Exercise no.

1
BINARY SOLID-LIQUID PHASE DIAGRAM

Jomari R. Noe; Ranelle dP. Acda; Rommel Yecla; Marielle A. Leysa; Maris L. Bayhon
Date of performance: 10 August 2015; Date submitted: 24 August 2015; Laboratory section:
CHEM 112.1 2L; Instructor: Anabelle T. Abrera

Abstract
A binary solid-liquid phase diagram has been constructed
from the cooling curves of mixtures containing varying amounts of
diphenylamine and naphthalene. The cooling curves were obtained
from heating the mixtures until molten and then cooling slowly.
From each of the cooling curve, the break and arrest temperatures
were determined. These temperatures were plotted against the
mole fraction of naphthalene in each mixture. From the constructed
phase diagram, the eutectic composition was graphically
determined. A is equal to 0.5190 while B is equal to 0.4810. The
eutectic temperature, calculated from the average of the arrest
temperatures is equal to 25.83C. The theoretical values of A and
B calculated using the Newton-Raphson method were 0.6419 and
0.3581, respectively. The theoretical eutectic temperature, on the
other hand, was 32.44C.

I.

Introduction

A phase is a form of matter that is

homogeneous,
uniform
in
chemical
composition, and physically distinct all
throughout. In a heterogeneous system,
phases can be defined by boundaries.
(Atkins, et al., 2006; Sivasankar, 2008). Solid,
liquid, and gas phases are the most common
phases of matter.
Matter can be converted from one
phase to another. This process is called
phase transition. Examples of phase
transition
include
gas
to
liquid
(condensation) or liquid to solid (freezing).
Phase transitions can suddenly and
spontaneously take place, in certain
temperature at a given pressure. For
instance, if a gas is a little above its
condensation point, a slight decrease in
temperature yields a liquid phase that

coexists with the gas phase. If the

temperature is decreased further, the system
which is initially gas becomes a single liquid
phase (Mortimer, 2008).
At a particular condition, maintaining
certain temperature and pressure, two or
more phases can coexist, as mentioned
previously (Monk, 2004). Normally, water
boils at 100C. At this temperature, vapour
pressure is equal to the atmospheric
pressure. Moreover, the liquid and gas states
of water coexist at equilibrium. This existing
equilibrium is dynamic that is, as liquid is
transforms into gas, an equal quantity is also
converted back to the liquid state.
Pressure and temperature values are
dependent on each other, therefore, a
change in pressure, equilibrium temperature
shifts consequently. By plotting the
experimental values of pressure and

temperature at which equilibrium occurs, we

obtain a phase diagram.

phase rule, the number of degrees of

freedom is equal to:
f=1-3+2=0
The system above in invariant (f = 0)
since the three phases of water coexist.
Moreover, neither the temperature nor the
pressure can be varied slightly without
causing one of the phase to disappear.
Looking at the phase diagram of water, the
point where the system in invariant is located
at the triple point.

Figure 1.1 Phase diagram of water (Source:

Atkins & de Paula, 2006)
This diagram is only for a onecomponent system. A component can be
defined as an independent chemical
component. The number of components in
a system refers to the smallest number of
independently
variable
chemical
constituents by which the composition of
each phase can be expressed directly or
through an equation (Sivasankar, 2008).
The Gibbs phase rule gives the
number of independent intensive variable in
a system that may have several phases and
components (Mortimer, 2008). It also
provides the relationship between the
degrees of freedom of a system f, the
number of phases p, and the number of
components
c
(Moore,
1962).
Mathematically, the Gibbs phase rule is
stated as:
f=cp+2

(eq. 1.1)

The constant 2 suggests that the

temperature and pressure are specified.
In a system consisting of ice, water,
and water vapour, the number of phases is
three (i.e., solid, liquid, and gas, respectively).
The number of component, on the other
hand, is one since the system can be
represented using a single chemical
constituent: water. Moreover, using Gibbs

When 2 phases are only present, the

system is univariant. Along the boundary
lines of the phase diagram of water, the
pressure can be varied with temperature
such that two phases may coexist.
Finally, when 1 phase is only present,
the system is bivariant. Pressure and
temperature can be varied independently
while maintaining only a single phase.
In this experiment, a mixture of
naphthalene and diphenylamine is used.
This number of components in this system is
two (c = 2) since each component behaves
independently and one component cannot
be represented by the other. Moreover, the
concentrations
of
naphthalene
and
diphenylamine can be varied independently
in various phases (Moore, 1962).
Such
system
may
also
be
represented through phase diagrams,
particularly, a binary solid-liquid phase
diagram.
In constructing the diagram for this
system, the pressure may be held constant,
thus, reducing equation 1.1 into:
f=cp+1

(eq. 1.2)

f=3-p
The method of thermal analysis is
usually done to construct binary phase
diagrams for eutectic systems like the
naphthalene-diphenylamine system.

