
y
Eqm. curve
y 1
y 2
x
x 1
x 0

Countercurrent Multiple-Contact Stages

To transfer more solute from the V 1 stream, for example, the single stage can be repeated by contacting the V 1 stream with fresh L 0 .

V

1

contacting the V 1 stream with fresh L 0 . V 1 V 2 More solute

V

2

the V 1 stream with fresh L 0 . V 1 V 2 More solute is

More solute is removed

with fresh L 0 . V 1 V 2 More solute is removed L 0 L

L 0

fresh L 0 . V 1 V 2 More solute is removed L 0 L 0
fresh L 0 . V 1 V 2 More solute is removed L 0 L 0
fresh L 0 . V 1 V 2 More solute is removed L 0 L 0
fresh L 0 . V 1 V 2 More solute is removed L 0 L 0

L

0

fresh L 0 . V 1 V 2 More solute is removed L 0 L 0

L

1

To conserve use of the L 0 stream and to get more concentrated product, countercurrent

multiple-stage contacting is generally used.

N = total number of ideal stages

V V V V 3 V n+1 V V V N-1 N 2 n N+1
V
V
V
V
3
V n+1
V
V
V N-1
N
2
n
N+1
1
n
N–1
N
1
2
L
L
0
L
L
L n
L N-1
N
1
2
L N-2
L n-1

Since the stages are ideal, any two streams leaving any stage are in equilibrium with

each other:

Example: V n and L n are in equilibrium

The two-phase system can be gas-liquid, vapor-liquid, liquid-liquid, etc.

Total overall balance on all stages,

L

0

V

N

1

L

N

V

1

= M

V N+1 and L N in mol/h M : total flow

Overall component balance on A, B or C,

L x

0

0

V y

1

N N

1

L x

N N

V y

1

1

= Mx M

x and y are mole fractions

For the first n stages ,

This is why we write n instead of N

first n stages , This is why we write n instead of N L L x

L L x V V y L  

0

0

0

n

1

n

1

n

n

1

1

V L x V y

n n

1

1

Solving for y n+1 ,

y  x  n  1 n V V n  1 n 
y
x
n
 1
n
V
V
n
1
n
1

L

n

V y

1

1

L x

0

0

slope

L

n

V

n

1

Highly important material balance equation

Called: Operating line

Relates y n+1 in V n+1 with x n in L n

V 1 , y 1 , L 0 and x 0 are constant and usually known or calculated using balance eqns above

Countercurrent Contact with Immiscible Streams

Stream V contains A and B with no C

L and V are immiscible in each other but only A being transferred

Stream L contains A and C with no B

If L and V vary from stage to stage, the slope L n /V n+1 varies

 Shown in the drawing: operating line and equilibrium line L V y  L
 Shown in the drawing: operating line and equilibrium line
L
V y
L x
operating
y
n
x
1
1
0
0
n
1
V
n
V
n
1
n
1
line
y 1
x 0
y
 The two plots can be
used to determine
the number of stages
N+1
4
y
stage 1
4
y 2
x 1
y
3
3
required to reduce
stage 2
equilibrium
the solute
concentration from
y 3
x 2
y
2
y
2
line
stage 3
y n = f(x n )
y N+1 to y 1
1
y
y 4
x 3
1
N = 4
x N
x
x
x
y N+1
x
x 4 = x N
0
1
2
3

x

Graphical procedure for counting number of stages

1.

Draw operating line.

2.

Draw equilibrium line (Henry’s law)

3.

Start at stage 1 by locating y 1 and x 0 on the operating line

4.

The vapor y 1 leaving is in equilibrium with the leaving x 1 and both points should be on the equilibrium line, thus locate this point by lying a horizontal line from the operating line at y 1 to the equilibrium line (one stage).

5.

Then y 2 and x 1 are on the operating line; locate this point by extending a vertical line from the equilibrium line at x 1 to the operating line.

6.

Then y 2 is in equilibrium with x 2 , and so on

7.

The steps are counted on the graph until y N+1 is reached

N.B. If A is dilute (< 10%) in both streams L and V, then the slope L n /V n+1 is constant and the operating line is essentially a straight line

Example 10.3-2: Absorption of Acetone in a Countercurrent Stage Tower

It is desired to absorb 90% of the acetone in a gas containing 1.0 mol% acetone in air in a

countercurrent stage tower. The total inlet gas flow to the tower is 30.0 kgmol/h, and the total inlet pure water flow to be used to absorb the acetone is 90 kgmol H 2 O/h. The process is to operate isothermally at 300 K and a total pressure of 101.3 kPa. The equilibrium relation for the acetone (A) in the gas-liquid is y A = 2.53x A . Determine the number of theoretical stages required for this separation.

