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Liquid Separation Processes

Introduction to Separations

The goal of a separations process is to purify solutions.

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

differential transport.

Examples:

Separation of blood

Purification of drugs

Purification of Au

Refining of crude oil

DNA testing

Purification of organics

mixed separated Purification of water

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-2

Introduction to Separations

1. Mixtures

Mixtures: 2 or more components

Mixture classification:

Homogeneous - single phase, gas or liquid

solid + liquid

solid + gas

liquid + gas

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-3

Introduction to Separations

2. Separation Types:

Separation:

Mixture Products that differ in composition

Classification:

Force field (mechanical)

Heterogeneous mixtures

point

Chemical - based on differences in reactivity

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-4

Mechanism of Separations

Phase contacts and component separation Phase Phase

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

1. Intimate contact of the two phases

2. Redistribution of the components between the two phases

3. Physical separation of the two phases

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.

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-5

Processing Methods

Single-stage process

P1 S

Mixing the two phases, eg. gas and liquid,

F P2

together in a vessel and then separated

Multiple-stage process

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

again

• 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.

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-6

Cascades

Three single section cascade configurations are:

P1 S

Countercurrent

F P2

S

Crosscurrent

F P1

P2 P3 P4

F P6

2-D diamond P5

P4

P1 P2 P3

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-7

Experimental Gas-Liquid Equilibrium Data

Example: SO2 – air – water system

1. An amount of SO2 , 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 pA

of SO2 (A) in the gas phase and the mole fraction xA in the liquid phase.

pA

xA

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-8

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 pA in the gas phase and xA can be expressed

by a straight-line Henry’s law equation:

pA

p A Hx A Henry’s

P y A H ' x A

xA

where,

pA = partial pressure of component A (atm).

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

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

XA = mole fraction of component A in liquid. ( dimension less )

YA = mole fraction of component A in gas = pA/P. ( dimensionless )

P = total pressure (atm).

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-9

Example 10.2-1: Dissolved Oxygen Concentration in Water

the solution is in equilibrium with air at 1 atm total pressure ? The Henry’s

law constant is 4.38 x 104 atm/mol fraction.

Solution:

pA Hx A

0.21=H xA = 4.38 x104 xA

This means that 4.80 x10-6 mol O2 is dissolved in 1 mole water plus oxygen.

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-10

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

V1 V2

known amounts and compositions.

After mixing and equilibrium, the two L0 L1

streams V1 and L1 can be separated

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

L0 x A0 V2 yA2 L1x A1 V1yA1 Mx AM (2)

L0 x C0 V2 yC2 L1x C1 V1yC1 = Mx CM (3)

An equation for B is not needed since xA + xB + xC = 1.0

Unknowns: L1, V1, xA1, xC1, yA1, yC1 Other three equations are needed??

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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.

V1 (A-B) V2 (A –B)

A

If L’ = mole of inert water C; V ’ = moles inert air B: L=L 1-x A L L/ 1-x A

L'0 L'1 L' and V2' V1' V ' V=V 1-y A V=V/ 1-y A

Since A is the only component that distributes between the two phases , moles balance on

solute A can be written as

x A0 ' y A2 ' x A1 ' y A1

L V L V where: y A1 H ' x A1

'

1 x A0 1 y A2 1 x A1 1 y A1

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-12

Example 10.3-1: Equilibrium Stage Contact for CO2 –Air-Water.

A gas mixture at 1.0 atm pressure abs containing air and CO2 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 CO2 of yA2 =

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.

V1 V2 = 100 kg mol/h

Solution yA1

1 atm yA2 = 0.20

L0 = 300 kg mol/h 293 K L1

xA0 = 0

xA1

(1) The inert water flow is L’ = L0 = 300 kg mol/h.

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

V'= V2 (1-yA2 )

= 100 (1-0.20)

= 80 kg mol/h .

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-13

A balance on CO2 (A):

x y x y

L' A0 V ' A2 L' A1 V ' A1

1 x A0 1 y A2 1 x A1 1 y A1

0 0.20 x A1 y A1

300 80

300

80 (1)

1 0 1 0.20 1 x A1 1 y A1

It is possible to calculate the yA1 by the use of Henry’s law because the gas and

liquid are in equilibrium

yA1 H' x A1

At 293 K, the Henry’s law constant H = 0.142 x 104 atm/mol frac. (Appendix A.3)

H' = H/P = 0.142 x 104 /1.0 = 0.142 x 104 mol frac. gas/mol frac. Liquid.

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-14

Solving equation (1) and (2) simultaneously,

get xA1 = 1.41 x 10-4 and yA1 = 0.20.

