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Solid-Liquid Equilibrium of the Naphthalene (1) /

Diphenylamine (2) System


Using Thermal Analysis to Generate the Solid-Liquid Equilibrium Phase Diagram
Abagon, Ma. Victoria1, Buendia, Neil Daniel2, Caracas, Corine Jasper3
Department of Chemical Engineering, College of Engineering
University of the Philippines - Diliman
Quezon City, Philippines
1
vicky.abagon@gmail.com | 2ndnbuendia@gmail.com | 3corinecaracas@gmail.com

AbstractUsing thermal analysis, cooling curves for eight


different compositions of the naphthalene (1) / diphenylamine (2)
system were generated. By plotting the temperature at thermal
arrest versus concentration, the solid-liquid equilibrium phase
diagram for the system was constructed and shown in Fig. 1. The
first three points of the plot represent the diphenylamine-rich
mixtures, and the last six points constitute the naphthalene-rich
mixtures. Following thermal analysis, two separate second-degree
curves were fit to the respective data points. The eutectic point is
determined to be the intersection of the two curves, with
composition = . at 300.15 K. The eutectic composition
deviated 14.99% from the literature value while the eutectic
temperature differed by 1.71%. The deviations may have been
incurred from material loss and sample contamination.

=
Defining the ratio, / as :
=

The ratio of fugacities at the temperature and pressure of the


system may be written in expanded form:
(, )
(, ) ( , )
=

(, )
( , ) ( , )
( , )

(, )

INTRODUCTION

Most substances found in the market are made up of multiple


compounds and rarely of a pure chemical. In manufacturing
these substances, it is important to know their physical and
chemical properties especially in ensuring that the desired state
of the final product is achieved. [1] Taking crystallization for
example, it is important to know the required temperature to
crystallize a solid of a certain composition. However, physical
and chemical property data like melting points are usually only
available for pure species and when they interact with other pure
species in mixtures, they may behave differently.
The study of solid-liquid equilibria (SLE) for a multiplecomponent system is useful in determining different
thermodynamic properties exhibited by various mixtures. The
simplest way to represent SLE would be a binary solid-liquid
phase diagram which gives information about the phase,
temperature and composition of the binary mixture. [2]
Theoretically, SLE is represented by the uniformity of the
temperature, pressure and fugacity for each chemical species
throughout both phases. Mathematically it is shown as:
=

(1)

Expressing the previous equation in terms of the activity


coefficient gives:

(3)

where is the composition in the liquid phase, is the


composition in the solid phase, and is the activity coefficient
for the liquid and solid phase respectively.

Keywords-eutectic temperature, eutectic composition, solidliquid equilibrium, thermal analysis, naphthalene, diphenylamine

I.

(2)

(4)

where is the melting point of pure species . The second


term is equal to unity since at the melting point the fugacity of
the species is equal for both phases. The equation could then be
simplified to:
=

(, )
( , )

( , )
(, )

(5)

This equation may be evaluated leading to an expression


where is a function of temperature:
= exp


(
)

(6)

Knowing , (3) may be used once the dependence of the


activity coefficient, on temperature and composition is
defined. Two limiting cases may be considered:
1.

An ideal solution behavior is assumed for both phases


(both activity coefficients are equal to 1 for all
temperatures and compositions).

2.

An ideal solution is assumed for the liquid phase ( =


1) along with a complete immisciblity of both species
in the solid phase ( = 1). [3]

Experimentally a solid-liquid phase diagram may be


generated using thermal analysis. A mixture of two solids is
heated until melting and a cooling curve is obtained for different
mixture compositions. This curve is then used to locate
significant temperature values. A change in slope, which is also
a change in the cooling rate, represents supercooling. This
temperature where the solid starts to separate from the liquid
mixture is the break point.
However, when the temperature of the mixture no longer
changes, thermal arrest happens. This temperature and
composition point is called the eutectic point. At this point, the
presence of two solid phases and a liquid phase is indicated.
[4][5]
In this experiment, the solid-liquid phase diagram of
diphenylamine and naphthalene is obtained using thermal
analysis. The data obtained were analyzed and compared with
the theoretical values.
II.

MATERIALS AND METHODS

The solid samples used were prepared using an analytical


balance and petri dish. The first mixture, which was composed
of pure naphthalene, was transferred to a 6-inch test tube.
To measure the temperature inside the test tube, a
thermocouple was inserted through the rubber stopper used to
seal the test tube. The test tube was placed in a boiling water bath
to heat the sample until all of the solids have melted. The test
tube was removed from the water bath and temperature was
taken at five-second intervals until all the samples in the test tube
solidified, or when temperature remained constant for three
consecutive readings.
The second mixture was prepared as specified in Table 1,
and the process of heating the sample and obtaining temperature
measurements were again administered. The succeeding
mixtures were then prepared accordingly.
However, mixtures 6, 7, and 8 were melted and recrystallized
using a different 6-inch test tube. A cold water bath is used to
recrystallize the diphenylamine-rich mixtures.
III.