Solution:

Identification of the data given :

y AN+1 = 0.01

x A0 = 0 V N+1 = 30.0 kg mol/h, L 0 = 90.0 kg mol/h.

(1 mole % of acetone in air entering)

(Pure water ) (total inlet gas flow to the tower ) (total inlet pure water )

V 1 L 0 y 1 x 0 stage 1 y 2 x 1 stage
V 1
L 0
y 1
x 0
stage 1
y 2
x 1
stage 2
y 3
x 2
stage 3
y 4
x 3
N = 4
x N
y N+1
V N+1
L N

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Chapter 3-25

Making an acetone material balance:

(1) amount of entering acetone = y AN+1 V N+1 = 0.01(30.0) = 0.3 kg mol/h.

(2) entering air = (1- y AN+1 )V N+1 = (1-0.01)(30.0) = 29.7 kg mol air/h

(3) acetone leaving in V 1 = 0.10(0.30) = 0.030 kg mol/h.

(4) acetone leaving in L N = 0.90(0.30) = 0.27 kg mol/h.

from the four steps above, V 1 , y A1 , L N ,and x AN can be calculated

V 1

y A1 = (0.030/29.73) = 0.00101

L N

x AN = (0.27/90.27)

= 29.7 + 0.03

= 29.73 kg mol air + acetone/h.

= 90.0 + 0.27

= 90.27 kg mol water + acetone /h.

= 0.0030.

Since the flow of liquid varies only slightly from L 0 = 90.0 at the inlet to L N = 90.27 at the the outlet and V from 30.0 to 29.73, the slope L n /V n+1 of the operating line is essentially constant.

This line is plotted, and the equilibrium relation of Henry y A = 2.53x A is also plotted.

Starting at point y A1 ,x A0 the stages are drawn. About 5.2 theoretical stages are required.

Mole fraction acetone in air, y A 0.012 y AN+1 Operating line 0.008 5 4
Mole fraction acetone in air, y A
0.012
y AN+1
Operating line
0.008
5
4
0.004
Equilibrium line
3
2
y A1
1
0 0
0.001
0.002
0.003
0.004
x A0
x AN

Mole fraction acetone in water, x A

Analytical Equations for Countercurrent Stage Contact

Assumptions:

1. Constant flow rates: L n = L N = constant = L and V n+1 = V N+1 = constant = V Operating line is straight

2. Equilibrium line is a straight line over the concentration range

Overall component balance on A :

Lx Vy

0

1

Lx Vy

N

Lx V y

n

1

Lx Vy

N

N

1

1

1

N

For the first n stages stages,

Lx

0

Vy

n

1

Combining (1) and (2):

Lx Vy

n

n

1

Or

Or

Or

Lx Vy Lx Vy

Lx Vy Lx Vy

0

1

N

N

1

0

1

n

n

1

L x

(

x

N

)

(

V y

n

y

n

1

N

1

)

(1)

(2)

Now, y n+1 and x n+1 are in equilibrium and the equilibrium is straight line:

y

L x

(

n

1

n

mx

n

1

x

N

)

and also

(

V mx

n

1

y

y

N

1

N

1

)

mx

N

1

Divide by mV:

A = absorption factor;

y

m

Ax

N 1

Ax

x n 1

n

N

where A = L/mV

S = 1/A = stripping factor

This equation can be used to count number of stages in stripping and absorption

Kremser Equations

For stripping section: transfer of solute A from phase L to phase V:

N

ln

x

0

(

y

N

1

/

m

)

(1

A

)

A

x

(

 

/

m

)

 

N

y

N 1

 
 

ln(1/

A

)

When A = 1,

x  x N  0 N x N  ( y / m )
x
 x
N 
0
N
x
N  (
y
/
m
)
N  1

For absorption section: transfer of solute A from phase V to phase L:

 y  mx  1  1  N  1 0 ln 1
 y
 mx
1 
1 
N
 1
0
ln
1 
y
 mx
A
A
1
0
N 
ln(A)

When A = 1,

N

y 1

mx

0

y N 1

y

1

If the equilibrium line is not straight but curved somewhat, the slop will vary and,

If the equilibrium line is not straight but curved somewhat, the slop will vary and, Hence, m and A = L/mV will vary.

Procedure (for varying A):

1. Calculate A 1 at L 0 & V 1 :

A 1

=L o /m 1 V 1

2. Calculate A N at L N &V N+1 : A N =L N /m N V N+1

3. Calculate the geometric A ave. =

4. Calculate N.

A A 1 N
A A
1
N

Example 10.3-3: Number of Stages by Analytical Equation.

Repeat Example 10.3-2 but use the Kremser analytical equation for countercurrent stage processes.

