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(VLE): Introduction

which no changes occur in a

macroscopic properties of a system

with time

1

The Phase Rule. Duhem’s Theorem

The phase rule:

by J. Willard Gibbs

F = 2 −π + N (1.1)

F = degree of freedom (dof)

π = # of phase(s)

N = # of chemical species

system of a single species of 2 phases

(e.g., liquid and vapour)

2

From the given information

π =

N=

Thermodynamic property in order to

identify the other properties of the

system

3

Consider a P-T diagram

S V

liquid zones (on which vapour and liquid

coexist in equilibrium), when we specify

the value of T, the value of P will

automatically be fixed, or vice versa

4

Example Determine a dof of a

system of a single species and a

single phase (e.g., either liquid or

vapour)

π =

N=

5

When considering a P-T diagram,

in order to be able to specify the

exact point on the liquid (i.e. LHS of

the dome) or vapour (i.e. RHS of the

dome) zone, we need both P and T;

only P or T does not suffice

6

Example Determine a dof of a “triple

point” of a pure species

L, & V) coexist in equilibrium)

Thus,

π =

N=1

7

This implies that, for any pure species

(a single species), when we know the

triple point, we will automatically know

the name of the substance, or vice

versa

We do NOT need to know any other

Thermodynamic properties

S V

Triple point

8

Duhem’s Theorem

Applied to “closed” systems

initially from given masses (or

moles) of prescribed chemical

species, the equilibrium state is

“completely determined” when

any “two” independent variables

are fixed”

9

For a 2 species system (i.e. a

binary mixture) with 2 phases (e.g.,

V+L), from the phase rule, we obtain

F = 2 −π + N

= 2−2+2

=2

In addition to T or P, we need to know

a chemical composition of a mixture, in

the from of either mole or mass fraction

Since it is a binary mixture, we need

to know mole or mass fraction of only

one substance; mole or mass fraction of

another substance will automatically be

fixed

Hence, dof = 1+1 = 2

10

For an n species system (i.e. N = n),

from the phase rule, we get

F = 2 −π + N

= 2−2+n

=n

This means that we need to know

either P or T, and mole (or mass)

fraction of n − 1 components

Hence, dof = 1+ ( n − 1) = n

11

VLE: Qualitative Behaviour

Gaseous phase

A+B

A+B

Liquid phase

Let

mole fraction of A in a liquid

phase = xA

and

mole fraction of A in a gaseous

phase = y A

12

At any given P, we vary T and

measure the values of xA and y A , and

then plot a graph between T and xA or

y A , or a Txy diagram as illustrated below

T Dew-point

Vapour curve

zone

T2 C

B

T1 A

T3

D

Bubble-point

curve

Liquid

zone

xA1 yA1

xA or yA

13

From a Txy diagram,

at any given T (e.g., T1)

Point A = saturated liquid state

of a liquid mixture at which the mole

fraction of species A = xA1

Point B = saturated vapour state

of a gaseous mixture where the mole

fraction of species A = yA1

species A in the range of xA1—yA1, the

mixture is in the form of a vapour-

liquid mixture

14

Additionally, at T = T1

• a mixture with a mole fraction

of A lower than xA1 is in the form

of compressed or sub-cooled

liquid

• a mixture with a mole fraction

of A higher than yA1 is in the

form of superheated vapour

15

At a given xA (e.g., xA1)

when T is increased from the

state of compressed liquid (e.g., at T

= T3) to the point where T = T1, the

mixture starts to boil at the point A

If T is kept increasing, the

mixture is in the form of the vapour-

liquid mixture until T = T2 (point C),

where the mixture changes to the

form of a saturated vapour

and if T is still increased, the

mixture is in the form of superheated

vapour

16

On the other hand, if T is

decreased from the vapour zone,

where the mole fraction of species A

= yA1, to the point at which T = T1

(point B), the mixture turns to be

saturated vapour (there is a first drop

of liquid at this point)

If T is kept decreasing, the mixture

is in the form of liquid-vapour mixture

until T = T3 (point D), where the

mixture turns to be liquid completely

(or becomes saturated liquid)

