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Equilibrium V
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Taken as three different two-component systems, we find that water and acetic acid are
miscible in all proportions, as are chloroform and acetic acid. However, water and
chloroform are only partially miscible. This is represented by the two phase region that
lies on the chloroform/water base of the triangle. Note that the compositions on the base
represent the compositions of water-rich and chloroform-rich phases in equilibrium at
this T and P.
Consider a starting solution consisting of 60 % water and 40% chloroform. We are in a 2
phase region along the base of the triangle. When a small amount of AA is added to the
mixture, the composition moves along the line towards the AA apex. The compositions
of the two phases in equilibrium change, and are defined by the ends of the tie line, which
in this case is not horizontal (but the Lever Rule still applies!) As more AA is added, the
solution eventually becomes one phase above the curve.
The point P is called the Plait Point, and it is another example of a critical point, where
the composition of the two phases is equal. At this point, the relative volumes of the two
phases are equal and the boundary vanishes as the system becomes homogeneous.
Equilibrium V
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At high temperatures, the two 2-phase regions are separated, as shown in (a). As the
temperature is decreased, the curves may overlap, resulting in two different possibilities.
In diagram (b), the two plait points merge and result in a 2-phase band. If the curves do
not join at the plait points, the diagram takes the form of (c). In this diagram, there are
three 2-phase regions. The points inside of the abc triangle correspond to a three phase
liquid region where the liquid layers have compositions equal to a, b and c. In general, if
there is a triangle within a ternary phase diagram, this corresponds to a three phase
region! We will see this again in the next example.
Equilibrium V
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In this diagram, point a represents a saturated solution (2 phase) of water and solid
ammonium chloride (in the absence of ammonium sulfate). The points between a and C
represent an unsaturated (1 phase) solution, while the lever rule between a and A
represent the relative amounts of solid ammonium chloride in equilibrium with the
saturated solution. (Likewise for the CB line with ammonium sulfate in the absence of
ammonium chloride.) Now, the addition of ammonium sulfate to the ammonium chloride
solution changes the solubility along line ac. (Likewise for the addition of ammonium
chloride to ammonium sulfate along line bc2.) Note that in the 2-phase regions, the apex
(pure component) is one end of the tie line, so the equilibrium phases consist of solid A
or B with a saturated solution. The points in the triangle AcB correspond to a three
phase region with solid ammonium chloride, solid ammonium sulfate and a saturated
solution with composition c all in equilibrium.
Now consider a solution at point P that is slowly evaporated isothermally. At point d, the
solution becomes saturated with ammonium chloride, which crystallizes. With further
evaporation, the composition of the saturated solution moves along the dc line. At point
e, ammonium sulfate begins to crystallize, and the two solids are in equilibrium with a
saturated solution at c. This continues until point f, when the solution disappears.
Equilibrium V
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