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You are on page 1of 16

What height should the nozzle

be?

What T and P should the drum

be?

Vapor-liquid equilibrium

(VLE)

What do we know?

Tvap, Pvap

yA , yB

yA + yB = 1

xA + xB = 1

yA xA

Tliq, Pliq

xA , xB

At equilibrium:

Tvap = Tliq

Pvap = Pliq

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

22+2=2

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

Specify P and T

2 graphs in one:

T vs. xA

T vs. yA

superheated vapor

2-phase

region

TA

A subcooled liquid

feed of composition

zA, heated to

temperature TA, will

separate

spontaneously into

2 phases,

Figure 2-3 Temperature-composition diagram

for of

xA and

From Separation Process Engineering, Third Edition by Phillipcomposition

C. Wankat

ethanol-water

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

reserved.

yrights

A

zA

subcooled liquid

yA

xA

point

Pure liquids have a

boiling point;

mixtures have a

boiling range,

delimited by their

bubble point and

dew point.

dew point

boiling

range

bubble point

xE,initial

yE,initial

that is 40 mol%

ethanol.

What is its bubble

point?

What is the

composition

2. Consider aof the

first

bubble? binary

superheated

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?

ethanol-water

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

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

Useful definitions

Boiling/bubble point Tbp: 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 < Tbp, by evaporation

Dew point Tdp: 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

will the flash drum produce?

F, L and V are extensive

variables

mass balance method OR

total mass balance (TMB):

F=L+V

component mass balance

(CMB):

F zA = L xA + V yA

L yA zA

rearrange:V zA xA

isotherm

L MV

V

LM

E

VL

e

lin

cr.

n

i

T

K = yE/xE

y=

For a binary

system at

constant P, if

one

composition (xA

or yA) is

VLE:

chosen, all

K = yA/xA

others are

fixed:

mole balance:

xA + xB = 1

yA + yB = 1

above y=x line if

plotted for the more

volatile component

volatility = K = K(T,

P, zi)

K(T)

azeotrope: K =

1.0

ethanol-water

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

how can we

break an

azeotrope?

volatility)

pure compound

T

P0

P*

Tbp

K = 1.0

K<1

DePriester Chart

temperature

total

pressure

K>1

for a given P, find Tbp (i.e., K = 1)

for a given T, find P0 (i.e., K = 1)

for a given P, T, find K

K > 1 prefers vapor phase

K < 1 prefers liquid phase

T*

the chart.

temperatures

volatility

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

Engineers)

the boiling point of

ethane?

At 15 C, what is

the saturated vapor

pressure of

isobutane?

At 0 C and 500

kPa, what is the

volatility of nhexane?

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

tables

vapor pressure

Raoults Law

0

P

x

P

(T )

ideal liquid:

A

A A

non-ideal liquid:

PA A xAPA0 (T )

activity coefficient

Daltons Law

ideal gas:

non-ideal gas:

yA

PA

PTOTAL

yA

PA

APTOTAL

fugacity coefficient

yA

PA0 (T )

PA0 (T )

KA

xA APTOTAL PTOTAL

for multi-component mixtures

Trial-and-error method

Given the composition of a subcooled liquid and P TOTAL,

find Tbp and (yi)bp

VLE:

yi K i xi

mole balance:

1.0

Algorithm:

1. Pick a temperature T and find

the corresponding Ki(T) values

for each component

2. Calculate the yi value for each

Ki(T)

3. Check to see if yi = 1

4. If not, pick a new temperature,

repeat

To achieve rapid

convergence:

T ziTi (K i 1)

Initial guess:

i

(weighted average of boiling points of pure

components)

Next guess:

pick a reference

component (A)

K A (Tnext )

K A (Tprev )

(y )

i prev

for multi-component mixtures

Trial-and-error method

Given the composition of a superheated vapor and P TOTAL,

find Tdp and (xi)dp

VLE:

mole

xi

yi

Ki

Algorithm:

corresponding Ki(T) values for

balance:

each component

2. Calculate the xi value for each

Ki(T)

xi 1.0

3. Check to see if xi = 1

i

4. If not, pick a new temperature and

repeat

K A (Tprev )

K A (Tnext )

(x )

i prev

Relative volatility

yA

KA

K A (T )

xA

volatility

yA

relative volatility

AB

KA

xA

K B yB

xB

strong function of

temperature

not a strong

function of

temperature; often

assumed

independent

yB 1 yA

xB 1 xA

AB xA

yA

1 ( AB 1)xA

using relative volatility

yi

sum:

Ki

xi

i

K ref K ref

yi i xi K ref

y 1.0 x K

i

K ref

ref

i xi

i

Algorithm:

given a solution composition (xi values), find relative volatilities (i values), then

1. guess Tinitial

2. calculate Kref

3. find T = T corresponding to K

volatilities

Find the bubble point of a mixture of n-pentane (x P = 0.3), n-hexane

(xX = 0.3) and n-heptane (xH = 0.4), at 1 atm total pressure. Find the

composition of the first vapor bubble.

i

XP

K

1.2

X

0.43

K P 2.8

K P (Tbp )

HP

K H 0.45

0.16

KP

2.8

1

1

2.0

i xi 0.3(1) 0.3(0.43) 0.4(0.16)

i

yi i xi K ref

Tbp = 58 C

yP 0.3(1)(2.0) 0.60

yX 0.3(0.43)(2.0) 0.26

yH 0.4(0.16)(2.0) 0.14

Check:

1.0

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