Vapor Liquid Equilibrium

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Vapor Liquid Equilibrium

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SEM 1 (2012/2013)

VAPOR LIQUID

EQUILIBRUIM

Dr. Hayder Kh. Q. Ali

hayderali@unimap.edu.my

1

The Phase rule.

VLE Quantitative Behavior

Raoults Law

VLE by Modified Raoults Law

consider two rules that give the number of independent variables required

to determine equilibrium states.

Then a qualitative discussion of vapor/liquid phase behavior.

Introduce the simplest formulations

temperatures,

pressures,

and

that

allow

phase compositions

calculation

for

systems

of

in

for systems at low to moderate pressures and in general only for systems

comprised of chemically similar species.

A modification of Raoult's law that removes the restriction to chemically

similar species is treated.

Finally the calculations based on equilibrium ratios or K-values are

considered.

3

Phase equilibrium

Application

Distillation, absorption, and extraction bring

phases of different composition into contact.

transfer depend on the departure of the

system from equilibrium.

Quantitative treatment of mass transfer

the equilibrium T, P, and phase

compositions must be known.

4

A static condition in which no changes

occur in the macroscopic properties of a

system with time.

At the microscopic level, conditions are not

static.

The average rate of passage of molecules is

the same in both directions, and no net

interphase transfer of material occurs.

vapor phases in intimate contact

eventually reaches a final state wherein no

tendency exists for change to occur within

5

the system.

theorem

fixed in a system at equilibrium) = (the number of

variables that characterize the intensive state of

the system) - (the number of independent

equations connecting

F 2 ( N 1)(the

) variable):

( 1)( N ) 2 N

Phase rule:

F 2 ( N 1)( ) ( 1)( N ) N 2

Duhems rule:

for any closed system formed initially from given masses

of prescribed chemical species, the equilibrium state is

completely determined when any two independent

variables are fixed.

Two ? When phase rule F = 1, at least one of the two

variables must be extensive, and when F = 0, both must

6

be extensive.

Vapor/Liquid equilibrium (VLE) is the state of coexistence of liquid and

vapor phases. In this qualitative discussion, we limit consideration to systems

comprised of two chemical species, because systems of greater complexity

cannot be adequately represented graphically.

When N = 2, the phase rule becomes F = 4 - . Since there must be at least

one phase ( = 1), the maximum number of phase-rule variables which must be

specified to fix the intensive state of the system is three: namely, P, T, and

one mole (or mass) fraction. All equilibrium states of the system can therefore

be represented in three dimensional P-T- composition space. Within this space,

the states of pairs of phases coexisting at equilibrium (F = 4 - 2 = 2) define

surfaces. A schematic three-dimensional diagram illustrating these surfaces for

VLE is shown in Fig. below:

7

which contain the equilibrium states of saturated vapor and

saturated liquid for a binary system:

The under surface contains the saturated-vapor states; it is

the P-T-yl surface.

The upper surface contains the saturated-liquid states; it is

the P-T-xl surface.

These surfaces intersect along the lines UBHC2 and RKAC1,

which represent the vapor pressure-vs.-T curves for pure species

1 and 2.

of binary VLE are usually depicted by two-dimensional graphs. The

three principal planes, each perpendicular to one of the coordinate

axes.

A vertical plane perpendicular to the temperature axis is outlined

as ALBDEA. The lines on this plane form a P-x1-y1 phase diagram at

constant T.

A horizontal plane perpendicular to the P axis is identified by

HIJKLH. Viewed from the top, the lines on this plane represent a

T-x1-y1 diagram at constant P.

10

11

composition axis, is indicated by MNQRSLM, this is the P-T

diagram.

At points A and B in Fig. 10.3 saturated-liquid and

saturated-vapor lines intersect. At such points a saturated

liquid of one composition and a saturated vapor of another

composition have the same T and P, and the two phases are

therefore in equilibrium.

12

13

14

coexisting at equilibrium define surfaces.

The subcooled-liquid region lies above the upper

surface; the superheated-vapor region lies below the

under surface.

UBHC1 and KAC2 represent the vapor pressure-vs.-T

curves for pure species 1 and 2.

C1 and C2 are the critical points of pure species 1 and

2.

L is a bubble point and the upper surface is the

bubblepoint surface.

Line VL is an example of a tie line, which connects

points representing phases in equilibrium.