L' 300

L1 4

300kgmol / h

1 x A1 1 1.4110

V' 80

V1 100kgmol / h

1 y A1 1 0.20

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-15

Graphical Representation

Cocurrent V1 V2

L1

L2

L1 V1 L2 V2

Total material balance:

Component A balance: L1 x A1 V1 y A1 L2 x A2 V2 y A2

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 y

X & Y

1 x 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

equipment.

Slope of operating line: obtained from the difference in compositions of any two

subsequence passing streams

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-16

Component A balance becomes:

1 x A1 1 x A2

or: L ( X 1 X 2 ) V (Y2 Y1 )

' '

y A1 y

Y1 , Y2 A2

L' Y2 Y1 1 y A1 1 y A2

V' X 2 X1

L'

Equation of a straight line which passes through the points (X1, Y1) and (X2, Y2) with a slop of

V'

For transfer of solute from heavy to light:

Y Eqm. curve

L solute

V

Operating line

X1 > X 2

Below equilibrium

Y2 > Y1 curve

Y2

-L’/V ’

Note that X2e and Y2e are the composition of the

Y1

heavy and light phases, respectively, if they

leave the stage in equilibrium X

X2 X1

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-17

For transfer of solute from light to heavy:

V solute

L Y Eqm. curve

Operating line Y1

X1 < X2

above equilibrium

Y 2 < Y1 curve Y2

X

X1 X2

When there are no inert

components in the phases, y Eqm. curve

operating line representing the

material balance can no longer y2

be a straight line, but becomes a

curve y1

x2 x1 x

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-18

Countercurrent V1 V2

Total material balance: L0 V2 L1 V1 L0

L1

Component A balance: L0 x A0 V2 y A2 L1 x A1 V1 y A1

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

L' Y2 Y1

L ( X 0 X 1 ) V (Y1 Y2 )

' '

operating line equation: '

V X1 X 0

For transfer of solute from heavy to light:

L solute

V Y Eqm. curve

X0 > X1

Y1 > Y2 Y1

Below equilibrium Y2

curve

X

X1 X0

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-19

For transfer of solute from light to heavy:

Y Eqm. curve

V L

solute

Y2

L’/V ’

X0 < X 1

Y1 < Y 2 Y1

Operating line

above equilibrium

curve X

X0 X1

components in the phases,

operating line representing the y1

material balance can no longer

be a straight line, but becomes a

y2

curve

x1 x0 x

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-20

Countercurrent Multiple-Contact Stages

To transfer more solute from the V1 stream, for example, the single stage can be

repeated by contacting the V1 stream with fresh L0.

L0

L0 L1

To conserve use of the L0 stream and to get more concentrated product, countercurrent

multiple-stage contacting is generally used. N = total number of ideal stages

V1 N–1

1 2 n N

L0 L1 L2 Ln-1 Ln LN-2 LN-1 LN

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

each other:

Example: Vn and Ln are in equilibrium

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

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-21

Total overall balance on all stages,

VN+1 and LN in mol/h

L0 VN 1 LN V1 = M

M : total flow

Overall component balance on A, B or C,

L0 x0 VN 1 yN 1 LN xN V1 y1 = MxM x and y are mole fractions

For the first n stages , This is why we write n instead of N

L0 Vn1 Ln V1

L0 x0 Vn1 yn1 Ln xn V1 y1

Solving for yn+1,

yn 1 n x n 1 1 0 0

Vn 1 Vn 1 Called: Operating line

Relates yn+1 in Vn+1 with xn in Ln

Ln

slope V1, y1, L0 and x0 are constant and usually

Vn 1 known or calculated using balance eqns above

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-22

Countercurrent Contact with Immiscible Streams

Stream V contains A and B with no C Stream L contains A and C with no B

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

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

Shown in the drawing: operating line and equilibrium line

Ln Vy L x operating

yn 1 xn 1 1 0 0

Vn 1 Vn 1 line

y1 x0 yN+1

The two plots can be 4

used to determine stage 1 y4

the number of stages y2 x1 3

y3

required to reduce stage 2

the solute y3 equilibrium

x2 2

concentration from y y2 line

stage 3 yn = f(xn)

yN+1 to y1 y4 y1 1

x3

N=4

yN+1 xN x0 x1 x2 x3 x4 = xN

x

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-23

Graphical procedure for counting number of stages

1. Draw operating line.

4. The vapor y1 leaving is in equilibrium with the leaving x1 and both points should be on

the equilibrium line, thus locate this point by lying a horizontal line from the operating

line at y1 to the equilibrium line (one stage).

