Aim: Study of the ternary phase equilibrium of acetic acid-chloroform-water at room

temperature and construction of the triangular plot phase diagram.

Theory: The phase equilibrium of the ternary system involving acetic acid (A), chloroform (C)
and water (W) has the characteristic feature that C and W are mutually practically immiscible,
while A is completely miscible with either C or W. So, a mixture of all three would be either a
one-phase system or a two-phase system, depending on whether proportion of A is, respectively,
sufficient or small. In presence of a small proportion of acetic acid, the mixture remains two-
phase, though both the phases would contain both chloroform and water, though in larger or
smaller proportions. Now, for any given proportion of C and W, there exists a minimum specific
proportion of A, above which proportion the system becomes one-phase.
The composition by mass of such a ternary system can be clearly expressed by using a triangular
phase diagram. In this diagram, the three pure substances are expressed as the three corner-points
of a symmetric triangle. Naturally, each of the three sides implies a binary mixture in which the
substance implied by the opposite corner is completely absent. The inside of the triangle,
however, means the true ternary solutions
with all the three components present. Within
such a triangular phase diagram, the A-C-W
system gives a binodal curve that would lie in
the opposite side of the A-corner. If the A
(acetic acid) corner-point is drawn in the top
position, as is popularly the convention, the
region above this binodal curve is one-phase,
while that below this curve is two-phase, as is
shown in the figure. Points belonging to this
binodal curve may be ascertained by starting
with binary chloroform-water mixtures of
various proportions, then by noting the
minimum amount of acetic acid that would
make the mixture clear, i.e., one-phase.
To mark a particular point corresponding to a given ternary mixture on this phase diagram, we
need to first calculate the masses of the three components in that mixture (say WA, WC and WW),
then calculate the mass fractions (fA = WA/WTot, fC = WC/WTot, fW = WW/WTot, where WTot = WA
+ WC + WW is the total mass) then use any two of these mass fractions (say fA and fW) of that
mixture to locate and mark the corresponding point, noting that fA, in this diagram, increases
from 0.0 at the bottom to 1.0 at the top vertex (i.e., as shown on the right hand side), whereas fW,
in this diagram, increases from 0.0 at the left corner to 1.0 at the right corner (i.e., as shown on
the bottom base side). The point to be located is on the intersection point of the two straight lines
corresponding to these fA and fW values.
Requirements: Graduated 2 mL pipettes, micro-burettes, glacial acetic acid, chloroform, distilled
water
Procedure:
(1) To a clean and dry ‘hard glass test tube’, added 3.0 mL (≡ 4.5 g) of chloroform from a micro-
burette. To this, added 0.5 mL (≡ 0.5 g) of water (thus forming a 10% w/w binary water solution)
and shaken vigorously. From another micro-burette, added glacial acetic acid in small increments
with vigorous shaking, until a clear (not turbid) solution is obtained. Noted the volume of acetic
acid required.
(2) To this mixture, added another 0.6 mL of water and shaken vigorously. From micro-burette,
added more glacial acetic acid in small increments with vigorous shaking, until a clear solution is
again obtained. Noted the additional volume of acetic acid required.
(3) This process (2) was repeated with additional volumes of water as (0.8 mL, 1.1 mL, 1.5 mL)
in three more steps, noting the additional volume of acetic acid required in each step.
(4) Cleaned and dried the hard glass test tube, then added 5.4 mL of water from a burette. To
this, added 0.4 mL (≡ 0.60 g) of chloroform (thus forming a 90% w/w binary water solution) and
shaken vigorously. From another burette, added glacial acetic acid in small increments with
vigorous shaking, until a clear solution is obtained. Noted the volume of acetic acid required.
(5) To this mixture, added another 0.5 mL (= 0.75 g) of chloroform and shaken vigorously. From
burette, added more glacial acetic acid in small increments with vigorous shaking, until a clear
solution is again obtained. Noted the additional volume of acetic acid required.
(6) This process (5) was repeated with additional volumes of chloroform 0.6 mL (= 0.90 g), 0.9
mL (= 1.34 g) and 1.2 mL (= 1.79 g) in three more steps, noting the additional volume of acetic
acid required in each step.

Observations and Calculations:

1. Table for increasing masses of water:
Volume Total
Mass Mass of Tot. Mass Mass of A Fraction Fraction
Sl. of A Mass of
of C, W added of W, WW (=1.049V) fA (= fW (=
No. added A, WA
WC (g) (g) (g) added (g) WA/WTot) WW/WTot)
V (mL) (g)
1 0.5 0.5
2 0.6 1.1
3 4.5 0.8 1.9
4 1.1 3.0
5 1.5 4.5

2. Table for increasing masses of chloroform:

Volume Total
Mass Mass of Tot. Mass Mass of A Fraction Fraction
Sl. of A Mass of
of W, C added of C, WC (=1.049V) fA (= fW (=
No. added A, WA
WW (g) (g) (g) added (g) WA/WTot) WW/WTot)
V (mL) (g)
1 0.60 0.60
2 0.75 1.35
3 5.4 0.90 2.25
4 1.34 3.59
5 1.79 5.38

Results:
The ten points indicated by the above (fA, fW) values were marked (omitting one
redundant point for fC ≈ fW) on a triangular graph paper with the three corners (A, C, W) marked
as shown above. Joining these nine points with free hand, the binodal curve was obtained.
Triangular Graph Paper for Plotting the Graph