In thermal analysis, a mixture with

known composition is heated until all solids
have melted. The mixture is allowed to slowly
cool and a cooling curve is constructed
(Mortimer, 2008). From these cooling curves,
break temperatures are obtained and plotted
against the composition of the mixture. On
the other hand, the mean arrest
temperatures of the cooling curves is
calculated and designated as the eutectic
temperature. In the phase binary phase
diagram, a straight horizontal line is drawn at
this temperature. Shown below is an
example of binary phase diagram of eutectic
systems.

and the liquid or melt naphthalene and

benzene disappear.
Point E is referred to as the eutectic
point. It is where the two liquidus curve meet.
This point is characterized by the eutectic
temperature and the eutectic temperature
(Patra and Samantray, 2011).
This exercise aims to construct a
solid-liquid phase diagram for a simple, nonreacting binary system and interpret this
diagram in terms of the eutectic composition,
the number of components, the number and
nature of phases present and the number of
degrees of freedom.
II.

Methodology

In a large test tube, specific amounts

of naphthalene and diphenylamine were
added. The amounts were based on Table
1.1 of the laboratory manual.
Eight runs were commenced in the
experiment. For each run, the large test tube
was heated in a water bath until all the solid
inside the tube has melted or a certain
temperature is reached. For runs 1-5, 90C
was used while 62 C was used for runs 6-8.
After all the solids have melted, the
test tube was inserted inside the Dewar flask
fill with crushed ice.
Figure 1.2 Binary phase diagram for
naphthalene and benzene (Source: Moore,
1962)
The figure is a binary diagram for
naphthalene-benzene system. The CE curve
marks the boundary where the first solid
naphthalene appears. On the other hand, the
curve DE marks the point where benzene
starts to solidify. These curves are referred
to as liquidus curves. Above these curves,
the system is entirely liquid.
The dashed line in the phase diagram
represents the solidus curve, below which
solid naphthalene and solid benzene coexist

The temperature was recorded for

every 10 seconds until 20C is reached. The
process is repeated for every run.
Only one trial was done due to time
constraints.
Mixtures are disposed in waste
bottles labelled Non-halogenated. On the
other hand, the test tube and stirrer were
washed with acetone and the washing was
disposed in the same container.
III.

Results and Discussion

Eight heating runs were made in the

experiment. For each run, a cooling curve
has been generated. Also, each run contains

varying amounts of (B) naphthalene and (A)

diphenylamine.
Table 1.1 Amount of A and B in each run
Run no.
1
2
3
4
5
6
7
8

Amount, g
5.0292 B
1.0002 A
1.5018 A
2.5003 A
5.0020 A
5.0003 A
1.0007 B
0.6707 B

A cooling curve can be constructed

by reversibly cooling a melted or liquid
substance (Kaurav, 2011). It shows how the
temperature of a substance falls with time. It
also exhibits the point at which temperature
does not change through some period of
time (Kakani, 2004). The constant
temperature is referred to as the arrest
temperature.
The cooling curve of a pure
substance slightly differs with that of a
mixture. In both cases, an arrest temperature
can be observed. However, the rate of
freezing is different.
For a pure substance, like
naphthalene, the rate of freezing remains
constant before it reaches the arrest
temperature. On the other hand, the rate of
freezing in a melted naphthalenediphenylamine mixture changes at some
point before reaching the arrest temperature.
This is caused by the change in the
concentration of the liquid mixture. As the
mixture cools down, one component begins
to solidify while the other remains in the liquid
state.
Shown below are the cooling curves
for a silver-copper system. The differences in
the cooling curves are associated on the
composition of each of the components in
the mixture.

