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Investigation of the Ternary Phase Diagram of Water—Propan-2-

ol—Sodium Chloride: A Laboratory Experiment
P r e ssu r e (M P a )
Physical Chemistry I Laboratory
1E+11 The Gibbs phase rule is given by the
1E+10
Ice VII 1E+09
Ice VI 1E+08 formula F = C –  + 2, where F is the
1E+07
Ice V 1E+06
number of degrees of freedom
1E+05
Ice III 1E+04
1E+03 (independent intensive variables), C is the
1E+02
L iqui d 0 200 400 600 800
Temperature (K) number of components, and  is the

number of phases in thermodynamic

equilibrium with each other. In the case of

Sol i d Ice I

a pure substance, the number of

components is 1, and therefore F = 3 – .

To see how this relates to a phase diagram

Vap o u r of a pure substance, we consider the

Figure 1. Phase diagram of water
phase diagram of water (Figure 1). If we

pick a pressure P and temperature T, we can determine how many phases are in equilibrium. For

example, at 298.15 K and 0.1 MPa (1 bar), there is one phase present (liquid), and the pressure and

temperature can both be varied slightly without affecting the number of phases (F=2). At 298.15K

and 0.003169 MPa (the vapor pressure of water at that temperature), or alternatively, at 373.15K

and 0.101325 MPa, there are two phases present, and therefore the number of degrees of freedom

becomes one. This means that if the temperature changes, the pressure of water must change as

well in order to maintain the equilibrium between liquid and vapor, or alternatively, one of the

phases must disappear.

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If we now consider a two-component system (C=2), a binary system, another degree of

freedom of the system has been introduced (F=3) because we have introduced another component.

In other words, not only can the pressure and temperature vary, but also the composition of the

system. In order to continue using a two-dimensional graph, or phase diagram, to depict the

system, one of these three variables must remain constant. It is convenient to let the pressure

remain constant, at 1 atmosphere. In this way, a graph of temperature versus composition can be

constructed at this standard, constant pressure. These binary phase diagrams are encountered in,

for example the solid-liquid equilibrium of naphthalene-biphenyl mixtures, the liquid-liquid

equilibrium of cyclohexane-methanol mixtures, and the liquid-vapor equilibrium of cyclohexane-

ethanol mixtures studied in other labs in this course.

Consider the vertical dotted line in

Figure 2. For a point in the liquid

region, there is only one phase present,

and therefore the temperature and

composition can be varied somewhat

and still retain one phase. As the

temperature falls, we enter the solid B +

liquid region. Here we have two phases,

and therefore the number of degrees of

Figure 2. Phase diagram of solid-liquid equilibria
freedom drops to one. The composition

of the two phases at a temperature T are given by a horizontal tie line at that temperature which

connects the phase boundaries (in this case, pure B would be one composition, the other would be

the phase boundary between the liquid region and the B + liquid region. If we add some more solid

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B at the same temperature, it just settles (assuming B is more dense than the liquid). If we add some

A at the same temperature, it must dissolve to produce more of the liquid phase with the same

composition (forcing some B to dissolve as well). Once the temperature reaches the eutectic

temperature, both solid A and B form at the eutectic composition (in addition to the B that has

already formed), in equilibrium with the remaining liquid (P=3) and therefore F=0. Because the

number of degrees of freedom is 0, the temperature must remain constant until all of the liquid has

solidified.

Consider a three component system (C=3), a ternary system. Another degree of freedom of

the system has been introduced (F=4). It is typical to constrain both the pressure and the

temperature in order to represent the variables on a two-dimensional graph. The two remaining

degrees of freedom can be expressed as either mass or mole fraction or percent. Typically, although

there are three components A, B, and C, there are only two compositions specified, because once x A

and xB are specified, then xC = 1 –xA-xB. One could plot any two of these on a rectangular grid (the

total range would consist of a right isosceles triangle on standard rectangular graphs, but this

involves choosing which two of the three variables to represent directly as your abscissa (x) and

ordinate (y) in the standard y versus x plots. However, most ternary phase diagrams are represented

using the equilateral triangle (an example of a

barycentric) plot, which emphasize all three

components, but are slightly harder to interpret. The

corners represent pure components A, B, or C, and

the sides represent binary mixtures of A-B, B-C, or

A-C, whereas any point on the interior represents a

true ternary mixture. Any line parallel to AB will

have a constant composition of C, i.e. is an isopleth

Figure 3. Ternary phase diagram components
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of xC. To read the composition at some point, one only needs to construct two of these parallel lines

and see where they intersect the correct axis. Lines which pass through the vertex C will have a

constant A:B ratio.

For a three-component mixture at fixed temperature and pressure, we have the following

possibilities.

(1) One phase (=1, F=2): We can add small amounts of any two components (or

alternatively, alter two of the mole fractions). The composition of the solution will

change.

(2) Two phases (=1, F=1): We can alter the mole fractions of any two components, and the

composition of both liquids, and their relative amounts, will change, constrained by the

total mass constraints. In these regions, tie lines connect the two parts of the phase

boundary and the total composition.