Solution,

At Stages 1
At Stages 1

V 1 = 29.73 kg mol/h, y A1 = 0.001001, L 0 = 90.0, and x A0 = 0.

Also, the equilibrium relation is y A = 2.53x A where m = 2.53.

Then,

A

1

L L

0

mV

mV

1

90.0

2.53

29.73

1.20

V N + 1 =30.0, y A N + 1 = 0.01, L N =

V N+1 =30.0, y AN+1 = 0.01, L N = 90.27, and x AN = 0.0030.

At Stage N
At Stage N
L 90.27 Then, A  N   1.19 N mV 2.53  30.0 N
L
90.27
Then,
A 
N
 1.19
N
mV
2.53
30.0
N  1
A 
A A
0.20
1.19
The geometric average,
1
N
 y
mx
1 
1 
N
1
0
ln
1 
y
mx
A
A
1
0
N
5.04

ln(A)

1.195

This compares closely with 5.2 stages using graphical method

Mass Transfer Between Phases

This concerns transfer of solute from one fluid phase by convection and then through a second fluid phase by convection

Example: diffusion of ammonia (solute) through air (gas phase) and then diffuse through and be absorbed in an adjacent and immiscible liquid phase, such as water.

The two phases should be in direct contact with each other, such as in a packed, tray, or spray type tower

Concentration gradient exist in each phase, causing mass transfer to occur.

Usually equilibrium exists at the interface between the two fluid phases.

At equilibrium, the chemical potential is equal in the two phases and not

concentration

The departure from equilibrium represents the driving force for diffusion

Equilibrium relations are important to determine concentration profiles for predicting rates of mass transfer.

Concentration Profiles in Interface Mass Transfer

Usually the two phases which present together with interface between them are essentially immiscible in each other

Consider the situation shown in the drawing when solute A diffuses from the bulk of gas phase G to the liquid phase L.

G phase

L phase

y AG y Ai
y AG
y Ai
phase G to the liquid phase L. G phase L phase y AG y Ai Intefcae

Intefcae

N A

x Ai x AL
x Ai
x AL

Solute A must pass through the interface

Concentration gradient must exist to cause mass transfer through the resistances in each phase.

cause mass transfer through the resistances in each phase. y A G = average bulk concentration

y AG = average bulk concentration of A in the gas phase = p A /P

x AL = average bulk concentration of A in the liquid phase

y AG to y Ai at the interface

Liquid A starts at x Ai at the interface and falls to x AL .

y Ai

f x

(

Ai

)

y Ai and x Ai are in equilibrium and are related by the equilibrium relation:

Mass Transfer Using Film Mass-Transfer Coefficients and Interface Concentrations 1. Equimolar Counterdiffusion  For A

Mass Transfer Using Film Mass-Transfer Coefficients and Interface Concentrations

1. Equimolar Counterdiffusion

For A diffusing from the gas to liquid and B in counter diffusion from liquid to gas,

N A

k

'

y

(

y y

AG

Ai

)

k x x

'

x

(

Ai

AL

)

y AG y Ai = driving force in the gas phase

N B G phase L phase y AG y Ai x Ai N A x
N B
G phase
L phase
y AG
y
Ai
x Ai
N A
x AL
Intefcae
x Ai – x AL = driving force in the liquid phase P Eqm. y
x Ai – x AL = driving force in the liquid phase
P
Eqm.
y AG
k '
 y
k '
line
Rearranging:
x
y AG
Ai
x
'
'
k y
 x
k y
x AL
Ai
y Ai
Graphical solution for the interface:
M
1. Determine points y AG and x AL by sampling
y
*
A
2. Locate point P (y AG , x AL )
*
3. From point P sketch line PM with slope –k ’ x /k ’
x
x AL
x Ai
A
y

4. intersection of line PM with eqm line would determine the interface compositions.

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Chapter 3-35

2. Diffusion of A Through Stagnant or Nondiffusing B

For A diffusing through a stagnant gas phase and then through a stagnant liquid phase

N

A

k y

(

y AG

y

Ai

)

k x x

x

(

Ai

AL

)

Now:

k

y

k

'

y

(1

y

)

A iM

,

k

x

k

'

x

(1

x

)

A iM

N B = 0 G phase L phase y AG y Ai N x Ai
N B = 0
G phase
L phase
y AG
y Ai
N
x Ai
A
x
AL
Intefcae

where:

(1

(1

y

)

A iM

x

)

A iM

(1

y

Ai

)

(1

 

y

AG

)

 

ln[(1

y

Ai

)/(1

y

AG

)]

(1

x

AL

)

