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**How big should the drum be?
**

What height should the nozzle be?

What T and P should the drum be?

What T and P should the feed be?

Vapor-liquid equilibrium (VLE)

Consider a binary (i.e., 2-component) system with 2-phases:

T

vap

, P

vap

y

A

, y

B

T

liq

, P

liq

x

A

, x

B

What do we know?

y

A

+ y

B

= 1 x

A

+ x

B

= 1

y

A

≠ x

A

At equilibrium: T

vap

= T

liq

P

vap

= P

liq

Gibbs’ Phase Rule:

degrees of freedom = # components (C) - # phases (P) + 2

For a binary, 2-phase system: 2 – 2 + 2 = 2

We can specify only 2 intensive variables (all others are fixed, by VLE)

Specify P and T

From Separation Process Engineering, Third Edition by Phillip C. Wankat

(ISBN: 0131382276) Copyright © 2012 Pearson Education, Inc. All rights reserved.

Figure 2-3 Temperature-composition diagram for ethanol-water

superheated vapor

subcooled liquid

2-phase

region

saturated vapor line

saturated liquid line

2 graphs in one:

T vs. x

A

T vs. y

A

A subcooled liquid feed

of composition z

A

,

heated to temperature

T

A

, will separate

spontaneously into 2

phases, of composition

x

A

and y

A

T

A

x

A

• •

y

A

•

z

A

•

From Separation Process Engineering, Third Edition by Phillip C. Wankat

(ISBN: 0131382276) Copyright © 2012 Pearson Education, Inc. All rights reserved.

Figure 2-3 Temperature-composition diagram for ethanol-water

bubble point

dew point

x

E,initial

y

E,initial

boiling

range

1. Consider a sub-cooled

binary liquid that is 40

mol% ethanol.

What is its bubble point?

What is the composition of

the first bubble?

2. Consider a superheated

binary vapor that is 40

mol% ethanol.

What is its dew point?

What is the composition of

the first drop?

3. What is the boiling range

of this mixture?

Boiling point, dew point, bubble point

Pure liquids have a

boiling point; mixtures

have a boiling range,

delimited by their

bubble point and dew

point.

Useful definitions

• Boiling/bubble point T

bp

: temperature at which the average

liquid molecule has just enough kinetic energy to escape from

the surface of the liquid into the gas phase

– Recall that kinetic energy follows a Boltzmann distribution, so

molecules with higher than average kinetic energy can still escape

from the surface at T < T

bp

, by evaporation

• Saturated liquid: a liquid at its boiling/bubble point

• Dew point T

dp

: temperature at which the average vapor

molecule has just enough kinetic energy to condense

• Saturated vapor: a vapor at its dew point

• Vapor pressure: pressure at which the liquid and vapor phase

are in equilibrium at a given temperature

• Azeotrope: a constant-boiling mixture, i.e., a mixture that

behaves like a single component

How much liquid and vapor

will the flash drum produce?

mass balance method

total mass balance (TMB):

F = L + V

component mass balance (CMB):

F z

A

= L x

A

+ V y

A

rearrange:

L

V

·

y

A

z

A

z

A

x

A

OR inverse lever-arm method

F, L and V are extensive variables

L

V

·

MV

LM

•

L

•

M

•

V

isotherm

For a given F, we can now compute L and V.

From Separation Process Engineering, Third Edition by Phillip C. Wankat

(ISBN: 0131382276) Copyright © 2012 Pearson Education, Inc. All rights reserved.

Figure 2-2 McCabe-Thiele diagram for ethanol-water

K = y

E

/x

E

volatility = K = K(T, P, z

i

)

≈ K(T)

azeotrope: K = 1.0

how can we “break”

an azeotrope?

Specify P and one composition (x

A

)

For a binary system

at constant P, if one

composition (x

A

or

y

A

) is chosen, all

others are fixed:

VLE:

K = y

A

/x

A

mole balance:

x

A

+ x

B

= 1

y

A

+ y

B

= 1

VLE line always lies above

y=x line if plotted for the

more volatile component

Specify two of (P, T, volatility)

t

o

t

a

l

p

r

e

s

s

u

r

e

t

e

m

p

e

r

a

t

u

r

e

K = 1.0

DePriester Chart

• for a given P, find T

bp

(i.e., K = 1)

• for a given T, find P

0

(i.e., K = 1)

• for a given P, T, find K

K > 1 prefers vapor phase

K < 1 prefers liquid phase

Don’t extrapolate beyond the range of the chart.