17

When we draw Txy diagrams at

various P, we get

T

CB

P3

CA

P2

CA

P1

xA or yA

18

Note that

CA & CB = critical P of A & B,

respectively

that

P1 < P2 < P3

and that

P1 < Pc of A & B

P2 is in between Pc of A & B

P3 > Pc of A & B

19

At any given T, a Pxy diagram can

be drawn as follows

Bubble-point

P curve

Liquid

zone

L+V

Vapour

zone

Dew-point

curve

xA or yA

20

Pxy diagrams at various T are as

illustrated below

T3 CB

CA

T2

CA

T1

xA or yA

21

Note that

CA & CB = critical T of A & B,

respectively

that

T1 < T2 < T3

and that

T1 < Tc of A & B

T2 is in between Tc of A & B

T3 > Tc of A & B

22

In the case where either a Txy or a

Pxy diagram is as follows

T

Q

xAQ

xA or yA

point

23

It is the point where the mixture

behaves as it is a pure substance

we cannot separate the mixture with

by distillation (WHY?)

24

At any mole fraction of A, we can

draw a P-T diagram as follows

P Critical

Bubble-point point

curve

Dew-point

curve

not be the highest T or P

25

When we combine a P-T diagram at

different mole fractions of A, we obtain

P

CA

Critical

locus

CB

species A & B, respectively

26

When we draw a graph of xA and

yA at a given T & P, we get

yA

yA = xA

xA

27

At the point where xA = yA, i.e. the

point where the composition of a

mixture in the gaseous phase is the

same as that in the liquid phase, we

cannot separate the mixture by

distillation

28

Simple Models for VLE Calculations

• Raoult’s law

• Henry’s law

Raoult’s law

Assumptions for a Raoult’s law

• The VAPOUR PHASE is an IDEAL

GAS

• The LIQUID PHASE is an IDEAL

SOLUTION

29

Hence,

• Raoult’s law is applicable for a

system where P is not too high

(in order that a vapour phase

behaves as an ideal gas)

• The mixture should be in similar

chemical nature and not too

different in size – in order that it

behaves as an ideal solution

30

Raoult’s law

y i P = xi Pi sat (4.1)

where

yi = mole fraction of species i

in a gaseous phase

xi = mole fraction of species i

in a liquid phase

P = total pressure of a system

Pi sat = vapour pressure of

species i

31

Since

y i P = Pi (4.2)

where

Pi = partial pressure of species i

in a gaseous phase

Pi = xi Pi sat (4.3)

32

How can we obtain the value of Pi sat ?

Example

Saturated propane: T-table

Specific Volume

T (oC) P (bar)

vf vg

0 4.743 … ….

.. … … ….

.. … … ….

20 8.362 … ….

.. … … ….

.. … … ….

40 13.69 … ….

33

From Charts (e.g., a Cox chart)

to determine vapour pressures of

propane at 0, 20, and 40 oC (32, 68,

and 104 oF), and compare the read

values with those from the Table on

Page 33

34

Using Empirical Equations

Example

⎛ C2 ⎞

P sat

= exp ⎜ C1 + + C3 ln T + C4 T C5 ⎟

⎝ T ⎠

(4.4)

where

P sat is in the unit of Pa

T is in the unit of K

C1 − C5 are properties of a

substance

Note that C1 – C5 can be obtained

from, e.g., Table 2.6, pp. 2-50 – 2-54 of

Perry’s Chemical Engineers’ Handbook (7th

ed.)

35

Example The values of C1 − C5 of

propane are as follows:

C1 = 59.078 ; C2 = −3492.6 ;

C3 = −6.0669 ; C4 = 1.0919 × 10 −5 ;

C5 = 2

Table is 8.362 bar

36

Another Empirical Equation

B

log P sat

= A− (4.5)

T +C

where

P sat is in the unit of bar

T is in the unit of oC

A − C are properties of a substance

Note that A – C are available in, e.g.,

Section D of Appendix A, pp. A.48 – A.60 of

The Properties of Gases and Liquids (5th ed.)

