Chemistry 3104, Physical Chemistry Lab I

Binary Phase Diagrams

I. Introduction

Phase diagrams of solid mixtures are used in material science, metallurgy, geology and chemical
industry to summarize the composition of the various phases of mixtures and show the conditions under
which each phase of a system is the most stable or conditions under which different phases can be in
equilibrium.1 In this experiment, a binary phase diagram is constructed using varying percent
compositions of naphthalene and p-dichlorobenzene. The eutectic and the melting points of both
components can then be determined.

II. The Phase Rule

Information regarding phase equilibria can be predicted by a simple rule (“Gibbs phase rule”):

f = c − p + 2 (Eq. 1)

where c is the number of components and p is the number of phases present in the system. The degrees
of freedom f, or variance, gives the number of variables (e.g., pressure, temperature, composition, etc.)
that must be given to completely describe the system, or to locate the state of the system on the phase
diagram.

For pure gas (i.e., consisting of one component) c = 1 so Eq. 1 becomes:

f=3–p

If only one phase is present, p=1 and according to Eq. 1 f = 2. This means that two variables are required
for complete description of the pure gas (i.e., any two of the three variables P, V or T). A general one
component phase diagram is shown below:

FIGURE 1: A schematic drawing of a one component phase diagram.

For pure phases (solid, liquid or vapor) f = 2 as mentioned above. When two phases are present
simultaneously meaning they are in equilibrium (e.g. the point resides on the lines separating the phases
in Fig. 1), only P or T can be varied independently and the phase rule gives f = 1. When all three phases
are present (i.e., the triple point), all variables must be fixed, and the phase rule says that f = 0.

III. Binary Systems

For binary systems (i.e., consisting of two components) c = 2 and Eq. 1 becomes:

f=4–p

If the system consists of only one phase, f = 3. The required three variables for describing such system
are: one for describing the relative composition (percentage or mole fraction) and one of the pairs (P, V),
(P, T), or (T, V). Note that if one mole fraction, xA, is given, the second can be obtained by xB = 1 -xA. Or if
the percent of one compound is given (compound A), the percentage of the second one (compound B) is
equal to 100-%A. Also in practice, the (P, T) pair is chosen. Usually, T is varied while P remains constant
at 1atm. If the system separates into two different phases, only f = 4 − 2 = 2 variables are needed (one
mass fraction and P or T, usually T). If 3 phases are present, then f = 1 which corresponds to the eutectic
point.

A binary phase diagram can give the following information: the eutectic point, the liquidus line,
the solidus line, and the three phases with respect to temperature and percent composition. The
following figure is an example of the simplest type of binary phase diagram of a mixture of A and B.

FIGURE 1 A theoretical binary eutectic phase diagram 2

Compositions are plotted across the x axis and can be expressed as either percentage of A or
percentage of B (in this case). Remember, the percentages of A and B must add up to 100. Compositions
can also be expressed as mole fraction of A or B and their total must add up to 1. Temperature or
pressure is plotted on the y axis. For the diagram above, the pressure is considered to be constant
atmospheric pressure (1atm), so temperature is plotted on the y axis.

On the diagram Liquid represents the liquid (melt) phase made out of liquid A and B (1 phase);
solid A + Liquid represents the conditions under which only A exists as a solid in equilibrium with Liquid
(2 phases); solid B + Liquid represents the conditions under which only B exists as a solid in equilibrium
with Liquid (2 phases); and solid A + solid B represents the conditions under which both components
exist in their solid phase and they are immiscible (2 phases). Point E represents the eutectic point; TmA is
the melting point of component A; and TmB is the melting point of component B. The eutectic point is
the point in which all three phases (melt phase, solid A, and solid B) of the binary system exist in
equilibrium. The curved lines from TmA to E and TmB to E represent the liquidus lines. Above the liquidus
lines the mixture exists in the liquid (melt) phase and below in a liquid-solid phase dependent on the
percent composition. The line at TE represents the solidus line, below which both components exist in
solid form, regardless of the percent composition. 3