RESULTS AND DISCUSSION

Temperature data recorded from the experiment were used


to obtain the melting point of pure naphthalene and
diphenylamine. The following shows the analysis of the
obtained melting point temperatures and the comparison to
theoretical data as well as the calculations undertaken to
generate the solid-liquid phase diagram of the system.
A. Interpretation of Data Gathered
The set of temperature readings per mixture was plotted
against time, and the cooling curves produced could be viewed
in the appendix.
After plotting the data, the thermal break points and thermal
arrest points were determined by calculating the slopes of the
cooling curves. The decrease in the slope of the cooling curve

TABLE 1. NAPHTHALENE-DIPHENYLAMINE MIXTURE PREPARATION


Mixture

Diphenylamine,
g

Naphthalene,
g

3.75

0.75

3.75

1.875

3.75

3.75

3.75

7.5

3.75

3.75

3.75

0.75

M6 + 0.75 naphthalene

3.75

1.2525

M7 + 1.2525
naphthalene

Mixture preparation

M1 + 0.75 g
diphenylamine
M2 + 1.875 g
diphenylamine
M3 + 3.75 g
diphenylamine
M4 + 7.5 g
diphenylamine

corresponds to the thermal break point, wherein the appearance


of the first solid could be observed. On the other hand, the point
where the temperature value becomes constant is defined to be
the thermal arrest point. This point, which is also the melting
point of the mixture, was used to generate the solid-liquid phase
diagram for the naphthalene (1) / diphenylamine (2) system. The
curves produced are shown in Fig. 1.
The first three points in the plot represent the
diphenylamine-rich mixtures and a second-degree polynomial
curve was fit into the three points. The same procedure was
observed for the last six points in the plot, which constitute the
naphthalene-rich mixtures.
The intersection of the two curves is the experimentallydetermined eutectic composition and temperature of the
naphthalene (1) diphenylamine (2) system. Under these
conditions, three phases could be observed. Hence, a horizontal
line passing through could be drawn, since at this point solidphase pure naphthalene ( = 1 ), solid-phase pure
diphenylamine ( = 0 ) and liquid-phase naphthalene
diphenylamine mixture ( = ) coexist.
As shown in Fig. 1, the curves divided the phase diagram
into four two-phase regions. Mixture compositions lying on the
first region is expected to split into a pure naphthalene solid and
a liquid with composition predicted by the curve fit. A similar
behavior is exhibited by mixtures within region II, but the solid
i1n equilibrium with the liquid is pure diphenylamine.
Moreover, in region III lies a single liquid phase, while in region
IV exists two distinguishable solid phases.
B. Comparison to Theoretical Data
Assuming that the system behaves as an ideal solution in the
liquid phase and is completely immiscible in the solid phase,
then 1 = 1 and 2 = 2 . Hence, using as defined in (6),
the following equations also apply.
1 = exp

1 1
(
)
1

1 = 1 exp

2 2
(
)
2

(7)

(8)

Temperature vs. x(1)


350
y = -69.377x2 + 148.1x + 263.22
R = 0.9838

Temperature, Kelvins

340
330

y = -343.52x2 + 22.454x + 325.45


R = 1

320
310
300
290
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

x(1)
Figure 1. SLE curve for the naphthalene (1) - diphenylamine (2) system at 101.325 kPa (constructed from experimental data)

The eutectic temperature and composition could be


calculated by simultaneously solving (7) and (8) while using the
theoretical values for diphenylamine and naphthalene shown in
Table 2. Shown below is the resulting equation from combining
(7) and (8).
1 exp

2
,2

,2

) = exp

1
,1

,1

(9)

