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Vapour/Liquid Equilibrium

(VLE): Introduction

Equilibrium = a static condition in


which no changes occur in a
macroscopic properties of a system
with time

1
The Phase Rule. Duhem’s Theorem

Recall from Chapter 1


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

Example Determine a dof of a


system of a single species of 2 phases
(e.g., liquid and vapour)

2
From the given information
π =

N=

Thus, from the phase rule

This means that we need only one


Thermodynamic property in order to
identify the other properties of the
system

3
Consider a P-T diagram

S V

On the line separating vapour and


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)

From the given information


π =

N=

Thus, from the phase rule

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

At the triple point, all 3 phases (S,


L, & V) coexist in equilibrium)
Thus,
π =

Since it is a pure species,


N=1

Hence, from the phase rule

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

“For any closed system formed


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

Consider VLE of a binary mixture


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

At T = T1, for the mole fraction of


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 Q is called an azeotropic


point
23
It is the point where the mixture
behaves as it is a pure substance

Thus, at this point (or at xA = xAQ),


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

Liquid L+V Vapour

Dew-point
curve

Note that a critical point needs


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

Note that CA & CB = critical points of


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

Two SIMPLEST models:


• 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 ?

From a Thermodynamic table

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)

Note: Try using the Cox chart above


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

From Eq. 4.4, at T = 20 oC, we obtain

Note that the value of Psat from the


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.)

Eq. 4.5 = “Antoine equation”

37
Example The values of A − C for
propane are as follows:
A = 3.92828

B = 803.9970

C = 247.040

From Eq. 4.5, at T = 20 oC, we get

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)

For a binary mixture, we obtain


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

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

When plotting a graph of P against


x1, we obtain a straight line with

• a slope of P1sat − P2sat


• a Y-intercept of
ƒ P2sat at x1 = 0
ƒ P1sat at x1 = 1

Examples of a plot between P and x1


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

is for bubble-point calculations

On the other hand, vapour starts


to condense when ∑x i = 1 or when

1
P= (4.10)
∑ i i )
( y / P sat

Hence, Eq. 4.10 is for dew-point


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)

to this Question gives


P = xpropane ( Ppropane
sat sat
− Pethane ) + Pethane
sat

Substituting the numerical values


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

the following Table


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

of various P can be calculated using


Eq. 4.1 (i.e. a Raoult’s law), as follows
sat
y propaneP = xpropanePpropane

........ xpropane
and y propane =
P

The results are as follows


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

We can rearrange an Antoine


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

T’s, for instance, at T = -22.0 oC, yields

51
Rearranging Eq. 4.9 results in
P − P2sat
x1 = sat
P1 − P2sat

Hence,
sat
P − Pethane
xpropane = sat sat
(4.13)
Ppropane − Pethane

Substituting the resulting values of


sat
Ppropane and Pethane
sat
, & the value of P

(= 10 bar in the case) into Eq. 4.13


yields
xpropane =

52
The value of y propane can then be

calculated as follows (using Eq. 4.1)


sat
xpropanePpropane
y propane =
P
=
=

Carrying out the same calculations


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”

Example 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

Applying a summation for all


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)

Since this is a binary mixture,


sat
P = xpropanePpropane sat
+ xethanePethane (4.14)

57
Given
P = 10 bar
xpropane = 0.3 Î xethane = 0.7

We need T to calculate the values


of Ppropane
sat
and Pethane
sat

Hence, we have to start our


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

We have to perform a Trial & Error


iteration until we obtain T that makes

∑ i i = 10 bar
x P sat

TRY DOING IT YOURSELF

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

Applying a summation for all


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 ⎠

Since it is a binary mixture,


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,

Substituting corresponding values


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

From a Raoult’s law


y i P = xi Pi sat (4.1)

in the case where a concentration


( 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

If we, however, desperately need


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

“Henry’s constant ( Η i )” replaces


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

Henry’s constant ( Η i ) depends on T


as same as vapour pressure ( P sat )

For instances,
Η i of CO2 at 10 oC = 900 bar

Η i of CO2 at 25 oC = 1670 bar

Henry’s constant ( Η i ) also depends


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 )

of CO2 at 25 and 10 oC are 1,670 and


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

On the other hand, we can use a


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

Accordingly, the total pressure of the


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

However, if T is increased to 25 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

If a refrigerator is not available


(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

Evidently, in order to keep CO2 in


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

From the assumptions of a Raoult’s


law, in which
• VAPOUR Phase = IDEAL GAS
• LIQUID Phase = IDEAL SOLUTION

it is found that, in the real situations,


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

The main cause of deviations,


however, comes from the assumption
that liquid phase = ideal solution

To enable a Raoult’s law to be


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

Additionally, we learned that


ˆfi
γi =
xi fi

which also indicates the deviation


from the ideal solution

Hence, an activity coefficient (γ i )

serves as a correction factor for the


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 )???

