Phase Equilibria Two-Component System

I. LIQUID-LIQUID SYSTEM
Ideal Solution
A(g) + B(g)

at equilibrium
i(g) = i(l) -------------------------eqn 1
if the vapor behaves ideally
i ( g ) io( g ) RT ln

A(l) + B(l)

Pi
Po

---------------eqn 2

Po standard state pressure of 1 bar

i (l ) io(l ) RT ln a i ------------------eqn

Substituting to eqn 1
io( g ) RT ln

Pi

io(l ) RT ln a i ---------------------------eqn

For pure liquid

ai = 1
io( g ) RT ln

Pi*
P

io( l )

- equilibrium pressure of pure i at temp. T

Subtracting from equation 4
Pi *

RT ln
ai

Pi
Pi*

Pi
Pi*

RT ln a i

---------------------------------------------------eqn 5

Thus if the vapor is ideal gas, the activity of a component of a solution is equal
to the ratio of its partial pressure above the solution to the vapor pressure of
the pure liquid.

Since for ideal solution, ai = xi; xi mole fraction of component I

Pi x i Pi*

Raoults Law

or
y i Pi x i Pi *

y mole fraction in the gas phase

Substituting to equation 3
i (l ) io(l ) RT ln x i --------------------------------------eqn 6
Total vapor pressure
P = P1 + P 2
P x1 P1* x 2 P2*
P P2* ( P1* P2* ) x1

Equation for the bubble point line

For any given system and temperature P1* & P2* are constant, and hence the
plot of P vs. x should be a straight line with P = P1* at x2 = 0 and P = P2*
at x1 = 0
T=k
L
P
Bubble point line
V
0

xi
Fig. 1

at a lower pressure P, bubbles of vapor will form

P1
x1 P1*
x1 P1*
y1

P1 P2 x1 P1* x 2 P2* P2* ( P1* P2* ) x1

Which means that there is a definite composition of vapor corresponding to

each composition of solution and very special case where P1* P2*
Total vapor pressure from vapor composition
P

P1* P2*
P1* ( P2* P1* ) y1

Equation for the dew point line

T=k
L
P
Dew point line
V
0

xi

Fig 2
To describe a two component system, the phase rule shows that F = 4 P. Since P
is 1 or greater, 3 variables at most must be specified to describe the system. Since
the plot of P vs. x/y, T is specified; only two additional variables are required to
describe the state of the system completely. These two variables may be P & x or P
& y. As a consequence, the pts, in Fig.1 & 2 describe the state of the system.

Representing both plot on a one diagram gives the phase diagram

(To describe the entire system)
T=k

correspond to the lowest pressures

at which liquid can exists by itself
(since vapor appearsif the pt. lies
on the curve)
l
L and V are at equilibrium

xi

v---l - tie line; points on the dew point line and bubble point line at the same
pressure represent the composition of the vapor and liquid phases that are
in equilibrium.
Liquid is stable above liquid curve, the vapor below the vapor curve.
Interpretation of P x or P y Diagram
T=k

Consider pt. a in the L V region

the value x corresponding to the
mole fraction of component in the
entire system L & V. Drawing a
tie line at constant P, the intersection
of this line with the liquid curve b
yield the value x, which describes
the composition of the liquid while
the intersection with the vapor curve
At c yield the value of y which
describe the composition of the vapor

L
P

x
V

xi

If two phases, L and V are present in equilibrium, then the variance of the system is
F = 4 2 = 2. Since the temperature is fixed the other variable any one of P, x,y is
sufficient to describe the system since x1 + x2 = 1 and y1 + y2= 1.

The Lever Rule

In any two phase region such as L-V, the composition of the entire systems may
vary between the limits x1 and y, depending upon the relative amount of L and V
present. If the state pt. a is very near the liquid line, the system would consists of a
large amount of liquid and relative amount of vapor or vice versa. The relative
amount of L and V present are calculated by the lever rule
x
ab

y
bc

Changes in State as the Pressure is Reduced Isothermally

The behavior of the system is now examined as the pressure is reduced from a very
high value to a very low value, keeping the overall composition constant at a mole
fraction of component 1 equal to x.
T=k
a
P

l
v
a
v

l
l

a
y
0

x
xi

.a - the system is entirely liquid

.l the first trace of vapor appears having
composition y
a liquid has a composition x
while vapor has a composition y
v only a trace of liquid of composition
x remains, the vapor has composition
x
a vapor has a composition of the
original liquid

