SAL COLLEGE OF ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

ALA
CHEMICAL ENGINEERING THERMODYNAMICS -II
( 2150503)

TOPIC : SIMPLE MODELS FOR VAPOUR/LIQUID EQUILIBRIUM,

RAOULTS LAW, DEWPOINT AND BUBBLE POINT CALCULATIONS WITH
RAOULTS LAW
YASHRAJ JADEJA (131130105016)
SANDIP KOLADIYA (131130105022) FACULTY:
MANAS DOSHI (131130105027) DR. BHAVNA SONI
MILAN DONGA (131130105032)
 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

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

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

Raoults Law Henrys Law

5
 RAULTS 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
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 Dewpoint & Bubblepoint Calculations with
Raoults 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
 Raoults 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 Raoults 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.

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;

P 41.98 83.21 41.980.6

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

yi P xi Pi sat

x1P1sat 0.683.21
y1 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

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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;

1
P
y1 P1 y2 P2
sat sat

For y1=0.6 and t=750C

1
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= 78C into (i) and (ii)
e.g; select T= 78C 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 0.515691.76
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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
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 Henrys 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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 Henrys 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. Henrys constant for
CO2 in water at 100C is about 990 bar and
x1=0.01.

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Henrys law for species 1 & Raoults 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 0.01990 0.99 0.01227

P 9.912 bar
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 Then by Raoults law, Eq. 1 written for species 2;

x2 P2sat 0.990.01227
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 RAOULTS LAW

The 2nd assumption of Raoults Law is abandoned,

taking into account the deviation from solution
ideality in L phase.

Thus, activity coefficient is introduced in Raoults
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 Raoults Law yi P xi Pi sat

sat
Pi
Ki 11

P
K-value for modified Raoults 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

31
K-value
from
DePriester
chart
-High T
range

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