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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
Substituting to eqn 1
io( g ) RT ln
Pi
io(l ) RT ln a i ---------------------------eqn
Pi*
P
io( l )
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.
Raoults Law
or
y i Pi x i Pi *
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
P1* P2*
P1* ( P2* P1* ) y1
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.
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
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.
y
bc
l
v
a
v
l
l
a
y
0
x
xi
v
v
y
0
a
v
a
l
a
x
xi / yi
l
l
x x
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.
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
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
Ao ( s, T ) Ao (l , T )
ln x A
RT
ln x A
fus G Ao (T )
RT
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
,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
Kb
2
RTvap
,AM A
vap H Ao
3. Osmotic Pressure ()
solution
solvent
Semipermeable membrane
At equilibrium
1o ( P, T ) 1 ( P , T , 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
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
1
1
T T
fusA
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
A
B
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.