The Thermodynamics of Mixing

1. The Gibbs free energy of mixing
mixG = RT(n1lnx1 + n2lnx2)

2. The Entropy of mixing

mixS= -R(n1lnx1 + n2lnx2)
3. The enthalpy of mixing
mixH = 0
4. The volume change of mixing
mixV = 0
Temperature Composition Diagram
The plot at constant pressure of boiling points versus composition for the ideal
solution is shown. Neither the liquid (Bubble point line) nor the vapor (Dew
point line) curve is a straight line
P=k

v
v
y
0

a
v
a

l
a
x
xi / yi

l
l

x x

.a - the system is entirely liquid

.l the first trace of vapor appears having
composition y
a liquid has a composition x
while vapor has a composition y
v only a trace of liquid of composition
x remains, the vapor has
composition x
a vapor has a composition of the
original liquid

Problem 1. At 60oC the vapor pressure of pure benzene and toluene are 0.513 bar
and 0.185 bar respectively. What are the equation of the bubble point line and
dew point line? For a solution with 0.6 mole fraction toluene what are the
partial pressure of toluene and benzene? What is the total vapor pressure and

composition of the vapor when boiling begins? What is the total pressure when
a trace of liquid remains? and what is the composition of this trace of liquid
Problem 2. Using data of problem 1. What are the activities of toluene and
benzene in a solution containing 0.6 mole fraction toluene?
Problem 3. What is the mole fraction of toluene in the toluene-benzene solution
that boils at 100oC, and what is the mole fraction of toluene in the vapor? The
vapor pressure of pure toluene and benzene at this temperature are 0.742 bar
and 1.800 bar respectively.

Non Ideal Solution / Mixtures

Most liquid solutions are not well described by Raoults Law. Figure 1
shows a system with pronounced positive deviation, and Figure 2 shows a system
with pronounced negative deviation.
Liquid

Gas

Liquid

Raoults law

Gas

Raoults law

x1 , y2
1
0
x1 , y2
1
Figure 1a
Figure 2a
In both cases the bubble point line and dew point line are horizontally
tangent to each other at the maximum or minimum. Systems with a maximum or
minimum are referred to as azeotropes. At the azeotropic composition, the vapor
has the same composition as the liquid. When a system has a minimum in the
vapor plot, it will have a maximum in the boiling point plot, while when it has a
maximum in the vapor pressure plot, it will have a a minimum in the boiling point
plot. As shown below Figure 1b and Figure 2b
Gas

Gas

T
Liquid

Liquid

0
x1 , y2
1
0
x1 , y2
1
When a systems forms an azeotrope, its components cannot be separated by
simple fractional distillation

Colligative Properties of an Ideal Solutions

- properties of dilute solution that depend on only the number of solute

molecules and not on the type of species present. (Latin colligatus,
meaning bound together)
1. boiling point elevation
2. Freezing point depression
3. Osmotic Pressure

can be related to a lowering of vapor

(P* - P) for dilute solute of nonelectrolyte
solute

To illustrate the change is to use the ordinary phase diagram of P against T for
water.
1 atm

Tf T*f

T*b Tb

1. Freezing Point Depression

Consider
Solution SolidA
Ao ( s, T ) A (l , T , x A )
Ao (l , T ) RT ln x A

Ao ( s, T ) Ao (l , T )
ln x A
RT
ln x A

fus G Ao (T )
RT

fusGoA(T) = fusHoA - TfusSoA

fus H T
o
A

fus H Ao
T fus , A


T
fus H Ao 1

T
fus , A

fus H Ao
ln x A

1
1

T T fus , A

fus H Ao
ln x A

T fus , A T

T fus , AT

fus H Ao
ln(1 x B )

T fus , A T

T fus , AT

If the freezing point depression is very small

2
RT fus

,A

T f

xB

H
fus

o
A

xB

T f

mB

mB M A

1
mB
MA

2
RT fus
, A M A mB

fus H Ao

K f mB

Where
Kf

2
RT fus
,A M A

fus H Ao

Kf - freezing point depression constant or

cryoscopic constant
2. Boiling Point Elevation
Tb K b m B

Kb

2
RTvap
,AM A

vap H Ao

3. Osmotic Pressure ()

solution

solvent

Semipermeable membrane
At equilibrium
1o ( P, T ) 1 ( P , T , x1 )