Using (9), the eutectic temperature and composition was


determined, since the said equation is could only be satisfied by
the conditions at the eutectic point. The deviation of the
theoretical values obtained were compared to the experimental
value determined from the intersection of the curves shown in
Fig. 1. A summary of calculated values is displayed in Table 3.
C. Sources of Deviation
The major sources of errors in this experiment are material
loss and sample contamination. The analytical balance used to
weigh the samples may incur deviations due to poor
maintenance of the instrument. The mass of the irrelevant
particles present in the platform contributed to the recorded
TABLE 2. PURE-SPECIES LITERATURE DATA
, kJ/kg
146.79
105.63

naphthalene
diphenylamine

, C
80.2
52.9

Data obtained from National Institute of Standards and Technology

TABLE 3. SUMMARY OF OBTAINED VALUES

, C

Experimental
0.306026561
27

Theoretical
0.360001299
32.21532052

deviation
14.99293 %
1.707896 %

mass, hence the actual amount of sample being processed is less


than recorded. This leads to a lower crystallization temperature
reading, as well as lower arrest and break temperature
measurements.
During the transfer of solids from the petri dish to the test
tube, material loss might have been incurred. A watch glass
should have been used instead of the plastic petri dish, as
suggested by [6]. The lack of glass instruments led to using the
petri dish to which the solids has higher affinity to. This caused
difficulty in transferring the sample from the dish to the test tube
which in turn led to material loss.
IV.

CONCLUSIONS AND RECOMMENDATIONS

The data obtained by utilizing the thermal analysis method


has been used to plot a phase diagram for the naphthalene
diphenylamine system, as shown in Fig. 1. From the phase
diagram constructed, the behavior of the system at various
combinations of mixture composition and temperature could be
predicted.
The eutectic point of the system at atmospheric pressure was
also determined using the data gathered. The experimental
eutectic composition and temperature are = 0.3060 and
27 C respectively. This is the intersection of the two curves
constructed from the locus of diphenylamine-rich mixture points
and the locus of naphthalene-rich mixture points.
These values obtained from experimentation were compared
to literature values, and deviations were recorded in Table 3. The
errors could be attributed to accumulated material loss mainly
from the transfer of samples from the balance, to the petri dish,
and to the test tube. Also, sample contamination might have
occurred which would have affected the temperature readings.
It is recommended that for the future experiments utilizing
the thermal analysis method, more mixtures of different
compositions should be prepared so that there would be more

data points involved in constructing the SLE curve. Also if


possible, at least two trials per mixture should be conducted so
that the data that would be used for calculations and plot
construction would be more accurate.
Moreover, appropriate glassware and equipment should be
used in performing the experiment to decrease the possibility of
material loss.

REFERENCES
[1]
[2]

[3]

[4]
[5]
[6]

Binary Solid-Liquid Phase Diagram in CHEM 366, vol I, pp 1-8.


J. Gallus, Q. Lin, S. Freiss, R. Hartmann, and E. Meister, Binary SolidLiquid Phase Diagrams of Selected Organic Compounds, Journal of
Chemical Education, vol. 78, no. 7, July 2001.
J.M. Smith, H.C. Van ness and M.M. Abbott, Introduction to Chemical
Engineering Thermodynamics, McGraw Hill, New York, pp. 220-222,
2005.
Solid Liquid Equilibrium,
http://www.scranton.edu/faculty/baumann/courses/labs/solliq.pdf
Department of Chemistry and Biochemistry, Binary Solid-Liquid Phase
Diagram, in Chemistry 4581, pp 1-7.
ChE 124 Chemical Engineering Thermodynamics Laboratory Manual,
Quezon City, 2013, pp. 39-42.

APPENDIX
Appendix A. Pure-Species Properties
Diphenylamine

Naphthalene

Density (g/cm3)

1.2

1.16

Melting Point (deg C)

53

80.2

169.22244

128.17052

Molecular Weight (g/mol)

Appendix B. Relevant Equations used


1 =


+
% =


100%

Appendix C. Cooling Curves

Mixture 1

Temperature (deg C)

120.0
100.0
80.0
60.0
40.0
20.0

0.0
0

50

100

150
Time (s)

200

250

300

Mixture 2

Temperature (deg C)

120.0
100.0
80.0
60.0
40.0
20.0
0.0
0

50

100

150

200

250

Time (s)

Mixture 3
Temperature (deg C)

120.0
100.0
80.0
60.0

40.0
20.0
0.0
0

100

200

300
400
Time (s)

500

600

700

Mixture 4
Temperature (deg C)

120.0

100.0
80.0
60.0
40.0
20.0
0.0
0

100

200

300
Time (s)

400

500

Mixture 5
Temperature (deg C)

120.0
100.0
80.0
60.0
40.0

20.0
0.0
0

50

100

150

200
Time (s)

250

300

350

400

250

300

350

400

250

300

350

400

Mixture 6
Temperature (deg C)

100.0
80.0
60.0
40.0
20.0
0.0
0

50

100

150

200
Time (s)

Mixture 7
Temperature (deg C)

100.0
80.0
60.0
40.0
20.0
0.0
0

50

100

150

200
Time (s)

Mixture 8
Temperature (deg C)

100.0
80.0
60.0
40.0
20.0
0.0
0

50

100

150

200
Time (s)

250

300

350

400