T

bp

P

0

pure compound

Consider a pure compound:

T´

P´

K > 1

T*

P*

K < 1

Figure 2-11 Modified DePriester chart (in S.I. units) at low temperatures

(D. B. Dadyburjor, Chem. Eng. Prog.,85, April 1978; copyright 1978, AIChE; reproduced by permission of the American Institute of Chemical Engineers)

From Separation Process Engineering, Third Edition by Phillip C. Wankat

(ISBN: 0131382276) Copyright © 2012 Pearson Education, Inc. All rights reserved.

At 2000 kPa, what is the

boiling point of ethane?

volatility

At 15 °C, what is the

saturated vapor pressure

of isobutane?

At 0 °C and 500 kPa,

what is the volatility of

n-hexane?

Using data from vapor pressure tables

Raoult’s Law

ideal liquid:

non-ideal liquid:

Dalton’s Law

ideal gas:

non-ideal gas:

P

A

· x

A

P

A

0

(T)

P

A

·

A

x

A

P

A

0

(T)

y

A

·

P

A

P

TOTAL

y

A

·

P

A

A

P

TOTAL

K

A

·

y

A

x

A

·

P

A

0

(T)

A

P

TOTAL

P

A

0

(T)

P

TOTAL

activity coefficient

fugacity coefficient

vapor pressure

Bubble point calculation

for multi-component mixtures

Trial-and-error method

Given the composition of a subcooled liquid and P

TOTAL

,

find T

bp

and (y

i

)

bp

VLE:

mole balance:

y

i

· K

i

x

i

y

i

i

·1.0

Algorithm:

1. Pick a temperature T and find the

corresponding K

i

(T) values for each

component

2. Calculate the y

i

value for each K

i

(T)

3. Check to see if Sy

i

= 1

4. If not, pick a new temperature, repeat

How to pick a temperature? How to pick the next temperature?

To achieve rapid convergence:

Initial guess:

(weighted average of boiling points of pure components)

T · z

i

T

i

i

(K

i

·1)

K

A

(T

next

) ·

K

A

(T

prev

)

(y

i

)

prev

i

Next guess:

pick a reference component (A)

find T

next

using DePriester Chart

Dew point calculation

for multi-component mixtures

Trial-and-error method

Given the composition of a superheated vapor and P

TOTAL

,

find T

dp

and (x

i

)

dp

VLE:

mole balance:

x

i

·

y

i

K

i

x

i

i

·1.0

Algorithm:

1. Pick a temperature T and find the

corresponding K

i

(T) values for each

component

2. Calculate the x

i

value for each K

i

(T)

3. Check to see if Sx

i

= 1

4. If not, pick a new temperature and repeat

K

A

(T

next

) ·

K

A

(T

prev

)

(x

i

)

prev

i

Relative volatility

volatility

K

A

·

y

A

x

A

· K

A

(T)

AB

·

K

A

K

B

·

y

A

x

A

y

B

x

B

strong function of

temperature

not a strong function of

temperature; often

assumed independent

relative volatility

for a binary system, substitute and rearrange:

y

A

·

AB

x

A

1+(

AB

1)x

A

y

B

·1 y

A

x

B

·1 x

A

Bubble point calculation

using relative volatility

K

ref

·

1

i

x

i

i

i

·

K

i

K

ref

·

y

i

x

i

K

ref

definition of relative volatility:

solve for y

i

:

y

i

·

i

x

i

K

ref

solve for K

ref

:

sum:

y

i

i

·1.0 ·

i

x

i

( )

i

K

ref

Algorithm:

given a solution composition (x

i

values), find relative volatilities (a

i

values), then

1. guess T

initial

2. calculate K

ref

3. find T = T

bp

corresponding to K

ref

Ex.: Finding T

bp

using relative volatilities

Find the bubble point of a mixture of n-pentane (x

P

= 0.3), n-hexane (x

X

=

0.3) and n-heptane (x

H

= 0.4), at 1 atm total pressure. Find the

composition of the first vapor bubble.

T

initial

· x

i

T

i

i

(K

i

·1) · 0.3(36) +0.3(68) +0.4(99) · 71°C

Designate n-pentane as the reference. At 71 °C, K

P

= 2.8.

XP

·

K

X

K

P

·

1.2

2.8

· 0.43

K

P

(T

bp

) ·

1

i

x

i

i

·

1

0.3(1) +0.3(0.43) +0.4(0.16)

· 2.0

Find T

bp

corresponding to K

P

= 2.0 (read from DePriester Chart): T

bp

= 58 °C

y

P

· 0.3(1)(2.0) · 0.60

y

i

·

i

x

i

K

ref

y

X

· 0.3(0.43)(2.0) · 0.26

y

H

· 0.4(0.16)(2.0) · 0.14

y

i

i

·1.0

Check:

HP

·

K

H

K

P

·

0.45

2.8

· 0.16

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