Figure 1.3 Cooling curves for the silvercopper system (Source: Mortimer, 2008)
In this experiment, a binary solidliquid phase diagram was constructed from
the cooling curve of each of the run. The
resulting phase diagram is shown below.
Two points were omitted from the set of data
to generate a better phase diagram.
80
70
60
50
40
30
20
10
0

I
III
II
e
IV
0

0.2

0.4

0.6

0.8

Figure 1.4 Constructed phase diagram for

the naphthalene-diphenylamine system
The different regions in the phase
diagram are labelled I, II, III, and IV. I is
composed of the molten naphthalene and
diphenylamine. This region is only composed
of one phase, the homogenous molten
mixture,
since
diphenylamine
and
naphthalene are miscible in the liquid phase.
Therefore, using equation 1.1, f is equal to 2.
Region II is composed of solid
naphthalene and the molten mixture. The
number of phases in this region is 2.
Therefore, f in this region is 1. Region III has
the same value of f it is composed of solid
diphenylamine and the molten mixture.

Region IV consists of solid

diphenylamine and solid naphthalene. The
solid phases are not miscible with each other
so p is equal to 2. Therefore, the value of f is
1.
The point labelled with e is the
eutectic point. It is at this point that the
molten mixture and the two solid phases
coexist. At this point, the number of phases
is equal to 3. So, f is 0.
The arrest temperature in each run
was obtained and their average was
calculated. The calculated temperature was
25.83 C. This temperature corresponds to
the eutectic temperature.
Also, at this temperature, the eutectic
composition was determined graphically
that is, 0.481 diphenylamine and 0.519
naphthalene.
The theoretical composition and
temperature can also be determined through
calculations. The following equations were
used for the calculation.

ln =

1
1
) (. 1.3)
(

ln =

1
1
)
(

(. 1.4)

where:
A diphenylamine
B -- naphthalene
From these equations, a single
function was derived.ln
ln

(1 )
+ = 0 (. 1.5)

where:
C=
D=

Y=

The theoretical eutectic composition

was first calculated through NewtonRaphson method.
+1 =

()
()

The calculated mole fraction form the

Newton-Raphson method was substituted to
equation 1.2 and the theoretical eutectic
temperature was calculated. The following
table lists the experimental and calculated
values for the eutectic temperature and
composition, as well as the percent error.
Table 1.2 Summary table for the eutectic
temperature and composition
Parameter

Theoretical

Experimental

% Error

0.6419

0.5190

19.15%

0.3581

0.4810

34.32%

Temperature

32.44 C

25.83 C

20.37%

The eutectic composition has the

lowest melting temperature than any
possible composition of the components in a
binary system. Its melting temperature is
lower than that of the individual components.
This temperature is referred to as the
eutectic temperature (Patra and Samantray,
2011).
The eutectic composition is very
significant in fields such as metallurgy and
material science. In foundry and casting, it is
the vital point since it has the lowest
temperature possible for the system. It also
helps in reducing energy cost.
Other applications of the eutectic
composition includes freezing mixtures,
eutectic alloys for soldering purposes (e.g.,
Pb and Sn). In inkjet printers, eutectic
mixtures are also used as inks.
Aside from cooling curve data, phase
diagrams may also be constructed through xray diffraction methods. It has become a
standard method in phase identification in
equilibrium studies (Hummel, 1984). This

method is used to establish loci of phase

boundaries and to determine gram atomic
volumes (Zhao, 2007).
Some studies that made use of x-ray
diffraction in establishing phase diagrams
include the investigation of a quasi-binary
system LiInSe2-CuInSe2 (Weise, et al., 1996)
and investigation of the phase equilibria in
CdI2-Bi2O3 (Vassilev, et al., 2004) and
GeSe2-SnTe systems (Vassilev, et al., 2003)

IV.

Conclusions

A phase diagram has been

successfully
constructed
for
the
naphthalene-diphenylamine system. The
constructed phase diagram also has a
distinguishable eutectic point.
The
experimental
eutectic
composition and temperature values are
relatively near the calculated theoretical
values. Errors may have risen from the
calculation of the mole fraction for the
graphical construction of the diagram. During
the experiment, some naphthalene and/or
diphenylamine adhere to the sides of the test
tube, affecting the composition of the mixture
during heating and cooling.

