NAME

ENROLLMENT NO.

ALAGIYA AMIT

131120105002

KARGAVKAR ASHISH

131120105018

PATEL NIKUNJ

131120105037

PATEL SAWAN

131120105041

PIPALIYA PRITESH

131120105043

THE NATURE OF EQUILIBRIUM

Equilibrium : A static condition in

which no changes occur in the

macroscopic properties of a system with
time.
The T, P,
composition
reaches final
value which will
remain fixed:
equilibrium

Measures of composition
Measures
of
composition

Mass or
mole fraction

mi m i
xi

m m

Molar
concentration

xi
Ci
V

Molar mass for

a mixture or
solution

M xi M i
i

PHASE RULE & DUHEMS THEORY

Equilibrium states are determined by;
Phase Rule
Duhems Theory

The Phase Rule

Number of variables that may be
independently fixed in a system at equilibrium
=
Difference between total number of variables
that characterize the intensive state of the
system and number of independent equation

F = 2-+N
Where : F degrees of freedom
No of phase
N No of species

Duhems Theory
For any closed system formed
initially from given masses of
prescribed chemical species, the
equilibrium state is completely
determined when any two (2)
independent variables are fixed

VLE: QUALITATIVE BEHAVIOR

VLE: State of
coexistence of L
& V phases

Fig. Shows the P-Tcomposition surfaces of

equilibrium states of
saturated V & saturated L
of a binary system

 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
As pressure reduces, more & more L
vaporizes until completed at W; point
where last drop of L (dew) disappear
dew point

SIMPLE MODELS FOR VLE

Simple Models
For VLE :

Find T, P, composition

Raoults Law

Henrys Law

Raoults 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)

yi P xi Pi

sat

i 1,2,..., N

Where;
xi : L phase mole fraction
yi : V phase mole fraction
Pi sat : Vapor pressure of pure species i
P : Total pressure

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

For binary systems to solve for

bubblepoint calculation (T is given);

y
i

P xi Pi
i

sat

PP

sat
2

x1 P1 sat
y1
P

sat
1

sat
2

Raoults law equation can be solved for

xi to solve for dewpoint calculation (T
is given)

i xi

sat
y
P
i i
i

1
P
sat
sat
y1 / P1 y2 / P2

y1 P
x1 sat
P1

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

Henrys Law

yi P xi H i

i 1,2,..., N

Where;
xi : L phase mole fraction

yi : V phase mole fraction

H i : Henry's constant
P : Total pressure

VLE

Raoults Law

Henrys Law

Modified
Raoults Law

K-Values

K-value for Raoults Law

yi P xi Pi

sat

sat

Pi
Ki
P

K-value for modified Raoults Law

i Pi
Ki
P

sat

yi P xi i Pi

sat

AZEOTROPE
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 it evaporates

Relative volatility;

y1 x1
12
y 2 x2

12 x 0
1

sat
1

exp A
sat
P2
sat
1

P
12 x1 1 sat
P2 exp A

(10.8)

If one limit is >1 &

the other limit is
<1; azeotrope
exists.

VLE FROM K-VALUE

CORRELATTIONS
The partition between liquid and vapor
phases of a chemical species is equilibrium
ratio, Ki.

yi
Ki
xi

This quantity is called K-value.

When given a mixture of composition at certain

T or P;
Bubble point

Dew point

-The given mole

fraction is yi

-System is almost
condensed
-The given mole
fraction is xi

- Need to satisfy
equation 10.14

- Need to satisfy
equation 10.13

- Composition of
dew is xi=yi/Ki

- Composition of
buble is yi=Kixi

- Insignificant L

For binary systems to solve for

bubble point calculation;

y
i

Hence,

Kx

i i

1
1

For binary systems to solve for

dew point calculation;

x
i

Hence,

yi
i K 1
i

Activity coefficients are function of T & liquid

phase composition, x
Since;

P xi i Pi

y
i

sat

1
For bubble point

i xi
1
P
sat
yi i Pi
i

1
For dew point

(See Example 10.3)

Bubble Point and Dew

Point with Raoult's Law
Bubble Point

 Therefore, if the temperature and overall

composition are known, the bubble
pressure can be determined directly.
If the pressure is held constant and the
bubble point temperature is required, it is
necessary to calculate the temperature by
an iterative method. The temperature
dependence is contained in the Antoine
equation for vapor pressure of each
component. One method to solve for the
temperature is
to:
1. Guess a temperature
2. Use the guess and the Antoine equation to
calculate the vapor pressure of each
component in the mixture.
3. Calculate an equilibrium pressure using
the bubble point pressure equation.
4. If the calculated pressure does not equal
the known pressure, it is necessary to
change the temperature and try again.

 If there is more than one

component, a similar
derivation yields the
following:

Dew Point
The Dew Point calculation is similar,
although the equation that results
from the derivation is
somewhat
more
complex.
The
starting point is the same: assume
that Raoult's Law applies to each
component.

U
O
Y
K
N
A
H
T