37

Example The values of A − C for

propane are as follows:

A = 3.92828

B = 803.9970

C = 247.040

38

Applying a summation for all

species to a Raoult’s law (Eq. 4.1)

y i P = xi Pi sat (4.1)

yields

∑ i

y P = P = ∑ ii

x P sat

(4.6)

P = x1P1sat + x2 P2sat (4.7)

and

x2 = 1− x1 (4.8)

39

Combining Eqs. 4.7 & 4.8 gives

P = x1P1sat + (1− x1 ) P2sat

= x1P1sat + P2sat − x1P2sat

x1, we obtain a straight line with

• a Y-intercept of

P2sat at x1 = 0

P1sat at x1 = 1

are illustrated in the next page

40

Note that dashed lines are the

P − x1 lines from a Raoult’s law

41

Since liquid boils when ∑y i = 1, Eq. 4.6

to condense when ∑x i = 1 or when

1

P= (4.10)

∑ i i )

( y / P sat

calculations

42

Example Draw a Pxy diagram of

propane for a propane + ethane

mixture at T = 75 oC using a Raoult’s

law and an Antoine equation

The values for an Antoine

equation for propane and ethane

are as follows

Propane: Ethane:

A = 3.92828 A = 3.95405

B = 803.9970 B = 663.720

C = 247.040 C = 256.681

43

Employing an Antoine equation to

calculate P sat of propane and ethane

at 75 oC yields

44

Applying Eq. 4.9

P = x1 ( P1sat − P2sat ) + P2sat (4.9)

P = xpropane ( Ppropane

sat sat

− Pethane ) + Pethane

sat

of Ppropane

sat

and Pethane

sat

into the above

equation results in

45

Using Eq. 4.11 to calculate the

values of P at various xpropane results in

xpropane P [bar]

0 89.7

0.2 77.2

0.4 64.6

0.6 52.1

0.8 39.5

1.0 27.0

46

When the values of P at different

xpropane are obtained, the values of y propane

Eq. 4.1 (i.e. a Raoult’s law), as follows

sat

y propaneP = xpropanePpropane

........ xpropane

and y propane =

P

xpropane P [bar] y propane

0 89.7 0

0.2 77.2 0.07

0.4 64.6 0.17

0.6 52.1 0.31

0.8 39.5 0.55

1.0 27.0 1.00

47

From the Table in the previous

page, we can plot a Pxy diagram as

follows

100

80 Bubble-point

P-x curve

60

P [bar]

P-y

40

Dew-point

20

curve

0

0 0.2 0.4 0.6 0.8 1

xpropane or ypropane

48

Example Draw Txy diagram of

propane for a propane + ethane

mixture at P = 10 bar using a Raoult’s

law and an Antoine equation

equation as follows

sat B

log P = A −

T+C

sat B

A − log P =

T+C

T+C 1

=

B A − log P sat

B

T= sat

−C

A − log P

49

Thus, T sat at a given P can be

calculated from the following

equation

B

T sat = −C (4.12)

A − log P

At P = 10 bar

50

We, then, pick T between -32.0 –

27.5 oC, for example,

-32.0, -22.0, -12.0, -2.0, 8.0, 18.0, 27.5 oC

Calculating Ppropane

sat

and Pethane

sat

at these

51

Rearranging Eq. 4.9 results in

P − P2sat

x1 = sat

P1 − P2sat

Hence,

sat

P − Pethane

xpropane = sat sat

(4.13)

Ppropane − Pethane

sat

Ppropane and Pethane

sat

, & the value of P

yields

xpropane =

52

The value of y propane can then be

sat

xpropanePpropane

y propane =

P

=

=

for other T’s results in

53

sat

T Ppropane sat

Pethane

xpropane y propane

[oC] [bar] [bar]

-32.0 1.547 10.00 0 0

-22 2.268 13.42 0.307 0.070

-12 3.218 17.44 0.523 0.168

-2 4.438 22.28 0.688 0.306

8 5.968 27.95 0.817 0.487

18 7.849 34.49 0.919 0.722

27.5 10.000 41.54 1.000 1.000

54

A Txy diagram can then be drawn

as follows

40

20

Dew-point T-y

curve

T [oC]

-20

T-x Bubble-point

curve

-40

0.0 0.2 0.4 0.6 0.8 1.0

xpropane or ypropane

55

Bubble-Point Calculations

When we know mole fraction of a

substance in liquid phase ( xi ) and T, we

can calculate a “bubble-point P”