V.

References

Atkins, P & J de Paula. 2006. Physical

Chemistry, 8th ed. NY: Oxford
University Press.
Hummel, FA. 1984. Introduction to Phase
Equilibria in Ceramic Systems. CRC
Press.
Kakani, SL & A Kakani. 2006. Material
Science. New Delhi: New Age
Internationa (P) Ltd., Publishers.
Kaurav, MS. 2011. Engineering Chemistry
with Laboratory Experiments. New
Delhi: PHI Learning Private Limited.
Monk,

P. 2004. Physical Chemistry:

Understanding Our Chemical World.
England: John Wiley & Sons Ltd.

Moore, WJ. 1962. Physical Chemistry, 4th ed.

USA: Longmans Green and Co. Ltd.
Mortimer, RG. 2008. Physical Chemistry, 3rd
ed. USA: Elsevier Academic Press
Patra, BB & B Samantray. 2011. Engineering
Chemistry I. India: Dorling Kindersley
Pvt. Ltd.
Sivansankar,
B.
2008.
Engineering
Chemistry. New Delhi: Tata McGrawHill Publishing Company Limited.
Zhao, JC. 2011. Methods for Phase Diagram
Determination. UK: Elsevier BV.

VI.

Calculations

Mole Fraction (A: Diphenylamine, B: Naphthalene)

Run 1:

=
=
+

5.0292
128.16/
1.00
0
5.0292
+
169.22/ 128.16/

= 1.00 = 1.00 1.00 = 0

Run 2:
= 0.8690950608
= 0.1309049392
Run 6:
Run 3:

= 1.00

= 0.7263318323

= 0

= 0.2736681677
Run 7:
Run 4:

= 0.7909858284

= 0.5703509791

= 0.2090141716

= 0.4296490209
Run 8:
Run 5:

= 0.693793818

= 0.3989950942

= 0.306206182

= 0.6010049058
Experimental Eutectic Temperature
=

(21 + 26 + 24 + 34 + 26 + 24)
=
= 25.83
.
6

Theoretical Eutectic Composition

ln =
ln =

1
1
)
(

ln =

17863.88 /
1
1
(
)
8.314 / 326.15

ln(1 ) =

8.314

1
1

= ln
+

326.15
17863.88

1
1
)
(

19305.48 /
1
1
(
)
8.314 / 353.35

8.314

1
1

= ln(1 )
+

353.35
19305.48

8.314

1
1

ln
+
= ln(1 )
+

326.15
353.35
17863.88
19305.48

8.314

4.654084107 104 ln + 3.066073892 103

= 4.306549229 104 ln(1 ) + 2.830055186 103
() = 4.654084107 104 ln + 4.306549229 104 ln(1 ) + 2.360187063 104 = 0
() =

4.654084107 104 4.306549229 104

=0
(1 )

+1 =

()
; = 0.5
() 1

= 0.6419450191
= 0.3580549809

ln =

17863.88 /
1
1
(
)
8.314 / 326.15

ln 0.6419450191 =

17863.88 /
1
1
(
)
8.314 / 326.15

= 305.5891595 273.15 = 32.43915948

Percent Error
Te
% =

25.83 C 32.44 C
100 =
100 = 20.37%

32.44 C

Eutectic Composition
= 19.14%

= 34.32%

80
70
60
50
40

Series1

30
20
10
0
0

100

200

300

400

500

600

700

70

60

50

40
Series1
30

20

10

0
0

100

200

300

400

500

600

700

800

900

80
70
60
50
40

Series1

30
20
10
0

100

200

300

400

500

600

700

70
60

Temperature (C)

50
40
30

Series1

20
10

0
0

50

100

150

200
Time (s)

250

300

350

400

80
70
60

50
40
30
20
10
0
0

100

200

300

400

500

600

70

60

50

40
Series1
30

20

10

0
0

50

100

150

200

250

300

350

Raw Data
Table 1.3 Data on mole fraction, break temperature and arrest temperature of each run
Run
6
7
8
5
4
3
2
1

B
0
0.2090141716
0.3062061820
0.3989950942
0.5703509791
0.7263318323
0.8690950608
1.00

Tb, C
40
42
47
54
46
67
65
68

Ta, C
26
24
34
24
26
21
-