(3) Three phases (=2, F=0): We can alter the mole fractions of any two components, but the

compositions of the phases are fixed, and only their relative amounts can change. This

necessarily means that three phase regions appear as triangles in ternary phase diagrams.

PROCEDURE

Materials

Culture tubes, disposable pipettes, spatula, sodium chloride (NaCl), 2-propanol ( iPrOH),

deionized water (H2O), toluidine blue solution in 2-propanol (0.020g/L), water bath at constant

temperature.

Procedure:

You should have the following two tables already prepared in your lab book before the

experiment commences. A spreadsheet may be used to calculate the quantities for the second

table.

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Sample # Mass tube (g) Mass tube + Mass tube + NaCl + Mass tube + NaCl + Obs. (#
i i
NaCl (g) PrOH (g) PrOH + H2O (g) phases)
1
2
3
4
5
6
…

Sample # Mass NaCl Mass iPrOH Mass H2O Total mass Mass Mass Mass
(g) (g) (g) (g) fraction fraction fraction
i
NaCl PrOH H2O
1
2
3
4
5
6
…
0 Record the water bath temperature.

You will weigh out various amounts of sodium chloride, 2-propanol (with a small amount of

toluidine blue for Stage 2 onwards), and water into the culture tubes to a total of approximately

10.0±0.5 g, cap, and shake vigorously. After allowing the mixture to equilibrate for a few minutes,

you will then record the number and nature (s-solid, l-liquid) of the phases. You should then plot

your observations on a triangular graph as you go.

Stage 1: First observe the phases of the three

● pure substances. These will be entries 1-3 of your

table and will serve as a reference for comparison of

your other visual observations. A represents water,

B represents 2-propanol, and C represents sodium

chloride. Because C is a different phase than A or B,

● ● there must be at least one phase boundary between

A and C and between B and C.

Figure 4. Points on the 100% 1-grid (by mass)
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Stage 2: Prepare and observe the

● phases of the three possible 50-50 (5g-

5g) mixtures. This helps to determine

● ● the mutual solubility of each of the

components in each other, and to more

accurately place the phase boundary.

● ● ● Note that we have systematically

subdivided the compositions. Do you

Figure 5. Points on the 100% 2-grid (by mass)
have any hypothesis about the mutual solubility of A and B?

Now things will start to get interesting. We will now subdivide so that all of our masses are

multiples of 2 g.

Stage 3a: Prepare and observe the binary mixtures

● indicated on the outside of the triangles

● ● (20%,40%,60%,80%). Does this support any

● ● ● hypothesis developed above? This should also more

● ●
● ● ● ● accurately locate any phase boundary between B

● ● ● ● ● and C, and A and C. Have you noticed any

● ● ● ●● ● ● difficulties regarding sample preparation yet? Based

on what was observed in Stage 2, could any of these

Figure 6. Points on the 100% 5-grid (by mass)
points have been excluded a priori?

Stage 3b: Form a hypothesis as to how many phase boundaries there are and its approximate

location for the ternary mixtures. Prepare the six remaining true ternary mixtures and observe. Does

this support your hypothesis? If not, revise your hypothesis.

Stage 4: Prepare and observe some additional ternary mixtures on the 10% grid. These will have to
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be chosen carefully to more precisely locate any additional phase boundaries and/or regions that

you may have discovered.

DATA TREATMENT

Construct a ternary plot of your data. In your discussion, answer the questions posed in the

procedure section. What are the possible sources of error? Can you think of any more efficient

ways of more precisely locating the phase boundaries?

BIBLIOGRAPHY

1. P. Atkins, J. de Paula, Physical Chemistry, 10th ed., W. H. Freeman, New York, 2014.

Chapters 4, 5

2. K. L. Singfield, Solid-Liquid Phase Equilibrium: An Investigation of the Thermal

Behaviour of a Binary System with Eutectic Melting, Saint Mary’s University, Chemistry 2312 Lab

Experiment, 2011.

3. K. L. Singfield, Liquid-Liquid Phase Equilibrium: Investigating Critical Solution Properties

of a Partially Miscible Mixture, Saint Mary’s University, Chemistry 2312 Lab Experiment, 2011.

4. K. L. Singfield, Liquid-Vapour Phase Equilibrium: A Study of the Effect of Composition on

Normal Boiling of an Azeotropic Solution, Saint Mary’s University, Chemistry 2312 Lab

Experiment, 2011.

5. W. Wagner, A. Saul, A. Pruss, International Equations for the Pressure along the Melting

and along the Sublimation Curve of Ordinary Water Substance, J. Phys. Chem. Ref. Data, 1994, 23

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(3) 515-525

6. W. Wagner, A. Pruss, The IAPWS Formulation 1995 for the Thermodynamic Properties of

Ordinary Water Substance for General and Scientific Use, J. Phys. Chem. Ref. Data, 2002, 31 (2)

387-535.