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THERMODYNAMICS

EQUILIBRIUM, RAOULT’S LAW, DEWPOINT AND

BUBBLE POINT CALCULATIONS WITH RAOULT’S LAW

VLE: QUALITATIVE BEHAVIOR

VLE: State of coexistence of L & V phases

A condition where a liquid phase and vapor phase

are in equilibrium with each other

At this condition:

rate of evaporation (liquid → vapor) =

rate of condensation (vapor → liquid)

e.g: mixture of liquid and vapor at an equilibrium

level

takes place when liquid and vapor are allowed to

contact to each other in a closed location

2

Under surface- sat. V states (P-T-y1)

Upper surface- sat. L states (P-T-x1)

Liquid at F, reduces pressure at constant T

& composition along FG, the first bubble

appear at L – bubble point: a point

when a liquid forms the first bubble

of vapor and begins to evaporate

As pressure reduces, more & more L

vaporizes until completed at W; point

where last drop of L (dew) disappear –

dew point: a point when a vapor

forms the first droplet of liquid and

begins to condense

surfaces of equilibrium states of

saturated V & saturated L of a binary

system

3

4

SIMPLE MODELS FOR VAPOUR

LIQUID EQUILIBRIUM

Simple Models

For VLE :

Find T, P, composition

5

RAULT’S LAW

Assumptions;

V phase is an ideal gas

Applicable for low to moderate pressure

L phase is an ideal solution

Valid only if the species are chemically similar (size, same

chemical nature e.g. isomers such as ortho-, meta- & para-

xylene)

6

yi P xi Pi sat

i 1,2,..., N 1

Where;

xi : L phase mole fraction

yi : V phase mole fraction

Pi sat : Vapor pressure of pure species i

P : Total pressure

7

Dewpoint & Bubblepoint Calculations with

Raoult’s Law

FIND GIVEN

BUBL P: Calculate {yi} and P, given {xi} and T

DEW P: Calculate {xi} and P, given {yi} and T

BUBL T: Calculate {yi} and T, given {xi} and P

DEW T: Calculate {xi} and T, given {yi} and P

8

For binary systems to solve for

bubblepoint calculation (T is given);

y i i 1

P xi Pi

i

sat

PP

2

sat

P 1

sat

P 2

sat

x

1

2

x1 P1 sat

y1 3

P

9

Raoult’s law equation can be solved for xi

to solve for dewpoint calculation (T is

given)

i xi 1

P

1 1

i i sat P 4

i

y P

y1 / P1 y2 / P2

sat sat

y1 P

x1 sat 5

P1

10

Example 1

Binary system acetonitrile(1)/nitromethane(2)

conforms closely to Raoult’s law. Vapor pressure

for the pure species are given by the following

Antoine equations:

2,945.47

ln P sat

kPa 14.2724 0 i

t C 224.00

1

2,972.64

ln P sat

kPa 14.2043 0 ii

t C 209.00

2

temperature 750C

b)Prepare a graph showing t vs. x1 and t vs. y1 for

11 a pressure of 70 kPa

a) BUBL P calculations are required. Since this is a

binary system, Eq. 2 may be used.

PP 2

sat

P 1

sat

P

2

sat

x1 ( A)

At 750C, the saturated pressure is given by Antoine

equation;

P1

sat

83.21 P 2

sat

41.98

Substitute both values in (A) to find P;

12 P 66.72kPa

The corresponding value of y1 is found from Eq. 1,

yi P xi Pi sat

y1

xP

1 1

sat

0.683.21

0.7483

P 66.72

x1 y1 P/kPa x1 y1 P/kPa

13

14

At point c, the vapor composition is y1=0.6, but

the composition of liquid at c’ and the pressure

must read from graph or calculated. Thus DEW P

calculations are required. By using Eq. 3;

1

P

y1 P1 y2 P2

sat sat

1

P 59.74kPa

0.6 83.21 0.4 41.98

15

And by Eq. 1,

y1 P 0.6 59.74

x1 sat 0.4308

P1 83.21

T2sat, with x1 & y1. T1sat & T2sat are calculated

from Antoine equation;

Bi

t sat

Ci

Ai ln P

i

16

For P=70kPa, T1sat=69.840C, T2sat=89.580C. Select T

between these two temperatures and calculate P1sat & P2sat

for the two temperatures.

Substituting T= 78˚C into (i) and (ii)

e.g; select T= 78˚C P1sat = 91.76 kPa

P2sat = 46.84 kPa

Evaluate x1 by Eq. (A). For example;

P P2sat 70 46.84

x1 sat x1 0.5156

P1 P2 sat

91.76 46.84

x1 P1sat 0.515691.76

17

y1 0.6759

P 70

Summary; x1 y1 T/˚C

(t2sat)

0.1424 0.2401 86

0.3184 0.4742 82

0.5156 0.6759 78

0.7378 0.8484 74

18

(t1sat)

19

Henry’s Law

Assumptions;

It is so low that it can be assume as ideal gas

liquid phase

20

Henry’s Law

yi P xi H i i 1,2,..., N 6

Where;

xi : L phase mole fraction

yi : V phase mole fraction

H i : Henry' s constant

P : Total pressure

21

Example 2

CO2(1) and H2O(2), determine the compositions of

the V & L phases in a sealed can of ‘soda’ & the P

exerted on the can at 100C. Henry’s constant for

CO2 in water at 100C is about 990 bar and x1=0.01.

22

Henry’s law for species 1 & Raoult’s law for species 2

are written;

y1P x1H1 y2 P x2 P 2

sat

P x1 H1 x P 2 2

sat

tables at 100C)

P 9.912 bar

23

Then by Raoult’s law, Eq. 1 written for species 2;

x2 P2sat 0.990.01227

y2 0.0012

P 9.912

nearly pure CO2, as expected.

24

VLE BY MODIFIED RAOULT’S LAW

taking into account the deviation from solution

ideality in L phase.

Thus, activity coefficient is introduced in Raoult’s

Law

yi P xi i Pi sat

i 1,2,..., N 7

25

Activity coefficients are function of T &

liquid phase composition, x

Since;

y i i 1

P xi i Pi sat

For bubble point 8

i xi 1

1 For dew point

P 9

y i

i i Pi sat

26

AZEOTROPE

constant composition of

liquid and vapor phase

When x1=y1, the dew

point and bubble point

curves are tangent to the

same horizontal line

A boiling L of this

composition produce a

vapor exactly the same

composition; L does not

change in composition as

it27evaporates

VLE FROM K-VALUE CORRELATTIONS

The partition between liquid and vapor phases

of a chemical species is equilibrium ratio, Ki.

yi

Ki 10

xi

This quantity is called K-value.

28

K-value for Raoult’s Law yi P xi Pi sat

sat

Pi

Ki 11

P

K-value for modified Raoult’s Law yi P xi i Pi sat

i Pi sat

Ki 12

P

29

For binary systems to solve for bubble

point calculation;

y i i 1

Hence,

Kxi i i 1 13

dew point calculation;

x i i 1

Hence, yi

i

Ki

1 14

30

K-value

from

DePriester

chart

-Low T

range

31

K-value

from

DePriester

chart

-High T

range

32

Tentukan K-value isobutana pada -100oC dan 100oC dan pada

tekanan 6 Mpa. Tentukan komposisi kesetimbangan uap-cair

campuran isobutana dan isopentana pada 100oC dan 6 MPa; dan

pada 100oC dan 1 Mpa

dePriester Chart

33

34

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