Vice versa, when we know mole

fraction of a substance in liquid phase

( xi ) and P, we can calculate a “bubble-

point T”

of a propane + ethane mixture at

P = 10 bar and xpropane = 0.3

56

At a bubble point, ∑y i =1

species to a modified Raoult’s law

y i P = xi Pi sat

xi Pi sat

yi = (4.1a)

P

xi Pi sat

∑ yi = ∑ P

1

1 = ∑ xi Pi sat

P

yields

P = ∑ xi Pi sat (4.6)

sat

P = xpropanePpropane sat

+ xethanePethane (4.14)

57

Given

P = 10 bar

xpropane = 0.3 Î xethane = 0.7

of Ppropane

sat

and Pethane

sat

calculations by guessing a value of T,

e.g., T = -20 oC, and then calculate

the values of Ppropane

sat

and Pethane

sat

at the

guessed T, as follows

58

Substituting the values of resulting

sat

Ppropane and Pethane

sat

into Eq. 4.14 yields

59

Since the resulting P is higher than

10.0 bar, it indicates that the guessed

value of T (-20 oC) are too high Î we

need a NEW GUESS

iteration until we obtain T that makes

∑ i i = 10 bar

x P sat

60

Dew-Point Calculations

When we know mole fraction of a

substance in gaseous phase ( yi ) and

T, we can calculate a “dew-point P”

Vice versa, when we know mole

fraction of a substance in gaseous

phase ( yi ) and P we can calculate a

“dew-point T”

61

Example Calculate a dew-point P of

a propane + ethane mixture at T =

0 oC and y propane = 0.6

At a dew point, ∑x i =1

species to a modified Raoult’s law

y i P = xi Pi sat

yi P

xi = sat

Pi

yi P

∑ xi = ∑ Psat

i

yi

1 = P∑ sat

Pi

62

results in

1

P= (4.10)

⎛ yi ⎞

∑ ⎜ Psat ⎟

⎝ i ⎠

1

P= (4.15)

y propane yethane

sat

+ sat

Ppropane Pethane

Given

T = 0 oC

y propane = 0.6 Î yethane = 0.4

63

Thus,

into Eq. 4.15 gives

64

Precautions for the use of Raoult’s law

• Can be used at not-too-high P

• Can be used at T < Tc

• Can be used with species whose

mole fractions approach 1 (if mole

fractions are too low, e.g., 5% or

0.05, Raoult’s law is NOT suitable)

• Can be used with a mixture whose

components are in chemical similar

nature and shape

65

Henry’s Law

y i P = xi Pi sat (4.1)

( xi ) of a solute is low (e.g., CO2 or air

dissolves in water) and the case

where T > Tc, a Raoult’s law is NOT

suitable and/or applicable for VLE

calculations

66

For example, a Raoult’s law is NOT

applicable when we want to perform

VLE calculations for the CO2 (Tc =

304.12 K) + water system at 373.15 K,

since, by using a Raoult’s law, we

shall NOT have vapour pressure data

of CO2 at the temperatures above its

critical point

to do the VLE calculations at those

conditions, what should we do?

67

Henry’s law can help you

Henry’s law

“The partial pressure of the

species in the vapour phase is

directly proportional to its

liquid-phase mole fraction”

y i P = xi Η i (4.16)

where

Η i = Henry’s constant

vapour pressure ( P sat ) in a Raoult’s

law equation (Eq. 4.1)

68

Thus, a unit of Henry’s constant is

the same as that of PRESSURE

as same as vapour pressure ( P sat )

For instances,

Η i of CO2 at 10 oC = 900 bar

on type of substance and is obtained

experimentally

69

Example Determine why we should

keep pop or soda at a low

temperature, using both Henry’s &

Raoult’s laws. Henry’s constants ( Η i )

900 bar, respectively. Vapour

pressures of water at 10 oC and 25 oC

are 0.01228 and 0.03169 bar,

respectively

70

Since CO2 can scarcely be dissolved

in water, its mole fraction of CO2 in

water is low

Hence, we should use a Henry’s law

for VLE calculations of CO2

Raoult’s law for VLE calculations of

water, as the mole fraction of water in

the CO2-water solution approaches 1

71

Hence,

for CO2:

PCO2 = yco2 P = xco2 Η co2

for water:

sat

Pwater = y water P = xwater Pwater

gaseous phase can be calculated from

the following equation

P = PCO2 + Pwater

sat

= xco2 Η co2 + xwater Pwater

72

Assume that 5% (by mol) of CO2 is

dissolved in water ( xCO 2

= 0.05 Î

xwater = 0.95 )

Thus, at 10 oC

while the total pressure is kept

constant (at 45.01 bar), mole fraction

of CO2 of the same solution changes

to

73

(Note that, since it is the same bottle, the

total pressure of gaseous phase is still the

same)

74

Approximately, the amount of CO2

dissolved in water reduces by half

(5% to 2.7%) when T is increased from

10 to 25 oC

(hence, we cannot keep the

temperature at 10 oC), but we have

a compressor,

“can we use a compressor to

keep CO2 in the solution?”

75

Assume that we use a compressor

to increase the total pressure of the

system from ~45 bar to 80 bar

Thus, the amount of CO2 dissolved

in the solution, at 25 oC, can be

calculated as follows

the solution, we can do 2 things:

76

• Keep T of a solution (soda/pop)

at low temperatures (and a

bottle should also be capped)

• Keep P of the system at high

pressures, using, e.g., a

compressor

77

VLE Calculations by a MODIFIED

Raoult’s Law

law, in which

• VAPOUR Phase = IDEAL GAS

• LIQUID Phase = IDEAL SOLUTION

assuming that vapour phase = ideal

gas causes only a small error in VLE

calculations, as, for most interested

systems:

• T are usually high

• P are normally low

78

hence, it is justified to assume that

VAPOUR Phase = IDEAL GAS

however, comes from the assumption

that liquid phase = ideal solution

applicable for real solutions (by

having an acceptable error) the

“original” Raoult’s law has to be

modified, as follows

y i P = xiγ i Pi sat (4.17)

where γ i = activity coefficient

79

From Lecture 3, we knew that

giE

ln γ i = (3.135)

RT

where giE = gi − giid , which indicates the

deviation from the ideal solution

ˆfi

γi =

xi fi

from the ideal solution

non-idealness of real solutions

80

We can use Eq. 4.17 to calculate a

bubble point and a dew point in the

same way we use Eqs. 4.6 and 4.10,

by keeping in mind that

• at a bubble point: ∑y i =1

• at a dew point: ∑x i =1

81

At a bubble point, ∑y i =1

Thus,

P = ∑ xiγ i Pi sat (4.18)

At a dew point, ∑x i =1

Hence,

1

P= (4.19)

⎛ yi ⎞

∑ ⎜ γ Psat ⎟

⎝ i i ⎠

82

How can we calculate activity

coefficients (γ i )???

and composition of each species in

the solution

Activity coefficient (γ i ) at given T

and composition (in case of binary

mixtures) can be calculated using

the following equations:

83

ln γ 1 = Ax22

ln γ 2 = Ax12

where

A = P + QT

on type of a binary system)

84

Example For a methanol (1) + methyl

acetate (2) binary mixture, activity

coefficients of methanol and methyl

acetate can be calculated using the

following equations: lnγ 1 = Ax22 and

ln γ 2 = Ax12 , where A = 2.771− 0.00523 T ( T in

K)

The values of A, B , & C for Antoine

equation are as follows

A = 5.20277 A = 4.18621

B = 1580.080 B = 1156.430

C = 239.500 C = 219.690

85

Determine

a) bubble-point P at T = 300 K and

x1 = 0.2

A=

=

Thus,

and

86

Vapour pressure of each

species can be calculated using an

Antoine equation, as follows

87

Hence, a bubble-point P can

be calculated as follows

composition of gaseous phase at the

bubble point, using Eq. 4.17

88

and

89

b) dew point T at P = 1 bar and y1 = 0.3

of xi , we cannot calculate the values

of γ i

We, however, can start with the

“original” Raoult’s law by assuming

that γ i = 1

know the value of T, we cannot

calculate Pi sat

90

Thus, we need to employ a

TRIAL & ERROR

technique

gives (Eq. 4.12)

B

T sat = −C (4.12)

A − log P

Thus,

91

Accordingly, the first guess of T

should be between 56.6 and 64.2 oC

(WHY??)