(1

 

x

Ai

)

ln[(1

x

AL

)/(1

x

Ai

)]

,

Substituting and rearranging:

k

'

x

/(1

x

)

A iM

 

'

k

y

/(1

y

)

A iM

y AG

y

Ai

x AL

x

Ai

P Eqm. y AG  k ' x /(1  x )  A iM
P
Eqm.
y AG
k
'
x /(1
 x
)
A iM
line
k
y /(1
'
 y
)
A iM
y
Ai
M
y
*
A
*
x AL
x Ai
x
A

Procedure for locating interface compositions is similar to the previous case; but involves trial and error as x Ai and y Ai are required to determine the slope for the PM line. For the first trial use (1-x A ) iM = (1-y A ) iM = 1 (i.e., dilute solution) and then iterate.

Example 10.4-1: : Interface Compositions in Interface Mass Transfer

The solute A is being absorbed from a gas mixture of A and B in wetted-wall tower with the liquid flowing as a film downward along the wall. At a certain point in the tower the bulk gas concentration y AG = 0.38 and the bulk liquid concentration is x AL = 0.10. The tower is operating at 298 K and 1.013×10 5 Pa and the equilibrium data are as follows

The solute A diffuses through stagnant B in the gas phase and then through nondiffusing liquid.

Given that k y = 1.465×10 -5 kgmol A/s.m 2 .mol frac and k x = 1.967×10 -3 kgmol/s.m 2 . mol frac; calculate the interface concentration y Ai and x Ai and the flux N A .

x A

y A

0

0

0.05

0.022

0.10

0.052

0.15

0.087

0.20

0.131

0.25

0.187

0.30

0.265

0.35

0.385

Solution

First we plot the equilibrium data

Now we need to find the point P on the graph

Since the correlations are for dilute solutions, (1-y A ) iM and (1-x A ) iM are approximately 1.0 and the coefficients are the same as k’ y and k’ x .

Point P is plotted at y AG = 0.380 and x AL = 0.1.

For the first trial (1-y A ) iM and (1-x A ) iM are assumed as 1.0 and the slope of line PM is,

slope 

 

'

k

x

/(1

x

)

A iM

 

'

k

y

/(1

y

)

A iM



1.967

10

3

/1.0

1.465

10

3

/1.0

 1.342

A line through point P with a slope of 1.342 is plotted in the figure intersecting the equilibrium line at M 1 , where

y Ai = 0.183

and

x Ai = 0.247.

Equilibrium data 0.4 P y D AG 0.3 0.2 y M Ai M 1 0.1
Equilibrium data 0.4 P y D AG 0.3 0.2 y M Ai M 1 0.1
Equilibrium data
0.4
P
y
D
AG
0.3
0.2
y
M
Ai
M 1
0.1
y
*
A
E
0 0
0.1
0.2 0.3
0.4
x AL
x Ai
x
*
A

For the second trial we use y Ai and x Ai from the first trial to calculate the new slope.

(1

(1

 

(1

y

Ai

)

(1

 

y

AG

)

 

y

)

A ln[(1

iM

y

Ai

)/(1

y

AG

)]

 

(1

x

AL

)

(1

 

x

Ai

)

x

)

A ln[(1

iM

x

AL

)/(1

x

Ai

)]

0.715

0.825

slope 

 

'

k

x

/(1

x

)

A iM

 

'

k

y

/(1

y

)

A iM



1.967

10

3

/ 0.825

1.465

10

3

/ 0.715

 1.163

A line through point P with a slope of 1.163 is plotted and intersects the equilibrium line at M, where y Ai = 0.197 and x Ai = 0.257. Using these new values for the third trial, the following values are calculated:

(1

y

)

A iM

(1

x

)

A iM

(1

0.197)

 

(1

0.380)

ln[(1

(1

0.197) /(1

0.38)]

0.1)

 

(1

0.257)

ln[(1

0.1) /(1

0.257)]

0.709

0.820

slope 

k

'

x

/(1

x

)

A iM



1.967

10

3

/ 0.820

 1.160

k

'

1.465

10

3

/ 0.709

 

y

/(1

y

)

A iM

This slope of 1.160 is essentially the same as the slope of 1.163 for the second trial. Hence, the final values are y Ai = 0.197 and x Ai = 0.257 and are shown as point M.

To calculate the flux,

N

N

A

A

k

'

y

(1

y

k

A

'

x

)

iM

(1

x

A

)

iM

(y

(x

AG

y

Ai

Ai

x

AL

)

)

1.465 10

3

0.709

1.967

10

3

0.820

(0.380

0.197)

(0.257

0.100)

3.78 10

4

kgmol/s.m

2

3.78 10

4

kgmol/s.m

2

Note that the flux N A