W is a dewpoint and the lower surface is the dewpoint

surface.

15

16

Fig 10.8

17

Fig 10.9

When thermodynamics is applied to vapor liquid

equilibrium, the goal is to find by calculation the temperatures,

pressures, and compositions of phases in equilibrium.

18

Raoults law:

the vapor phase is an ideal gas (apply for low to

moderate pressure)

the liquid phase is an ideal solution (apply when

the species that are chemically similar)

yi P xi Pi sat

(i 1, 2, ..., N )

where xi is a liquid-phase mole fraction, yi is a vaporphase mole fraction, and Pi sat is the vapor pressure

of pure species i at the temperature of the system. The

product yi P on the left side of Eq. is known as the partial

pressure of species i

19

phases wherein the molecular species are not too different

in size and are of the same chemical nature

although it provides a realistic description of actual

behavior for a small class of systems, it is valid for any

species present at a mole fraction approaching unity,

provided that the vapor phase is an ideal gas.

20

Calculations with Raoult's Law

Engineering interest centers on dewpoint and bubblepoint calculations;

there are four classes:

BUBL (vapor) or a DEW (liquid) composition and either P or T. Thus,

one must specify either the liquid-phase or the vapor-phase composition

and either T or P.

21

yi P xi Pi

sat

(i 1, 2, ..., N )

P xi Pi sat

(i 1, 2, ..., N )

1

yi / Pi sat

(i 1, 2, ..., N )

Binary system

22

23

pressures for the pure species are given by the following Antoine equations:

sat

1

ln P

2945.47

2972.64

sat

/ kPa 14.2724

ln P2 / kPa 14.2043

t / C 224.00

t / C 209.00

(a) Prepare a graph showing P vs. x1 and P vs. y1 for a temperature of 75C.

(b) Prepare a graph showing t vs. x1 and t vs. y1 for a pressure of 70 kPa.

(a) BUBL P

At 75C

e.g. x1 = 0.6

P 66.72

x1 P1sat (0.6)(83.21)

y1

0.7483

P

66.72

At 75C, a liquid mixture of 60 mol-% (1) and 40 mol-% (2) is in equilibrium with a vapor

containing 74.83 mol-% (1) at pressure of 66.72 kPa.

Fig. 10.11

24

25

Fig. 10.11

Select t

P1sat

P2sat

2945.47

2972.64

sat

ln

P

/

kPa

14

.

2043

2

t / C 224.00

t / C 209.00

P P2sat

x1 sat

P1 P2sat

t vs. x1

y1

26

sat

1 1

xP

P

t vs. y1

Fig. 10.12

Account is taken of deviation from solution

ideality in the liquid phase by a factor

inserted into Raoults law:

yi P xi i Pi sat

(i 1, 2, 3, ...N )

P xi i Pi sat

i

1

P

yi / i Pi sat

i

27

28

For the system methanol (1)/methyl acetate (2), the following equations provide a reasonable

correlation for the activity coefficients:

The Antoine equations provide vapor pressures:

3643.31

T ( K ) 33.424

2665.54

T ( K ) 53.424

Calculate

(a): P and {yi} for T = 318.15 K and x1 = 0.25

(b): P and {xi} for T = 318.15 K and y1 = 0.60

(c): T and {yi} for P = 101.33 kPa and x1 = 0.85

(d): T and {xi} for P = 101.33 kPa and y1 = 0.40

(e): the azeotropic pressure and the azeotropic composition for T = 318.15 K

(a) for T = 318.15, and x1 = 0.25

P1sat 44.51 P2sat 65.64 1 1.864 2 1.072

i

yi P xi i Pi sat

y1 0.282 y2 0.718

29

P1sat 44.51 P2sat 65.64

An iterative process is applied, with

1

P

yi / i Pi sat

1 1 2 1

x1

Converges at: P 62.89 kPa 1 1.0378

y1 P

1 P1sat

x2 1 x1

2 2.0935 x1 0.8169

T1sat 337.71 T2sat 330.08

A iterative process is applied, with

3643.31

T ( K ) 33.424

1 ... 2 ...

P xi i Pi sat

i

P1sat ...

Converges at:

T 331.20 K

1 1.0236 2 2.1182

y1 30

0.670

y2 0.330

T1sat 337.71 T2sat 330.08

A iterative process is applied, with

1 1 2 1

ln Pi sat / kPa Ai

3643.31

T ( K ) 33.424

P1sat ...