T = 60 oC (333 K)

equation), we get

92

At a dew point, ∑x i =1

Thus,

1

P= (4.20)

⎛ yi ⎞

∑ ⎜ γ Psat ⎟

⎝ i i ⎠

values (at T = 60 oC) into Eq. 4.20

yields

93

However, the total pressure has

to be 1 bar

error, but we can use P obtained

recently to calculate the values of xi

as follows

94

and

calculate the values of γ i at 60 oC, as

follows

A=

=

95

Since T is still the same (= 60 oC),

Pi sat is also still the same

96

Substituting new corresponding

values into Eq. 4.20 results in

Î another Trial & Error

(= 1.07 bar) to calculate x1 and x2 as

follows

97

and

98

Trial & Error Procedure

• Calculate γ 1 and γ 2 from x1

and x2

• Guess new T

• Calculate Pi sat at new guessed T

• Calculate P and determine if it

is close to 1 bar (in an

acceptable level), if NOT,

another Trial & Error

99

c) if an azeotropic point exists at T = 300

K. If so, determine the composition of

each species at the azeotropic point

azeotropic point

x1 = y1 Î x2 = y2

y i P = xiγ i Pi sat (4.17)

results in

y i γ i Pi sat

=

xi P

100

Thus,

y1 γ 1P1sat

= (4.21)

x1 P

y2 γ 2 P2sat

and = (4.22)

x2 P

(4.21)/(4.22) yields

y1 γ P sat

1 1

x1

= Psat

y2 γ 2 P2

x2 P

y1 / x1 γ 1P1sat

= α12 = (4.23)

y 2 / x2 γ 2 P2sat

101

From the relationships

ln γ 1 = Ax22

ln γ 2 = Ax12

we obtain

ln γ 2 = Ax12 = 0 Î γ 2 = 1

ln γ 1 = Ax12 = 0 Î γ 1 = 1

and ln γ 2 = A Î γ 2 = exp ( A)

102

Hence, in the case where x1 = 0

P1sat exp ( A)

α12 = (4.24)

P2sat

and when x1 = 1

P1sat

α12 = sat (4.25)

P2 exp ( A)

x2 = y2 Î α12 = 1

(27 oC), P1sat = 0.188 bar , P2sat = 0.315 bar ,

and A = 1.202

103

Substituting corresponding

values into Eqs. 4.24 & 4.25 yields

104

From the values of α12 (@ x1 = 0 )

between x1 = 0 and x1 = 1 where α12 = 1

exists an azeotropic point between

x1 = 0 and x1 = 1

105

At the azeotropic point, α12 = 1

Hence,

γ 1P1sat

= α12 = 1

γ 2 P2sat

P1sat γ 2

=

P2sat

γ1

Substituting corresponding

values (from Question a)) gives

P1sat

sat

=

P2

106

ln γ 1 = Ax22 and ln γ 2 = Ax12

Hence,

γ2

ln γ 2 − ln γ 1 = ln = A ( x12 − x22 )

γ1

γ2 1

ln = A ( x1 − x2 )( x1 + x2 )

γ1

= A ( x1 − x2 )

= A ( 2 x1 − 1)

Thus,

107

The composition at the

azeotropic point of species 1 is

………………………………………………

108

VLE from K-value Correlations

yields the results close to

experimental data, VLE calculations

using modified Raoult’s law are

relatively complicated

109

DePriester, C.L. (1953) constructed

the relationship between yi and xi in the

form of Ki , as follows

yi

Ki = (4.26)

xi

yi

xi = (4.27)

Ki

y i = xi Ki (4.28)

110

At a bubble point, ∑y i =1

∑y = ∑x K

i i i =1 (4.29)