For ideal solution

1o ( P, T ) 1o ( P , T , ) RT ln x1

since
d = V1dP
thus
1o ( P , T ) 1o ( P, T )

V1o dP

1o ( P , T ) 1o ( P, T ) V1o

substituting
V1o RT ln x1 RT ln(1 x 2 ) )

V1o RTx 2

RTx 2 n 2 RT

CRT
V
V

Solid-Liquid System
I. Simple Eutectic Diagram

Consider a system in which the components are completely miscible in the

liquid state and completely immiscible in the solid state, so that only the pure solid
phases separate out on cooling. Example: Bismuth-Cadmium System
350oC 0%Cd 20%Cd 40%Cd
100%Cd
A
80%Cd
I

300oC
B

250oC

G
C

200oC

D
Bi + liquid

150oC

Cd + liquid
K

H
Bi + Cd

100oC
Time

0
Bi

20

40
60
Weight % Cd

80

100
Cd

Cooling curves and the temperature-concentration phase diagram for the

system bismuth-cadmium at constant pressure
In the area above JKL there is one liquid phase, the phase rule is F = 3 - p,
there are two degrees of freedom which can be taken as temperature and one mole
fraction.
Along JK bismuth freezes out; along KL, cadmium. Thus in the area under
JK and down to the eutectic temperature K there are two phases: solid bismuth and
a solution. Similarly in the area under KL and down to eutectic temperature K there
are two phases: solid Cadmium an d a solution. In this region F = 1; only
temperature or composition nee to be specified.
At the eutectic point K there are three phases: solid bismuth, solid cadmium,
and liquid solution containing 40% cadmium. Then F = 0

The area below eutectic temperature K is a two-phase area in which solid

bismuth and solid cadmium are present. F = 1. Only temperature need to be
specified
The solubility xA of A in solvent B is given by
fus H Ao
x A exp
R

1
1
T T
fusA

II. Compound Formation with Congruent Melting point

The components of a binary system may react to form a solid compound that
exists in equilibrium with liquid over a range of composition. If the formation of a
compound leads to a maximum in the temperature-composition diagram, we may
say there is a congruently melting compound.
700OC
E
Liquid
600OC

C
F

500OC

MgZn2
+
solution

MgZn 2
+
solution

Mg
+
solution

A
400OC

Zn + B
solution
D

300OC

Zn + MgZn2
MgZn 2 + Mg

200OC
0

20

Zn
Ternary Phase Diagrams

40

60

Mole percent Mg

80

100

Mg

In ternary systems involving 3 components the Gibbs phase rule predicts a

maximum of:
F = C-P+2 = 3-1+2 = 4
degrees of freedom, when only a single phase is present. In depicting these
diagrams usually both pressure and temperature are held constant and the
composition variables plotted against each other on a triangular diagram:
C

A
B

Locate the system on this diagram that is 30% B and 55% A.

Problems:
1. From the following data for the system o-dinitrobenzene- p-dinitrobenzene
Mol% of pInitial Melting

dinitrobenzene
Point, oC
100
173.5
90
167.7
80
161.2
70
154.5
60
146.1
50
136.6
40
125.2
30
111.7
20
104.0
10
110.6
0
116.9
Construct a temperature-composition diagram for the system, and
determine there from the eutectic temperature and composition.
2. Using the plot constructed in the preceding problem, find graphically the
maximum percentage of p-dinitrobenzene which can be recovered pure
by crystallization from mixture of two compound containing originally 95%
of p-dinitrobenzene.
3. The following data are for the system water-alcohol-benzene at 25OC. The
first two columns give the percentages by weight of alcohol and benzene
in one layer, while the third column gives the percentage by weight of
water in the layer conjugate to these.
Layer 1
Layer 2
% C6H6
% C2H5OH
% H2O
1.3
38.7
9.2
50.8
20.0
52.3
3.2
30.0
49.5
5.0
40.0
44.8
6.5
60.0
33.9
13.5
80.0
17.7
34.0
95.0
4.8
65.5
Construct the phase diagram for the system, and draw in the tie-lines.
4. An aqueous solution contains 46% by weight of ethyl alcohol. Using the
diagram of the preceding problem, find how much alcohol would be
extracted from 25 g of this solution by 100 g of C6H6.