Two component system containing liquid phases 1

1- Introduction:
Systems containing more than one component are
best discussed as condensed systems.
Condensed systems are systems in which the
vapor phase* is ignored and only solid and liquid
phases are considered.
Phase*:
is homogeneous physically distinct
portion of the system, which is
separated from other parts of the
system by bounding surfaces.

Systems containing liquids often are classified as:

• Completely Immiscible (such as mercury and water).
• Completely miscible in all proportions (e.g., ethanol and water).
• Partially miscible (e.g., phenol and water).

For two components systems:

C=2 , F=C–P+2⟹F=4–P Note:
P = 1 at least, so F is 3 at most. P = No. of phase.
Three variables are required: temperature, pressure and
C = No. of components.
composition.
If the pressure is fixed: F = degree of freedom.
C=2 , F=C–P+1⟹F=3-P
P = 1 at least, so F is 2 at most.
Only are temperature and composition are required.

Phase diagrams for two component systems are commonly constructed with
temperature and composition as the coordinates (see Fig. 1). Usually, the
composition is expressed as mole fraction or percent by weight (w/w %).

2- Phase diagrams of two component system containing liquid phases:

To explain the effect of concentration and temperature on the miscibility of tow
liquid that are partially miscible, we prepare the following concentration of phenol
in water by (w/w %) as the total weight is (10 gm):
(2% , 7% , 9% , 11% , 24% , 40% , 55% , 63% , 70% , 75%)

Note:
2% means:
0.2 gm phenol.
9.8 gm water.
Two component system containing liquid phases 2
Then we draw graph paper of temperature versus concentration depending on
miscible the phenol and water or not at certain concentration and temperature as
showing in the following diagram:

Fig. 1: Temperature-composition diagram for the system consisting of water and phenol.

From the above diagram we can see:

▪ Curve gbhci shows the limits of temperature and concentration within which two
liquid phases exist in equilibrium. The region outside this curve contains systems
having but one liquid phase. This curve called binodal curve.

▪ Starting at the point a, equivalent to a system containing 100% water (i.e., pure
water) at 50° C, adding known increments of phenol to a fixed weight of water,
the whole being maintained at 50° C, will result in the formation of a single liquid
phase until the point b is reached, at which point a minute amount of a second
phase appears.

▪ Mixtures (b to c) are containing increasing amounts of phenol. Thus, systems in

which the amount of the phenol-rich phase (B) continually increases and the
amount of the water-rich phase (A) decreases. Once the total concentration of
phenol exceeds 63% at 50° C, a single phenol-rich liquid phase is formed.

▪ The maximum temperature at which the two-phase region exists is termed the
critical solution, or upper consolute temperature. In the case of the phenol-
water system, this is 66.8o C (point h). All combinations of phenol and water
above this temperature are completely miscible and yield one phase liquid
systems.
Two component system containing liquid phases 3
▪ The line bc drawn across the region containing two phases is termed a tie line; it
is always parallel to the base line in two component systems.

▪ An important feature of phase diagrams is that all systems prepared on a tie line,
at equilibrium, will separate into phases of constant composition. These phases
are termed conjugate phases. For example, any system represented by a point on
the line bc at 50o C separates to give a pair of conjugate phases whose
compositions are b and c.

▪ It is seen that if the temperature is given, the compositions of the two phases are
fixed by the points at the ends of the tie lines, for example, points b and c at 50°
C. The compositions (relative amounts of phenol and water) of the two liquid
layers are then calculated by the following method:
If we prepare a system containing 24% by weight of phenol and 76% by weight
of water (point d), at equilibrium we have two liquid phases present in the tube.
The upper one (A) has a composition of 11% phenol in water (point b), whereas
the lower layer (B) contains 63% phenol (point c). Phase (B) will lie below phase
(A) because it is rich in phenol, and phenol has a higher density than water, so
the formula of the relative weights of the two phases will be:
Weight of phase A Length dc
=
Weight of phase B Length bd
point b = 11% , point c = 63% , point d = 24%
The ratio dc/bd = (63 - 24)/(24 - 11) = 39/13 = 3/1. for every 10 gm of a liquid
system in equilibrium represented by point d, one finds 7.5 mg of phase (A) and
2.5 gm of phase (B).

One phase Two phases

 Two component system containing liquid phases 4
The phase diagram is used in practice to formulate systems containing more than one
component where it may be advantageous to achieve a single liquid-phase product. For
example, the handling of solid phenol, a necrotic agent, is facilitated in the pharmacy if
a solution of phenol and water is used. A number of solutions containing different
concentrations of phenol are official in several pharmacopeias.
Not all system has upper consolute temperature like
phenol in water, some systems may contain a lower
critical temperature instead of upper critical
temperature such as triethylamine in water.

While others may contain both upper and lower

critical temperature such as nicotine in water.

3- Experimental work:
To prepare system containing phenol and water by weight (w/w %) in the labrotary,
we do the following steps:

• Prepare the following percent by weight (phenol/water) with total weight (10
gm):
2% ,7% , 9% , 11% , 24% , 40% , 55 % , 63% , 70% , 75%.

• Put test tube in a fixed temperature in water bath (25 o C) or (left test tube at room
temperature) and keep it for 10 minutes at that temperature.

• Take the test tubes out and before their temperature has changed record which
one has two phases and which has one phase.
Two component system containing liquid phases 5
• Repeat the work at higher temperature using the following temperature: 40o C,
50o C, 70o C. Write the results as the following table:

% Weight
25o C 40o C 50o C 70o C
Temperature
2%
7%
9%
11%
24%
40%
55%
63%
70%
75%

• Draw a curve temperature verses concentrations showing your two phases area
and one phase area in the curve as showing in the following diagram:

• Draw tie line for each temperature.

• Mention the upper consulate temperature.

 Two component system containing liquid phases 6
Reference:
[1] Patrick J. Sinko, “Martin’s physical pharmacy and
pharmaceutical sciences”, sixth edition, (2011).

[2] Alexander T. Florence, David Attwood,

“Physicochemical Principles of Pharmacy” sixth edition,
(2015).