At a dew point, ∑x i =1

yi

∑ xi = ∑ K = 1 (4.30)

i

111

Example Determine a bubble-point T

at 150 psia of a mixture comprising

10 mol% methane, 20% ethane, and

70% propane

At bubble point, ∑y = ∑x K

i i i =1

Given

xCH4 = 0.10

xC2H6 = 0.20

xC3H8 = 0.70

112

Try T = 50 oF as the first guess

chart at T = 50 oF and P = 150 psia

results in

KCH4 =

KC2H6 =

KC3H8 =

Thus,

113

Guess a new T Î T = 0 oF

chart at T = 0 oF & P = 150 psia gives

KCH4 =

KC2H6 =

KC3H8 =

Hence,

obtain T that makes ∑y i =1

114

The resulting T is bubble-point T at

P = 150 psia

Try doing it yourself

(the answer is -50 oF)

error technique, the calculations are not

too complicated, but rather

straightforward

Additionally, this technique is good

for the mixtures with more than 2

components

Accordingly, this technique is widely

used for VLE calculations, especially for

hydrocarbon mixtures

115

116

117

Flash Calculations

into a low-P tank (called a “flash

tank”), the feed divides into 2

phases: liquid & vapour

In other words, the feed, especially

for components whose vapour

pressures are high, partially

evaporates

118

Suppose F mol of feed with a

composition of each species of zi is

introduced into a flask tank

Let

V is the number of moles of feed

that evaporates

and

L is the number of moles of liquid

(or the number of moles of feed that

does not evaporate)

vapour and liquid phases are denoted

as yi and xi , respectively

119

Material Balance

Overall balance

F=V+L (4.31)

Species balance

z i F = y i V + xi L

(4.32)

fi = vi + li

y i = Ki xi (4.28)

into Eq. 4.32 yields

z i F = Ki xi V + xi L

= xi ( Ki V + L )

⎛ V ⎞

= xi ⎜ Ki + 1⎟ L

⎝ L ⎠

120

Rearranging gives

zi F

li = Lxi =

⎛ V ⎞

⎜ Ki + 1⎟

⎝ L ⎠

At a dew point, ∑x i =1

Thus,

zi F

∑ li = ∑ Lxi = L∑ xi = L = ∑ ⎛ V ⎞

⎜ Ki + 1⎟

⎝ L ⎠

results in

zi F

L = ∑ li = ∑ (4.33)

⎛V ⎞

Ki ⎜ ⎟ + 1

⎝L⎠

121

Substituting Eq. 4.26

yi

xi = (4.26)

Ki

yi

zi F = y iV + L

Ki

y i Ki V + y i L

=

Ki

z i Ki F = y i Ki V + y i L

= y i ( Ki V + L )

⎛ L⎞

= y i ⎜ Ki + ⎟ V

⎝ V⎠

Rearranging gives

z i Ki F

vi = y i V =

⎛ L⎞

⎜ Ki + ⎟

⎝ V⎠

122

At a bubble point, ∑y i =1

Hence,

z i Ki F

∑ vi = ∑ yiV =V ∑ yi = V = ∑ ⎛ L ⎞

⎜ Ki + ⎟

⎝ V⎠

gives

z i Ki F

V = ∑ vi = ∑ (4.34)

L

Ki +

V

123

Example Perform a flash calculation

for the following mixture:

methane 10% mol

ethane 20% mol

propane 70% mol

fed into a tank with P = 200 psia and

T = 50 oF

Thus,

100 = V + L

124

Since there are 2 unknowns (V &

L), but we have only ONE equation,

we need to use a trial & error

technique

(or L). Let’s start with V = 30 kmol Î

L = 70 kmol

fi zi Ki F

vi =

Component zi Ki Ki +

L

[kmol] V

Methane 10 0.10 9.8 ( 0.10 )( 9.8 )(100 ) = 8.11

70

9.8 +

30

Propane 70 0.70 0.52 12.76

100 1.00 Σ = 29.44

125

The resulting value of ∑v i or V is

is still not close enough

and another guess, if the resulting

and guessed values are still not close

to each other

guessed value of V is 28.7, we get

126

fi z i Ki F

vi =

Component zi Ki L

[kmol] Ki +

V

Methane 10 0.10 9.8 ( 0.10 )( 9.8 )(100 ) = 8.04

71.3

9.8 +

28.7

Propane 70 0.70 0.52 12.30

100 1.00 Σ = 28.69

CLOSE ENOUGH!!

127

The results of the flash calculation

are summarised in the following Table

fi vi li

Component

[kmol] [kmol] [kmol]

Methane 10 8.04 10 – 8.04 = 1.96

Ethane 20 8.35 11.65

Propane 70 12.30 57.70

100 28.69 71.31

128