5. Then y2 and x1 are on the operating line; locate this point by extending a vertical line

from the equilibrium line at x1 to the operating line.

6. Then y2 is in equilibrium with x2, and so on

7. The steps are counted on the graph until yN+1 is reached

N.B. If A is dilute (< 10%) in both streams L and V, then the slope Ln/Vn+1 is

constant and the operating line is essentially a straight line

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-24

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 H2O/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 yA = 2.53xA. Determine the number of

theoretical stages required for this separation.

V1 L0

Solution: y1 x0

Identification of the data given : stage 1

y2 x1

yAN+1= 0.01 (1 mole % of acetone in air entering) stage 2

xA0 = 0 (Pure water )

y3 x2

VN+1 = 30.0 kg mol/h, (total inlet gas flow to the tower )

L0 = 90.0 kg mol/h. (total inlet pure water ) stage 3

y4 x3

N=4

yN+1 xN

VN+1 LN

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-25

Making an acetone material balance:

(2) entering air = (1- yAN+1 )VN+1 = (1-0.01)(30.0) = 29.7 kg mol air/h

(3) acetone leaving in V1= 0.10(0.30) = 0.030 kg mol/h.

from the four steps above, V1 , yA1 , LN ,and xAN can be calculated

yA1 = (0.030/29.73) = 0.00101

LN = 90.0 + 0.27 = 90.27 kg mol water + acetone /h.

xAN = (0.27/90.27) = 0.0030.

Since the flow of liquid varies only slightly from L0 = 90.0 at the inlet to LN =

90.27 at the the outlet and V from 30.0 to 29.73, the slope Ln /Vn+1 of the operating

line is essentially constant.

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-26

This line is plotted, and the equilibrium relation of Henry yA = 2.53xA is also

plotted.

Starting at point yA1 ,xA0 the stages are drawn. About 5.2 theoretical stages are

required.

Mole fraction acetone in air, yA

0.012

yAN+1

Operating line

0.008

5

4

0.004

3 Equilibrium line

yA1 2

00 1 0.002 0.003 0.004

0.001

xA0 xAN

Mole fraction acetone in water, xA

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-27

Analytical Equations for Countercurrent Stage Contact

Assumptions:

1. Constant flow rates: Ln = LN = constant = L and Vn+1 = VN+1 = constant = V

→ Operating line is straight

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

Lx0 Vy N 1 LxN Vy1 Or Lx0 Vy1 LxN Vy N 1 (1)

For the first n stages stages,

Lx0 Vyn1 Lxn V1 y1 Or Lx0 Vy1 Lxn Vyn1 (2)

Combining (1) and (2):

Lxn Vyn1 LxN Vy N 1 Or L( xn xN ) V ( yn1 y N 1 )

Now, yn+1 and xn+1 are in equilibrium and the equilibrium is straight line:

yn1 mxn1 and also y N 1 mx N 1

L( xn xN ) V (mxn1 yN 1 )

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-28

Divide by mV: A = absorption factor;

y N 1

xn1 Ax n Ax N where A = L/mV

S = 1/A = stripping factor

m

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:

x0 ( y N 1 / m) x0 xN

ln (1 A) A N

xN ( y N 1 / m)

When A = 1,

xN ( y N 1 / m)

N

ln(1 / A)

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

y mx 0 1 1 y N 1 y1

ln N1 1 N

y1 mx 0 A A When A = 1,

y1 mx0

N

ln(A)

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-29

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

Hence, m and A = L/mV will vary.

4. Calculate N.

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-30

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

V1 = 29.73 kg mol/h,

yA1 = 0.001001,

L0 = 90.0, and

xA0 = 0.

Then,

L L0 90.0

A1 1.20

mV mV1 2.53 29.73

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-31

At Stage N

VN+1 =30.0,

yAN+1 = 0.01,

LN = 90.27, and

xAN = 0.0030.

LN 90.27

Then, AN 1.19

mVN 1 2.53 30.0

y N1 mx 0 1 1

ln 1

y1 mx 0 A A

N 5.04

ln(A)

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-32

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.

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Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-33

Concentration Profiles in Interface Mass Transfer

Usually the two phases which present together with interface between them are

essentially immiscible in each other

G phase

Consider the situation shown in the drawing when

L phase

solute A diffuses from the bulk of gas phase G to the yAG

liquid phase L. yAi

xAi NA

• Solute A must pass through the interface

xAL

Intefcae

• Concentration gradient must exist to cause

mass transfer through the resistances in each phase.

xAL = average bulk concentration of A in the liquid phase

yAG to yAi at the interface

Liquid A starts at xAi at the interface and falls to xAL.

yAi and xAi are in equilibrium and are related by the equilibrium relation:y Ai f ( x Ai )

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-34

Mass Transfer Using Film Mass-Transfer Coefficients and

Interface Concentrations

1. Equimolar Counterdiffusion

NB G phase

For A diffusing from the gas to liquid and

L phase yAG

B in counter diffusion from liquid to gas, yAi

xAi

N A k ' y ( y AG y Ai ) k ' x ( x Ai x AL ) xAL

NA

Intefcae

yAG – yAi = driving force in the gas phase

xAi – xAL = driving force in the liquid phase yAG P Eqm.