Activity coefficient depends on T


and composition of each species in
the solution

Activity Coefficient Calculations


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

( P & Q = constant and depend


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

At T = 300 K (27 oC)


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

We can then calculate


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

Since we do not have the data


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

In addition, since we do not


know the value of T, we cannot
calculate Pi sat

90
Thus, we need to employ a
TRIAL & ERROR
technique

Modifying an Antoine equation


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??)

Let the first guess be that


T = 60 oC (333 K)

Hence, from Eq. 4.5 (Antoine


equation), we get

92
At a dew point, ∑x i =1

Thus,
1
P= (4.20)
⎛ yi ⎞
∑ ⎜ γ Psat ⎟
⎝ i i ⎠

Substituting the corresponding


values (at T = 60 oC) into Eq. 4.20
yields
93
However, the total pressure has
to be 1 bar

Hence, we need another trial &


error, but we can use P obtained
recently to calculate the values of xi
as follows

94
and

We can use these x1 and x2 to


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

Close to 1 bar, but not 1 bar yet


Î another Trial & Error

We can use P obtained recently


(= 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

We have known that, at the


azeotropic point
x1 = y1 Î x2 = y2

Rearranging Eq. 4.17


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

when x1 = 0 Î x2 = 1 (binary solutions),


we obtain
ln γ 2 = Ax12 = 0 Î γ 2 = 1

and lnγ 1 = A Î γ 1 = exp ( A)

and when x1 = 1 Î x2 = 0 , we get


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)

At an azeotropic point, x1 = y1 &


x2 = y2 Î α12 = 1

From Question a, at T = 300 K


(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 )

and α12 (@ x1 = 1) , it was found that

α12 (@ x1 = 0 ) > 1 while α12 (@ x1 = 1) < 1

indicating that there is a point


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

This, in turn, means that there


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

Although a modified Raoult’s law


yields the results close to
experimental data, VLE calculations
using modified Raoult’s law are
relatively complicated

Is there any other (easier) method?

109
DePriester, C.L. (1953) constructed
the relationship between yi and xi in the
form of Ki , as follows
yi
Ki = (4.26)
xi

Rearranging Eq. 4.26 results in


yi
xi = (4.27)
Ki

y i = xi Ki (4.28)

110
At a bubble point, ∑y i =1

Hence, from Eq. 4.28,

∑y = ∑x K
i i i =1 (4.29)

At a dew point, ∑x i =1

Thus, from Eq. 4.27,


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

Reading the Ki values from the


chart at T = 50 oF and P = 150 psia
results in
KCH4 =
KC2H6 =
KC3H8 =

Thus,

Guessed T was too high

113
Guess a new T Î T = 0 oF

Reading the Ki values from the


chart at T = 0 oF & P = 150 psia gives
KCH4 =
KC2H6 =
KC3H8 =

Hence,

Still to high Î guess new T, until we


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)

Although we have to use a trial &


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

When a liquid feed is introduced


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)

Mole fraction of each species in the


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

Substituting Eq. 4.28


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 ⎠

Rearranging the above equation


results in
zi F
L = ∑ li = ∑ (4.33)
⎛V ⎞
Ki ⎜ ⎟ + 1
⎝L⎠

121
Substituting Eq. 4.26
yi
xi = (4.26)
Ki

into Eq. 4.32 yields


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⎠

Rearranging the above equation


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

Basis: 100 kmol of mixture ( F )

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

We start by guessing a value of V


(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

Ethane 20 0.20 1.75 8.57


Propane 70 0.70 0.52 12.76
100 1.00 Σ = 29.44

125
The resulting value of ∑v i or V is

close to 30 (the guessed value), but it


is still not close enough

Try another guess, another guess,


and another guess, if the resulting
and guessed values are still not close
to each other

It was found that, when the


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

Ethane 20 0.20 1.75 8.35


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