Bi

T ( K ) Ci

P2sat ...

P xi i Pi sat

i

x1 ...

x2 ...

1 ... 2 ...

P1sat ...

Converges at:

T 326.70 K

1 1.3629 2 1.2523

P2sat ...

x1 31

0.4602 x2 0.5398

(e): the azeotropic pressure and the azeotropic composition for T = 318.15 K

y1

Define the relative volatility:

Azeotrope

12

x1 0

12

y2

y1 x1 y2 x2

yi P xi i Pi sat

x1

x2

1 P1sat

12

2 P2sat

12 1

2.052 12

sat

P2

P1sat

0.224

x1 1

sat

P2 exp( 2.771 0.00523T )

There exists the azeotrope!

1 P1sat

12

1

sat

2 P2

1az P2sat

sat 1.4747

az

2

P1

ln 2 (2.771 0.00523T ) x12

ln

1

(2.771 0.00523T )( x2 x1 ) (2.771 0.00523T )(1 2 x1 )

2

x 0.325 y

az

1

az

1

1az 1.657

32

P az

correlations

A convenient measure, the K-value:

Ki

yi

xi

its tendency to favor the vapor phase.

When Ki is greater than unity, species i

exhibits a higher concentration in the vapor

phase; when less, a higher concentration in

the liquid phase, and is considered a "heavy"

constituent.

33

The Raoults

Pi sat

law:K i P

i Pi sat

Ki

law:

P

34

Fig 10.13

35

Fig 10.14

36

For a mixture of 10 mol-% methane, 20 mol-% ethane, and 70 mol-% propane at 50F,

determine: (a) the dewpoint pressure, (b) the bubblepoint pressure. The K-values are given by

Fig. 10.13.

(a) at its dewpoint, only an insignificant amount of liquid is present:

Species

Methane

Ethane

Propane

yi

0.10

0.20

0.70

P = 100 (psia)

Ki

yi /Ki

20.0

0.005

3.25

0.062

0.92

0.761

(yi /Ki) = 0.828

P = 150 (psia)

Ki

yi /Ki

13.2

0.008

2.25

0.089

0.65

1.077

(yi /Ki) = 1.174

P = 126 (psia)

Ki

yi /Ki

16.0

0.006

2.65

0.075

0.762

0.919

(yi /Ki) = 1.000

Species

Methane

Ethane

Propane

xi

0.10

0.20

0.70

P = 380 (psia)

Ki

x i Ki

5.60

0.560

1.11

0.222

0.335

0.235

(xi Ki) = 1.017

P = 400 (psia)

Ki

xi Ki

5.25

0.525

1.07

0.214

0.32

0.224

(xi Ki) = 0.963

P = 385 (psia)

Ki

x i Ki

5.49

0.549

1.10

0.220

0.33

0.231

(xi Ki) = 1.000

37

Flash calculations

A liquid at a pressure equal to or greater than its

bubblepoint pressure flashes or partially

evaporates when the pressure is reduced,

producing a two-phase system of vapor and liquid

in equilibrium.

Consider a system containing one mole of

nonreacting chemical species:

L V 1

The moles of vapor

The moles of liquid

zi xi L yiV

zi xi (1 V ) yiV

The liquid mole fraction

38

yi

zi K i

1 V ( K i 1)

zi K i

1 V ( K 1) 1

i

The system acetone (1)/acetonitrile (2)/nitromethane(3) at 80C and 110 kPa has the overall

composition, z1 = 0.45, z2 = 0.35, z3 = 0.20, Assuming that Raoults law is appropriate to this

system, determine L, V, {xi}, and {yi}. The vapor pressures of the pure species are given.

Do a BUBL P calculation, with {zi} = {xi} :

Do a DEW P calculation, with {zi} = {yi} :

Pdew

1

101.52 kPa

sat

sat

sat

y1 / P1 y2 / P2 y3 / P3

L 1 V 0.2636 mol

Since Pdew < P = 110 kPa < Pbubl, the system is in the two-phase region,

Pi sat

Ki

P

zi K i

1 V ( K 1) 1

i

yi

x1 0.2859

x2 0.3810

x3 0.3331

Ki

yi

xi

V 0.7364 mol

zi K i

1 V ( K i 1)

y1 0.5087

y2 0.3389

39

y3 0.1524

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