Rearranging: k ' x y AG y Ai

line

k 'x

k y' x AL x Ai k y'

yAi

Graphical solution for the interface: M

1. Determine points yAG and xAL by sampling

y*A

2. Locate point P (yAG, xAL)

3. From point P sketch line PM with slope –k’x/k’y xAL xAi x*A

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 NB = 0 G phase

and then through a stagnant liquid phase L phase yAG

yAi

N A k y ( y AG y Ai ) k x ( x Ai x AL ) xAi NA

xAL

' ' Intefcae

k k

Now: ky y

, kx x

(1 y A )iM (1 x A )iM yAG P Eqm.

k ' /(1 x A )iM line

'x

where: (1 y A )iM (1 y Ai ) (1 y AG ) , k y /(1 y A )iM

ln[(1 y Ai ) /(1 y AG )]

(1 x AL ) (1 x Ai ) yAi

(1 x A )iM M

ln[(1 x AL ) /(1 x Ai )]

y*A

Substituting and rearranging:

xAL xAi x*A

k ' x /(1 x A )iM y AG y Ai

'

k y /(1 y A )iM x AL x Ai

Procedure for locating interface compositions is similar to the previous case; but

involves trial and error as xAi and yAi are required to determine the slope for the PM

line. For the first trial use (1-xA)iM = (1-yA)iM = 1 (i.e., dilute solution) and then iterate.

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-36

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 yAG = 0.38 and the bulk liquid

concentration is xAL = 0.10. The tower is operating at 298 K and 1.013×105 Pa

and the equilibrium data are as follows

xA yA

The solute A diffuses through stagnant B in the gas phase 0 0

0.05 0.022

and then through nondiffusing liquid.

0.10 0.052

0.15 0.087

0.20 0.131

Given that k’y = 1.465×10-5 kgmol A/s.m2.mol frac and 0.25 0.187

k’x = 1.967×10-3 kgmol/s.m2. mol frac; calculate the 0.30 0.265

interface concentration yAi and xAi and the flux NA. 0.35 0.385

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-37

Solution

Now we need to find the point P on the graph

Since the correlations are for dilute solutions, (1-yA)iM and (1-xA)iM are approximately

1.0 and the coefficients are the same as k’y and k’x .

Point P is plotted at yAG = 0.380 and xAL = 0.1.

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

slope ' 3

1.342

k y /(1 y A )iM 1.465 10 / 1.0

A line through point P with a slope of –1.342 is plotted in the figure intersecting the

equilibrium line at M1, where

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-38

Equilibrium data

0.4 P

yAG D

0.3

yAi 0.2 M

M1

0.1

y*A

E

0

0 0.1 0.2 0.3 0.4

xAL xAi x*A

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-39

For the second trial we use yAi and xAi from the first trial to calculate the new slope.

(1 y Ai ) (1 y AG )

(1 y A )iM 0.715

ln[(1 y Ai ) /(1 y AG )]

(1 x AL ) (1 x Ai )

(1 x A )iM 0.825

ln[(1 x AL ) /(1 x Ai )]

slope ' 3

1.163

k y /(1 y A )iM 1.465 10 / 0.715

A line through point P with a slope of –1.163 is plotted and intersects the

equilibrium line at M, where yAi = 0.197 and xAi = 0.257. Using these new values

for the third trial, the following values are calculated:

(1 0.197) (1 0.380)

(1 y A )iM 0.709

ln[(1 0.197) /(1 0.38)]

(1 0.1) (1 0.257)

(1 x A )iM 0.820

ln[(1 0.1) /(1 0.257)]

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-40

k x' /(1 x A )iM 1.967 103 / 0.820

slope ' 3

1.160

k y /(1 y A )iM 1.465 10 / 0.709

This slope of –1.160 is essentially the same as the slope of –1.163 for the second

trial.

Hence, the final values are yAi= 0.197 and xAi = 0.257 and are shown as point M.

k 'y 1.465 103

NA (yAG yAi ) (0.380 0.197) 3.78 104 kgmol / s.m 2

(1 yA )iM 0.709

NA (x Ai x AL ) (0.257 0.100) 3.78 104 kgmol / s.m 2

(1 x A )iM 0.820

Note that the flux NA through each phase is the same as in other phase, which should

be the case at steady state.

