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CHEMICAL ENGINEERING

THERMODYNAMICS

TOPIC : SIMPLE MODELS FOR VAPOUR/LIQUID


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)

Binary mixture: Mixture that contains two constituents


 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

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 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

Fig. 10.1 – Shows the P-T-composition


surfaces of equilibrium states of
saturated V & saturated L of a binary
system
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SIMPLE MODELS FOR VAPOUR
LIQUID EQUILIBRIUM
Simple Models
For VLE :
Find T, P, composition

Raoult’s Law Henry’s Law

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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)

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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
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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

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For binary systems to solve for
bubblepoint calculation (T is given);

y i i 1

P   xi Pi
i
sat
PP
2
sat
 P  1
sat
P 2
sat
x
1
2

x1 P1 sat
y1  3
P

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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
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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

a)Prepare a graph showing P vs. x1 and P vs. y1 at


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.

PP 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;

P  41.98  83.21  41.980.6


12 P  66.72kPa
The corresponding value of y1 is found from Eq. 1,

yi P  xi Pi sat

y1 
xP
1 1
sat

0.683.21
 0.7483
P 66.72
x1 y1 P/kPa x1 y1 P/kPa

0.0 0.0000 41.98 0.6 0.7483 66.72

0.2 0.3313 50.23 0.8 0.8880 74.96

0.4 0.5692 58.47 1.0 1.0000 83.21


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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;

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P
y1 P1  y2 P2
sat sat

For y1=0.6 and t=750C

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P  59.74kPa
0.6 83.21  0.4 41.98
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And by Eq. 1,
y1 P 0.6 59.74 
x1  sat   0.4308
P1 83.21

This is the liquid-phase composition at point c’

b) When P is fixed, the T varies along T1sat and


T2sat, with x1 & y1. T1sat & T2sat are calculated
from Antoine equation;

Bi
t sat
  Ci
Ai  ln P
i

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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

Get y1 from Eq. 1


x1 P1sat 0.515691.76
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y1    0.6759
P 70
Summary; x1 y1 T/˚C

0.0000 0.0000 89.58


(t2sat)

0.1424 0.2401 86

0.3184 0.4742 82

0.5156 0.6759 78

0.7378 0.8484 74

1.0000 1.0000 69.84


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(t1sat)
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Henry’s Law
Assumptions;

1. For pressure low


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

2. For species present as a very dilute solution in


liquid phase

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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
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Example 2

Assuming that carbonated water contains only


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.

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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

With H1=990 bar & P2sat = 0.01227 bar (from steam


tables at 100C)

P  0.01990  0.99 0.01227 


P  9.912 bar
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Then by Raoult’s law, Eq. 1 written for species 2;

x2 P2sat 0.990.01227 
y2    0.0012
P 9.912

Whence y1=1-y2=0.9988, and the vapor phase is


nearly pure CO2, as expected.

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VLE BY MODIFIED RAOULT’S LAW

The 2nd assumption of Raoult’s Law is abandoned,


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

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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

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AZEOTROPE

A mixture that has a


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.

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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

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For binary systems to solve for bubble
point calculation;

y i i 1

Hence,
Kxi i i 1 13

For binary systems to solve for


dew point calculation;

x i i 1
Hence, yi
 i
Ki
1 14

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K-value
from
DePriester
chart
-Low T
range

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K-value
from
DePriester
chart
-High T
range

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 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

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