The red dots on the diagram indicate what happens if a liquid mixture of composition X (80% A
and 20% B) is gradually cooled. Composition X will be all liquid above the temperature T 1, because it lies
in the region of Liquid. If the temperature is lowered to T 1, which is a point on the liquidus line, solid A
(crystals of A) will begin to form. If the temperature decreases further, below T 1, more solid A forms
(crystals come out of solution). As solid A forms, the composition of the liquid becomes more enriched
in compound B. Based on the diagram, as temperature decreases from T 1 to T2 to T3 to TE, the
composition of the liquid will change from point 1 to point 2 to point 3 to point E respectively. Between
temperatures T1 and TE, two phases will be present in the system: liquid and crystals of A. At the eutectic
temperature, TE, solid B (crystals of B) will start forming, and three phases will coexist: solid A, solid B,
and liquid. The temperature will remain at T E (eutectic halt) until the liquid phase solidifies completely
and only pure solid A and pure solid B remain. The mixture of solid A and solid B will be in the
proportions of the original mixture (composition X), that is 80% A and 20% B. 2

The eutectic composition is the composition with the lowest melting point. Eutectic comes from
the Greek word εΰτηϰτος which means ‘easily melted’. One eutectic with important applications in
technology is solder; it is a metal alloy that consists of 67% tin and 33% lead and melts at 183°C. Solder,
which has a much lower melting temperature than other metals, is used in soldering, a process in which
two or more electronic parts are joined by melting solder around the connection.
Chemistry 3104, Physical Chemistry Lab I

IV. Experimental Procedure

1. The following compositions of naphthalene and p-dichlorobenzene will be used to construct a

Test
Composition of p-Dichlorobenzene (%) Composition of Naphthalene (%)
Tube
A 100 0
B 95 5
C 90 10
D 85 15
E 80 20
F 75 25
G 70 30
H 65 35
I 60 40
J 55 45
K 50 50
L 45 55
M 40 60
N 35 65
O 30 70
P 25 75
Q 20 80
R 15 85
S 10 90
T 5 95
U 0 100

2. The solid mixtures of naphthalene and p-dichlorobenzene are prepared in 20×150 mm test
tubes which are enclosed and sealed with a rubber stopper containing a thermometer in the
hole of the stopper. The thermometer should be submerged in the solid naphthalene/p-
dichlorobenzene mixture. The test tubes are labeled as corresponding to the table above.
3. Submerge the mixture in a hot water bath to melt the solid. Do not overheat the mixtures.
4. After the solid is completely melted, remove the test tube from the hot water bath using a test
tube clamp.
5. Allow the test tube to cool. When the first crystals begin to form from the liquid mixture (not on
the sides of the test tube) record the temperature.
6. Let the test tubes cool for 10 minutes and repeat this procedure twice three more times until
you get three measurements that are close to each other.
Chemistry 3104, Physical Chemistry Lab I

V. Data Analysis

Be sure to record the temperatures obtained in your lab notebook for every composition. Calculate the
average freezing/melting temperature for each test tube/composition and then plot it as a function of
composition. Use Excel or other plotting software for the plot but draw by hand the two liquidus lines.
Do not just connect the points. Do the best fitting lines. Then draw the solidus line based on your
eutectic mixture.

VI. Division of Labor

The test tubes should be divided between the groups. Each group should have at least as many test
tubes as members, possibly more since all the class needs to get data for all the compositions.

VII. Lab Report

The data obtained in this experiment will be combined with data from the Multiple Phase Diagrams
(experiment 5, the next experiment) and will count towards 20% of your grade. Graph the binary phase
diagram for naphthalene and p-dichlorobenzene using graphing software (i.e. Excel, Origin) and find
curves of best fit for the data points. Be sure to label the regions on the phase diagram, including the
eutectic point (composition and temperature). Include this in your lab report as well as theory behind
binary and multiple phase diagrams (it may be a good idea to look up why they are important and for
what purposes they are used).

VIII. References

1. Atkins, P.; de Paula, J.; Keeler, J. Physical Chemistry, 11 th Edition; Oxford University Press: Oxford,
UK, 2018; pp 177-179.
2. http://www2.tulane.edu/~sanelson/eens211/2compphasdiag.html
3. Fitcher, Lynn. "Binary Eutectic Phase Diagram." JMU Geology. N.p., 29 2000. Web. 14 Nov 2012.
<http://csmres.jmu.edu/geollab/fichter/IgnRx/BinryEu.html>.