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-41

Overall Mass-Transfer Coefficients and Driving Forces

Single phase mass transfer coefficients k’x and k’y (or kx and ky) are difficult to measure

experimentally; it is rather overall mass transfer coefficients K’x and K’y can be

measured based on liquid phase or gas phase

The overall mass transfer K’y is defined as:

L phase

where K’y is based on the overall gas-phase driving in yAi

yAG

kg mol/s.m2.mol frac. xAi NA

xAL

Intefcae

y*A : the value that would be in equilibrium with xAL.

Eqm.

line

N A K x' x*A x AL

in kg mol/s.m2.mol frac. y*A

x*A : the value that would be in equilibrium with yAG. xAL x*A

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-42

1. Equimolar counterdiffusion and/or diffusion in dilute solutions

For this case, the following equations are valid: yAG D Eqm.

line

N A k ' y ( y AG y Ai ) k ' x ( x Ai x AL )

m”

According to the figure: yAi

y AG y y AG y Ai y Ai y

M

*

A

*

A

m’

y Ai y *A y*A

Between point E and M, the slope m’ is: m

'

E

x Ai x AL xAL xAi

y AG y A y AG y Ai m x Ai x AL

* ' x*A

Total resistance 1/K’y =

Or: NA NA ' NA 1 1 ' 1 gas film resistance 1/k’y

' m ' m

K y' ky kx K y' k y' k x' + liquid film resistance m’/k’x

Similarly:

y AG y Ai 1 1 1

x y AL x x Ai x Ai x AL

* *

& m"

K x' m" k y' k x'

A A

x*A x Ai

If m’ is small: gas solute A is very soluble in the liquid phase 1 / K y' 1 / k y'

“gas-phase is controlling” Or M moves to E: y AG y *A y AG y Ai

If m” is small: solute A is very insoluble in the liquid phase 1 / K x' 1 / k x'

“liquid-phase is controlling” Or M moves to D: x Ai x*A

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-43

2. Diffusion of A through stagnant or nondiffusing B

k'y k 'x

NA ( y AG y Ai ) ( x Ai x AL )

(1 y A )iM (1 x A )iM

y AG y*A y AG y Ai m' x Ai x AL

In case of A diffusing through nondiffusing B, overall coefficients are defined as:

K y' K x' *

NA

y AG y A

*

xA xAL

(1 y )

A *M (1 x A )*M

K y'

where: K y overall gas mass-transfer coefficient for stagnant diffusion

(1 y A )*M

K x'

Kx overall liquid mass-transfer coefficient for stagnant diffusion

(1 x A )*M

1 1 m' (1 y *A ) (1 y AG )

' ' where (1 y A )*

K y /(1 y A )*M k y /(1 y A )iM k x /(1 x A )iM

'

ln[(1 y *A ) /(1 y AG )]

1 1 1 *

" ' ' where (1 x A )*

(1 x AL ) (1 x A)

K x /(1 x A )*M m k y /(1 y A )iM k x /(1 x A )iM

'

ln[(1 x AL ) /(1 x*A )]

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-44

Example 10.4-2: Overall Mass-Transfer Coefficients from Film Coefficients

Using the same data as in the previous example, calculate the overall mass-transfer

coefficient K’y, the flux, and the percent resistance in the gas and liquid films. Do this for

the case of A diffusing through stagnant B.

Solution

yAG 0.4 P D

From the figure, y*A = 0.052, which is in equilibrium 0.3

with the bulk liquid xAL = 0.1

yAi 0.2 M

For yAi = 0.197 and xAi = 0.257, the slope m is: m M1

0.1

y Ai y*A y*

m' 0.923 A

E

x Ai x AL 00

0.1 0.2 0.3 0.4

xAL xAi x*A

From Example 10.4-1:

and

(1 y A )iM 0.709 (1 x A )iM 0.820

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-45

(1 y*A ) (1 y AG )

(1 yA )* 0.733

ln[(1 y A ) /(1 y AG )]

*

1 1 m'

' '

K y /(1 y A )*M k y /(1 y A )iM k x /(1 x A )iM

'

1

1

0.923 K 'y 8.90 104

K 'y / 0.733 1.465 103 / 0.709 1.967 10 3 / 0.820

K 'y

NA 4

y AG y A 3.78 10 kg mol/s.m

* 2

(1 y A )*M

JUST

Department of Chemical Engineering Mass Transfer – ChE 461 Chapter 3-46

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